WO2021221025A1 - Method for manufacturing structure, and structure - Google Patents

Method for manufacturing structure, and structure Download PDF

Info

Publication number
WO2021221025A1
WO2021221025A1 PCT/JP2021/016684 JP2021016684W WO2021221025A1 WO 2021221025 A1 WO2021221025 A1 WO 2021221025A1 JP 2021016684 W JP2021016684 W JP 2021016684W WO 2021221025 A1 WO2021221025 A1 WO 2021221025A1
Authority
WO
WIPO (PCT)
Prior art keywords
pattern
light
layer
photosensitive resin
mass
Prior art date
Application number
PCT/JP2021/016684
Other languages
French (fr)
Japanese (ja)
Inventor
慎一 漢那
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2022518063A priority Critical patent/JPWO2021221025A1/ja
Priority to CN202180031425.7A priority patent/CN115486211A/en
Priority to KR1020227037777A priority patent/KR20220162158A/en
Publication of WO2021221025A1 publication Critical patent/WO2021221025A1/en

Links

Images

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material

Definitions

  • This disclosure relates to a method for manufacturing a structure and the structure.
  • Conductive patterns such as thin metal wires are used for various purposes.
  • Applications of the conductive pattern include, for example, a touch sensor of a touch panel, an antenna, a fingerprint authentication unit, a foldable device, and a transparent FPC (Flexible Printed Circuits).
  • a fine conductive pattern is formed on the base material.
  • the base material for example, a film, a sheet, a metal substrate, a ceramic substrate, or glass is used.
  • a subtractive method and a semi-additive method are known (for example, Patent Document 1 and Patent Document 2).
  • a conductive pattern can be formed by protecting the conductive layer on the base material with a resist pattern and then removing the conductive layer not protected by the resist pattern by etching.
  • an electroless copper plating layer called a seed layer is provided on the base material, and then a resist pattern is further provided on the electroless copper plating layer.
  • the unnecessary resist pattern and the electroless copper plating layer are removed.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2015-225650
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2015-065376
  • a thick conductive pattern may be formed.
  • the resist pattern is protected by a phenomenon in which etching proceeds isotropically in the in-plane direction of the base material on which the conductive layer is arranged (for example, referred to as "side etching").
  • the conductive layer may also be eroded by the chemical solution. Since the occurrence of side etching affects the morphology (eg, shape and dimensions) of the conductive pattern formed through etching, it may be difficult to form, for example, a rectangular conductive pattern. ..
  • the semi-additive method it is a problem that the formation of the conductive pattern becomes unstable due to the adhesion between the seed layer and the resist pattern. Further, since a part of the conductive pattern may be removed when the unnecessary seed layer is removed, the semi-additive method has the same problems as the subtractive method.
  • the problem to be solved by one embodiment of the present disclosure is the occurrence of morphological abnormalities (generation of tapered shape due to cracking, peeling, chipping or side etching, or dimensional fluctuation due to etching variation. The same shall apply hereinafter. ) Is to provide a method of manufacturing a structure having a reduced pattern. Another problem to be solved by other embodiments of the present disclosure is to provide a structure having a pattern in which the occurrence of morphological abnormalities is reduced.
  • Means for solving the above problems include the following aspects. ⁇ 1> A negative type that is arranged on the transparent base material, the light-shielding pattern 1 arranged on the transparent base material, the transparent base material, and the light-shielding pattern 1 and is in contact with the transparent base material. A part of the negative type photosensitive resin layer N from a surface opposite to the surface of the transparent base material provided with the light-shielding pattern 1 in the step of preparing a laminate having the photosensitive resin layer N. The step of irradiating the transparent substrate with light, the step of forming the resin pattern 2 on the transparent substrate by developing the negative type photosensitive resin layer N irradiated with light, and the light-shielding pattern 1 and the resin.
  • a method for producing a structure comprising the step of forming a pattern 3 in a region defined by the pattern 2 and the obtained structure having the resin pattern 2 as a permanent film.
  • ⁇ 5> The method for producing a structure according to any one of ⁇ 1> to ⁇ 4>, wherein the light-shielding pattern 1 and the pattern 3 contain the same kind of material.
  • ⁇ 6> The structure according to any one of ⁇ 1> to ⁇ 5>, wherein the negative photosensitive resin layer N contains an alkali-soluble polymer, an ethylenically unsaturated compound, and a photopolymerization initiator. Production method.
  • ⁇ 7> The method for producing a structure according to ⁇ 6>, wherein the ethylenically unsaturated compound contains a trifunctional or higher functional ethylenically unsaturated compound.
  • ⁇ 8> The method for producing a structure according to ⁇ 6> or ⁇ 7>, wherein the ethylenically unsaturated compound contains a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure.
  • ⁇ 9> The structure according to any one of ⁇ 1> to ⁇ 5>, wherein the negative photosensitive resin layer N contains a polyfunctional epoxy resin, a hydroxy group-containing compound, and a photocationic polymerization initiator. Production method.
  • ⁇ 10> The method for producing a structure according to any one of ⁇ 1> to ⁇ 9>, wherein the negative photosensitive resin layer N contains a metal oxidation inhibitor.
  • ⁇ 12> The method for producing a structure according to any one of ⁇ 1> to ⁇ 11>, wherein the average thickness of the pattern 3 is thicker than the average thickness of the light-shielding pattern 1.
  • ⁇ 13> The method for producing a structure according to any one of ⁇ 1> to ⁇ 12>, wherein the transparent base material is a transparent film base material.
  • ⁇ 14> The method for producing a structure according to any one of ⁇ 1> to ⁇ 13>, further comprising a step of performing at least one of post-exposure and post-heating on the resin pattern 2.
  • ⁇ 15> The method for producing a structure according to any one of ⁇ 1> to ⁇ 14>, wherein the negative photosensitive resin layer N is a layer formed of a photosensitive transfer material.
  • the obtained structure is one type of structure selected from the group consisting of a touch sensor, an electromagnetic wave shield, an antenna, a wiring substrate, a conductive heating element, and a viewing angle control film ⁇ 1> to ⁇ 15.
  • the method for manufacturing a structure according to any one of. ⁇ 17> The transparent base material, the light-shielding pattern 1 arranged on the transparent base material, and the transparent base material arranged adjacent to the light-shielding pattern 1 on the transparent base material and on the transparent base material.
  • the resin pattern 2 in contact with the light-shielding pattern 1 and the pattern 3 in the region defined by the light-shielding pattern 1 and the resin pattern 2 are provided, and the average thickness of the light-shielding pattern 1 is 2 ⁇ m or less, and the resin pattern 2
  • the average thickness of the pattern 3 exceeds 2 ⁇ m, the average thickness of the pattern 3 is thicker than the average thickness of the light-shielding pattern 1, and the structure has the resin pattern 2 as a permanent film.
  • the numerical range represented by using “-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • “(meth) acrylic” represents both acrylic and methacrylic, or either
  • “(meth) acrylate” represents both acrylate and methacrylate, or either.
  • the amount of each component in the composition is the sum of the plurality of applicable substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Means quantity.
  • the term "process” is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
  • the notation not describing substitution and non-substitution includes those having no substituent as well as those having a substituent.
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure as used herein includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam.
  • the emission line spectrum of a mercury lamp far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams (active energy rays) are used.
  • EUV light extreme ultraviolet rays
  • X-rays active rays
  • active energy rays active energy rays
  • chemical structural formula in the present specification may be described by a simplified structural formula in which a hydrogen atom is omitted.
  • “% by mass” and “% by weight” are synonymous, and “parts by mass” and “parts by weight” are synonymous.
  • a combination of two or more preferred embodiments is a more preferred embodiment.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.). It is a molecular weight converted by detecting with a solvent THF (tetrahydrofuran) and a differential refractometer by a gel permeation chromatography (GPC) analyzer and using polystyrene as a standard substance.
  • THF tetrahydrofuran
  • GPC gel permeation chromatography
  • alkali-soluble means the property that the solubility of sodium carbonate in an aqueous solution (100 g, sodium carbonate concentration: 1% by mass) is 0.1 g or more at a liquid temperature of 22 ° C.
  • conductive means a property in which an electric current easily flows. The required current flowability is not limited and may be as long as it is necessary for the purpose and application.
  • the conductivity is expressed by the volume resistivity, the volume resistivity is preferably less than 1 ⁇ 10 6 ⁇ cm, and more preferably less than 1 ⁇ 10 4 ⁇ cm.
  • light means electromagnetic waves including ultraviolet rays, visible rays, and infrared rays.
  • the light is preferably light having a wavelength in the range of 200 nm to 1,500 nm, more preferably light having a wavelength in the range of 250 nm to 450 nm, and particularly preferably light having a wavelength in the range of 300 nm to 410 nm. preferable.
  • the "solid content” means a component obtained by removing a solvent from all the components of an object.
  • the method for producing a structure according to the present disclosure includes a transparent base material, a light-shielding pattern 1 arranged on the transparent base material, a transparent base material, and a light-shielding pattern 1 arranged on the transparent base material and the light-shielding pattern 1.
  • a step of preparing a laminate having a negative type photosensitive resin layer N in contact with the transparent base material hereinafter, also referred to as a “preparation step” and the light-shielding pattern 1 of the transparent base material are provided.
  • a step of irradiating a part of the negative type photosensitive resin layer N with light from a surface opposite to the surface (hereinafter, also referred to as “exposure step”), the negative type photosensitive resin layer N irradiated with light.
  • exposure step a step of forming the resin pattern 2 on the transparent substrate
  • pattern 3 forming step a region defined by the light-shielding pattern 1 and the resin pattern 2
  • the structure including the step of forming the pattern 3 has the resin pattern 2 as a permanent film.
  • FIG. 1 is a schematic cross-sectional view showing an example of a method for manufacturing a structure according to the present disclosure.
  • FIG. 1A shows an example of the preparation step.
  • FIG. 1B shows an example of the exposure process.
  • FIG. 1C shows an example of the developing process.
  • FIG. 1D shows an example of the pattern 3 forming step.
  • the laminate 100 shown in FIG. 1A has a transparent base material 10, a light-shielding pattern 20 (light-shielding pattern 1), and a negative-type photosensitive resin layer 30 (negative-type photosensitive resin layer N). Have.
  • the surface of the transparent base material 10 opposite to the surface facing the light-shielding pattern 20 that is, the surface to be exposed 10a
  • the surface to be exposed 10a is irradiated with light.
  • the light incident on the exposed surface 10a of the transparent base material 10 passes through the exposed portion 30a of the negative photosensitive resin layer 30 via the transparent base material 10.
  • the exposed portion 30a of the negative type photosensitive resin layer 30 is selectively exposed.
  • the negative type photosensitive resin layer 30 is developed to remove the portion of the negative type photosensitive resin layer 30 other than the exposed portion 30a, and the transparent base material 10 and the light-shielding pattern 20 are removed.
  • the resin pattern 40 (resin pattern 2) is formed in the region (that is, the groove) defined by. As shown in FIG.
  • a pattern 50 (pattern 3) is formed on the light-shielding pattern 20.
  • the pattern 50 is formed in a region (ie, a groove) defined by a light-shielding pattern 20 that functions like a mold and a resin pattern 40.
  • the pattern 50 can be easily formed. Therefore, according to the method for manufacturing a structure according to the present disclosure, a pattern (preferably a conductive pattern) in which the occurrence of morphological abnormalities is reduced is formed.
  • the obtained structure has the above resin pattern 2 as a permanent film.
  • the "permanent film” is a film (layer) that remains even after the completion of an article having the above structure (including a product and the case where the structure itself is an article).
  • Specific examples of the permanent film include an insulating film, a protective film, a spacer, and the like.
  • the structure obtained by the method for manufacturing a structure according to the present disclosure is one type of structure selected from the group consisting of, for example, a touch sensor, an electromagnetic wave shield, an antenna, a wiring substrate, a conductive heating element, and a viewing angle control film. It is preferably a body.
  • the method for producing a laminate according to the present disclosure is a transparent base material, a light-shielding pattern 1 arranged on the transparent base material, a transparent base material, and a light-shielding pattern 1 arranged on the transparent base material and the light-shielding pattern 1.
  • the step (preparation step) of preparing a laminate having the negative type photosensitive resin layer N in contact with the transparent base material is included.
  • "preparation” means making an object ready for use.
  • the laminated body may be a laminated body manufactured in advance.
  • the laminate may be a laminate produced in the preparatory step. That is, the preparation step may include a step of manufacturing the laminate.
  • the laminate has a transparent substrate.
  • transparent means that the transmittance of the exposure wavelength in the exposure step is 50% or more.
  • the transmittance of the exposure wavelength defined by the term “transparent” is preferably 80% or more, more preferably 90%, and particularly preferably 95%.
  • the "transmittance of an exposure wavelength” means the transmittance of a wavelength included in the light that reaches an object (for example, a transparent substrate) in the exposure process.
  • the “transmittance of the exposure wavelength” means the transmittance of the wavelength of 365 nm.
  • transmittance refers to the intensity of incident light when light is incident in a direction perpendicular to the main surface of the object to be measured (that is, in the thickness direction), and is emitted through the object to be measured. It is the ratio of the intensity of the emitted light.
  • the transmittance is measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
  • the transparent substrate preferably has a light transmittance of 80% or more at a wavelength of 400 nm to 700 nm.
  • the shape of the transparent base material is not limited.
  • the transparent base material for example, a film-shaped or plate-shaped transparent base material is preferably used. Above all, the transparent base material is preferably a transparent film base material.
  • the transparent substrate examples include a resin substrate (for example, a resin film) and a glass substrate.
  • the resin substrate is preferably a resin substrate that transmits visible light.
  • Preferred components of the resin substrate that transmits visible light include, for example, polyamide-based resin, polyethylene terephthalate-based resin, polyethylene naphthalate-based resin, cycloolefin-based resin, polyimide-based resin, and polycarbonate-based resin. More preferable components of the resin substrate that transmits visible light include, for example, polyamide, polyethylene terephthalate (PET), cycloolefin polymer (COP), polyethylene naphthalate (PEN), polyimide, and polycarbonate.
  • PET polyethylene terephthalate
  • COP cycloolefin polymer
  • PEN polyethylene naphthalate
  • polyimide polyimide
  • the transparent substrate is preferably a polyamide film, a polyethylene terephthalate film, a cycloolefin polymer (COP), a polyethylene naphthalate film, a polyimide film, or a polycarbonate film, and more preferably a polyethylene terephthalate film.
  • COP cycloolefin polymer
  • the transparent base material examples include paper phenol, paper epoxy, glass composite, glass epoxy, polytetrafluoroethylene, and a rigid flexible material in which a hard material and a soft material are combined.
  • the transparent base material may be a porous transparent base material.
  • the transparent substrate may contain a filler and an additive.
  • the surface of the transparent base material may be modified by, for example, alkali treatment or energy ray irradiation.
  • the structure of the transparent base material may be a single-layer structure or a multi-layer structure.
  • the transparent substrate may include, for example, a functional layer.
  • the functional layer include an adhesive layer, a hard coat layer, and a refractive index adjusting layer.
  • the thickness of the transparent substrate is not limited.
  • the thickness of the transparent substrate is preferably in the range of 10 ⁇ m to 200 ⁇ m, more preferably in the range of 20 ⁇ m to 120 ⁇ m, and particularly preferably in the range of 20 ⁇ m to 100 ⁇ m.
  • the thickness of the transparent substrate is measured by the following method. A scanning electron microscope (SEM) is used to observe a cross section in a direction perpendicular to the main surface of the transparent substrate (ie, in the thickness direction). Based on the obtained observation image, the thickness of the transparent substrate is measured at 10 points. The average thickness of the transparent substrate is obtained by arithmetically averaging the measured values.
  • the total light transmittance of the transparent substrate is preferably high.
  • the total light transmittance of the transparent substrate is preferably 50% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more.
  • the upper limit of the total light transmittance of the transparent substrate is not limited.
  • the total light transmittance of the transparent substrate may be determined in the range of 100% or less. The total light transmittance is measured by the method specified in JIS K 7361-1 (1997).
  • the laminate has a light-shielding pattern 1 on a transparent substrate.
  • a part of the negative photosensitive resin layer can be selectively exposed in the exposure step.
  • "light shielding" means that the transmittance of the exposure wavelength is less than 50%.
  • the transmittance of the exposure wavelength defined by the term "light shielding” is preferably less than 30%, more preferably less than 10%, and particularly preferably less than 1%.
  • the light-shielding pattern 1 preferably has a light transmittance of less than 30% at a wavelength of 400 nm to 700 nm.
  • the light-shielding pattern 1 preferably has conductivity.
  • the conductive light-shielding pattern 1 can function as an electric conductor (for example, a seed layer) when plating is performed in the pattern 3 forming step described later, for example.
  • the seed layer can function as a cathode in, for example, electroplating.
  • the light-shielding pattern 1 preferably contains a metal.
  • Examples of the component of the light-shielding pattern 1 include metal.
  • Examples of the metal include Nb (niobium), Al (aluminum), Ni (nickel), Zn (zinc), Mo (molybdenum), Ta (tantalum), Ti (titanium), V (vanadium), and Cr (chromium). , Fe (iron), Co (cobalt), W (tungsten), Cu (copper), Sn (tin), and Mn (manganese).
  • the light-shielding pattern 1 preferably contains a metal from the viewpoint of conductivity, and is composed of Nb, Al, Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn and Mn.
  • the light-shielding pattern 1 may contain one kind alone or two or more kinds of metals.
  • the metal contained in the light-shielding pattern 1 may be a single metal or an alloy.
  • the light-shielding pattern 1 preferably contains Cu or an alloy of Cu.
  • the metal element contained in the light-shielding pattern may be the same as or different from the metal element contained in the conductive pattern described later.
  • the light-shielding pattern 1 preferably contains the same metal element as the metal element contained in the conductive pattern.
  • the light-shielding pattern 1 may contain an element other than a metal element.
  • elements other than metal elements include C (carbon), P (phosphorus), and B (boron).
  • Elements other than metal elements may form alloys with metal elements.
  • the shape of the light-shielding pattern 1 is not limited.
  • the shape of the light-shielding pattern 1 may be determined, for example, according to the shape of the target conductive pattern.
  • the structure of the light-shielding pattern 1 may be a single-layer structure or a multi-layer structure.
  • the components of each layer of the light-shielding pattern 1 having a multi-layer structure may be the same or different.
  • the thickness of the light-shielding pattern 1 is not limited.
  • the average thickness of the light-shielding pattern 1 is preferably 3 ⁇ m or less, more preferably 2 ⁇ m or less, further preferably 1 ⁇ m or less, and particularly preferably 0.5 ⁇ m or less.
  • the average thickness of the light-shielding pattern 1 is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more, and particularly preferably 0.3 ⁇ m or more.
  • the average thickness of the light-shielding pattern 1 is 0.05 ⁇ m or more, the transmittance of the exposure wavelength can be reduced. Further, when the light-shielding pattern 1 is used as the seed layer, the productivity of the conductive pattern can be improved.
  • the average thickness of the light-shielding pattern 1 is measured by a method according to the method for measuring the average thickness of the transparent substrate.
  • the width of the light-shielding pattern 1 is not limited.
  • the width of the light-shielding pattern 1 is the length of the light-shielding pattern 1 in the direction perpendicular to the longitudinal direction of the light-shielding pattern 1 in the surface direction of the transparent base material.
  • the width of the light-shielding pattern 1 is the length of the line pattern in the lateral direction.
  • the width of the light-shielding pattern 1 is the minimum diameter in the circular or elliptical shape.
  • the width of the light-shielding pattern 1 may be determined, for example, according to the width of the conductive pattern formed in the pattern 3 forming step.
  • the average width of the light-shielding pattern 1 is preferably 50 ⁇ m or less, more preferably 10 ⁇ m or less, further preferably 5 ⁇ m or less, and particularly preferably 2 ⁇ m or less.
  • the average width of the light-shielding pattern 1 is preferably 0.1 ⁇ m or more, and more preferably 0.5 ⁇ m or more.
  • the average width of the light-shielding pattern 1 is an arithmetic mean of the width of the light-shielding pattern measured at five points.
  • the light-shielding pattern 1 may be in contact with the transparent substrate directly or via another layer.
  • the other layer include an adhesion layer.
  • the laminate may have an adhesion layer between the transparent substrate and the light-shielding pattern 1.
  • the components of the adhesion layer are not limited.
  • the components of the adhesion layer are, for example, the adhesion between the transparent base material and the light-shielding pattern 1, and the stability of the conductive pattern obtained by the method for producing the structure according to the present disclosure in the usage environment (for example, humidity and temperature). It may be decided according to the sex.
  • the adhesion layer preferably contains at least one selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn.
  • the adhesion layer may further contain at least one selected from the group consisting of C (carbon atom), O (oxygen atom), H (hydrogen atom), and N (nitrogen atom).
  • the adhesion layer may be a blackening layer. The blackened layer can suppress the reflection of light due to the light-shielding pattern in the exposure process.
  • the adhesion layer preferably contains, for example, a Ni—Cu alloy.
  • the adhesion layer that functions as a blackening layer may further contain at least one selected from the group consisting of C, O, H, and N.
  • the thickness of the adhesion layer is not limited.
  • the average thickness of the adhesion layer is preferably 3 nm to 50 nm, more preferably 3 nm to 35 nm, and particularly preferably 3 nm to 33 nm.
  • the laminate has a negative photosensitive resin layer N that is arranged on the transparent base material and the light-shielding pattern 1 and is in contact with the transparent base material.
  • the negative photosensitive resin layer N may be in contact with the light-shielding pattern 1 directly or via another layer.
  • the negative photosensitive resin layer N is preferably in contact with the light-shielding pattern 1.
  • a known negative type photosensitive resin layer can be used as the negative type photosensitive resin layer N.
  • the negative photosensitive resin layer N preferably contains a polymer A described later, a polymerizable compound B described later, and a photopolymerization initiator.
  • the negative type photosensitive resin layer N includes 10% by mass to 90% by mass of the polymer A and 5% by mass to 70% by mass of the polymerizable compound B with respect to the total mass of the negative type photosensitive resin layer N. It is preferable to contain 0.01% by mass to 20% by mass of a photopolymerization initiator.
  • the negative photosensitive resin layer N preferably contains an alkali-soluble polymer, an ethylenically unsaturated compound, and a photopolymerization initiator.
  • the negative photosensitive resin layer N preferably contains an alkali-soluble polymer, an ethylenically unsaturated compound, and a photoacid generator from the viewpoint of curability and developability. Further, the negative photosensitive resin layer N preferably contains a polyfunctional epoxy resin, a hydroxy group-containing compound, and a cationic polymerization initiator from the viewpoint of strength and durability of the obtained resin pattern 2 as a permanent film. ..
  • the negative type photosensitive resin layer N will be specifically described.
  • the negative photosensitive resin layer N preferably contains an alkali-soluble polymer.
  • alkali-soluble means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22 ° C. is 0.1 g or more.
  • the alkali-soluble polymer preferably has an acid value of 60 mgKOH / g or more from the viewpoint of developability, for example.
  • the alkali-soluble polymer is, for example, a resin having a carboxy group having an acid value of 60 mgKOH / g or more (so-called carboxy group-containing resin) from the viewpoint that it is easily crosslinked with a crosslinked component by heating to form a strong film.
  • an acrylic resin having a carboxy group having an acid value of 60 mgKOH / g or more is particularly preferable.
  • the acrylic resin refers to a resin having a structural unit derived from a (meth) acrylic compound, and the content of the structural unit is preferably 30% by mass or more with respect to the total mass of the resin. , 50% by mass or more is more preferable.
  • the alkali-soluble polymer is a resin having a carboxy group
  • the three-dimensional crosslink density can be increased by adding a heat-crosslinkable compound such as a blocked isocyanate compound and heat-crosslinking.
  • the carboxy group of the resin having a carboxy group is anhydrous and hydrophobized, the wet heat resistance can be improved.
  • the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as the above acid value conditions are satisfied, and can be appropriately selected from known acrylic resins and used.
  • carboxy group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraphs 0025 of JP2011-95716A, carboxy group-containing acrylic resins having an acid value of 60 mgKOH / g or more, and the polymers described in paragraphs 0033 to 0052 of JP2010-237589A.
  • a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be preferably used.
  • the alkali-soluble polymer is preferably an acrylic resin or a styrene-acrylic copolymer from the viewpoint of suppressing development residue, moisture permeability of the obtained cured film, and adhesiveness of the obtained uncured film. More preferably, it is a styrene-acrylic copolymer.
  • the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth) acrylic compound, and the structural unit derived from the styrene compound and the (meth) compound.
  • the total content of the constituent units derived from the acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total mass of the copolymer.
  • the content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and 5% by mass or more and 80% by mass with respect to the total mass of the copolymer. It is particularly preferable that it is% or less.
  • the content of the structural unit derived from the (meth) acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass, based on the total mass of the copolymer. It is particularly preferable that it is% or more and 95% by mass or less.
  • examples of the (meth) acrylic compound include (meth) acrylate compound, (meth) acrylic acid, (meth) acrylamide compound, and (meth) acrylonitrile. Among them, at least one compound selected from the group consisting of (meth) acrylate compound and (meth) acrylic acid is preferable.
  • the negative photosensitive resin layer N preferably contains the polymer A.
  • the polymer A is preferably an alkali-soluble polymer.
  • Alkali-soluble polymers include polymers that are easily soluble in alkaline substances.
  • "alkali-soluble” means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22 ° C. is 0.1 g or more.
  • the acid value of the polymer A is preferably 220 mgKOH / g or less, and less than 200 mgKOH / g, from the viewpoint of more excellent resolution by suppressing the swelling of the negative photosensitive resin layer N due to the developing solution. It is more preferable, and it is particularly preferable that it is less than 190 mgKOH / g.
  • the lower limit of acid value is not limited.
  • the acid value of the polymer A is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, further preferably 150 mgKOH / g or more, and 170 mgKOH / g or more, from the viewpoint of more excellent developability. It is particularly preferable that it is g or more.
  • the acid value of the polymer A can be adjusted, for example, by the type of the structural unit constituting the polymer A and the content of the structural unit containing an acid group.
  • the acid value is the mass (mg) of potassium hydroxide required to neutralize 1 g of the sample.
  • the unit of acid value is described as mgKOH / g.
  • the acid value can be calculated, for example, from the average content of acid groups in the compound.
  • the weight average molecular weight (Mw) of the polymer A is preferably 5,000 to 500,000. It is preferable that the weight average molecular weight is 500,000 or less from the viewpoint of improving the resolvability and the developability.
  • the weight average molecular weight of the polymer A is more preferably 100,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less.
  • the weight average molecular weight of the polymer A is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more.
  • the dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and even more preferably 1.0 to 4.0. It is particularly preferably 0.0 to 3.0.
  • the degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).
  • the polymer A preferably has a structural unit having an aromatic hydrocarbon group from the viewpoint of suppressing the line width thickening when the focal position is deviated during exposure and the deterioration of the resolution, and the polymer A preferably contains an aromatic hydrocarbon group. It is more preferable to have a structural unit derived from the monomer having.
  • aromatic hydrocarbon group examples include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.
  • the content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, preferably 30% by mass or more, based on the total mass of the polymer A. More preferably, it is more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more.
  • the upper limit of the content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group is not limited.
  • the content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is preferably 95% by mass or less, preferably 85% by mass or less, based on the total mass of the polymer A. Is more preferable.
  • the content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group is determined as a weight average value.
  • the monomer having an aromatic hydrocarbon group examples include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-). Vinyl benzoic acid, styrene dimer, and styrene trimmer).
  • the monomer having an aromatic hydrocarbon group is preferably a monomer having an aralkyl group or styrene.
  • aralkyl group examples include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferable.
  • Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate.
  • Examples of the monomer having a benzyl group include a (meth) acrylate having a benzyl group (for example, benzyl (meth) acrylate and a chlorobenzyl (meth) acrylate), a vinyl monomer having a benzyl group (for example, vinylbenzyl chloride, and the like). Vinyl benzyl alcohol).
  • the monomer having a benzyl group is preferably a benzyl (meth) acrylate.
  • the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is the structural unit derived from the benzyl (meth) acrylate
  • the benzyl (meth) acrylate single amount in the polymer A is used.
  • the content ratio of the structural unit derived from the body is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, and 70% by mass, based on the total mass of the polymer A. It is more preferably% to 90% by mass, and particularly preferably 75% by mass to 90% by mass.
  • the content ratio of the structural unit derived from styrene in the polymer A is determined. It is preferably 20% by mass to 55% by mass, more preferably 25 to 45% by mass, further preferably 30% by mass to 40% by mass, and 30% by mass, based on the total mass of the polymer A. It is particularly preferably from mass% to 35% by mass.
  • the polymer A having a structural unit derived from a monomer having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group, a first monomer described later, and a monomer described later. It is preferable that the copolymer is obtained by polymerizing at least one selected from the group consisting of the second monomer.
  • the copolymer is a group consisting of a structural unit derived from a monomer having an aromatic hydrocarbon group, a structural unit derived from the first monomer, and a structural unit derived from the second monomer. It has at least one selected from.
  • the polymer A may be a polymer having no structural unit derived from a monomer having an aromatic hydrocarbon group.
  • the polymer A having no structural unit derived from the monomer having an aromatic hydrocarbon group is at least one kind of the first monomer (excluding the monomer having an aromatic hydrocarbon group) described later. It is preferable that the polymer is obtained by polymerizing the above, and at least one of the first monomer (excluding the monomer having an aromatic hydrocarbon group) described later and the second simpler described later. It is more preferable that it is a copolymer obtained by polymerizing at least one of a dimer (excluding a monomer having an aromatic hydrocarbon group).
  • the polymer A is preferably a polymer obtained by polymerizing at least one of the first monomers described later, and is preferably the same as at least one of the first monomers described below. It is more preferable that the copolymer is obtained by polymerizing with at least one of the second monomers described later.
  • the copolymer has a structural unit derived from the first monomer and a structural unit derived from the second monomer.
  • the first monomer is a monomer having a carboxy group and a polymerizable unsaturated group in the molecule.
  • the first monomer may be a monomer having no aromatic hydrocarbon group in the molecule.
  • Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid semiester.
  • the first monomer is preferably (meth) acrylic acid.
  • the content ratio of the structural unit derived from the first monomer in the polymer A is preferably 5% by mass to 50% by mass, and 10% by mass to 40% by mass, based on the total mass of the polymer A. Is more preferable, and 15% by mass to 30% by mass is particularly preferable.
  • the second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule.
  • the second monomer may be a monomer having no aromatic hydrocarbon group in the molecule.
  • Examples of the second monomer include a (meth) acrylate compound, an ester compound of vinyl alcohol, and (meth) acrylonitrile.
  • (meth) acrylonitrile includes acrylonitrile, methacrylonitrile, or both acrylonitrile and methacrylonitrile.
  • Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. Examples thereof include tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
  • Examples of the (meth) acrylate compound include those having an alicyclic alkyl group, a linear alkyl group, and a branched alkyl group.
  • ester compound of vinyl alcohol examples include vinyl acetate.
  • the second monomer is preferably at least one selected from the group consisting of methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-butyl (meth) acrylate, and is preferably methyl (meth). More preferably, it is an acrylate.
  • the content ratio of the structural unit derived from the second monomer in the polymer A is preferably 5% by mass to 60% by mass, and 15% by mass to 50% by mass, based on the total mass of the polymer A. Is more preferable, and 20% by mass to 45% by mass is particularly preferable.
  • the polymer A is composed of a structural unit derived from a monomer having an aralkyl group and a structural unit derived from styrene from the viewpoint of suppressing the line width thickening when the focal position is deviated during exposure and the deterioration of resolution. It is preferable to include at least one selected from the group.
  • the polymer A is a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from benzyl methacrylate, a structural unit derived from styrene, a structural unit derived from methacrylic acid, and methyl. It is preferably at least one selected from the group consisting of copolymers containing a structural unit derived from methacrylate, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene.
  • the polymer A contains 25% by mass to 60% by mass of a structural unit derived from a monomer having an aromatic hydrocarbon group and 20% by mass or more of a structural unit derived from a first monomer.
  • a polymer containing 55% by mass and 20% by mass to 55% by mass of a structural unit derived from the second monomer is preferable.
  • the structural unit derived from the monomer having an aromatic hydrocarbon group is 25% by mass to 40% by mass
  • the structural unit derived from the first monomer is 20% by mass to 35% by mass, and the like.
  • a polymer containing 30% by mass to 45% by mass of a structural unit derived from the second monomer is more preferable.
  • the polymer A contains 70% by mass to 90% by mass of structural units derived from a monomer having an aromatic hydrocarbon group, and 10% by mass of a structural unit derived from a first monomer. It is preferably a polymer containing up to 25% by mass.
  • the glass transition temperature (Tg) of the polymer A is preferably 30 ° C to 135 ° C.
  • Tg of the polymer A is more preferably 130 ° C. or lower, further preferably 120 ° C. or lower, and particularly preferably 110 ° C. or lower.
  • the Tg of the polymer A is 30 ° C. or higher from the viewpoint of improving the edge fuse resistance.
  • the Tg of the polymer A is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher, and most preferably 70 ° C. or higher. preferable.
  • the polymer A may be a commercially available product or a synthetic product.
  • Polymer A is synthesized, for example, by diluting at least one of the above-mentioned monomers with a solvent (for example, acetone, methyl ethyl ketone, or isopropanol) and a radical polymerization initiator (for example, benzoyl peroxide or azoisobuty) in a solution. Butyronitrile) is preferably added in an appropriate amount, and then heated and stirred. In some cases, the synthesis is carried out while dropping a part of the mixture into the reaction solution. After completion of the reaction, a solvent may be further added to adjust the concentration to a desired level.
  • a solvent may be further added to adjust the concentration to a desired level.
  • the synthesis means bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
  • the negative type photosensitive resin layer N may contain one kind alone or two or more kinds of alkali-soluble polymers.
  • the content ratio of the alkali-soluble polymer is preferably 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, based on the total mass of the negative photosensitive resin layer N. It is particularly preferably 40% by mass to 60% by mass. It is preferable that the content ratio of the alkali-soluble polymer to the negative photosensitive resin layer N is 90% by mass or less from the viewpoint of controlling the developing time. On the other hand, it is preferable that the content ratio of the alkali-soluble polymer with respect to the negative photosensitive resin layer N is 10% by mass or more from the viewpoint of improving the edge fuse resistance.
  • the negative type photosensitive resin layer N contains two or more kinds of alkali-soluble polymers
  • the negative type photosensitive resin layer N has two or more kinds having a structural unit derived from a monomer having an aromatic hydrocarbon group. It does not have a structural unit derived from an alkali-soluble polymer or a monomer having an aromatic hydrocarbon group, and an alkali-soluble polymer having a structural unit derived from a monomer having an aromatic hydrocarbon group. It preferably contains an alkali-soluble polymer.
  • the content ratio of the alkali-soluble polymer having a structural unit derived from the monomer having an aromatic hydrocarbon group is preferably 50% by mass or more with respect to the total mass of the alkali-soluble polymer. , 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the negative photosensitive resin layer N preferably contains a polymerizable compound.
  • the "polymerizable compound” means a compound having a bond or a polymerizable group involved in a polymerization reaction and polymerizing under the action of a polymerization initiator described later.
  • the polymerizable compound in the present disclosure is a compound different from the alkali-soluble polymer, and preferably has a molecular weight of less than 5,000.
  • an ethylenically unsaturated compound is preferable.
  • the ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an acid group from the viewpoints of the strength of the obtained cured film, substrate adhesion, development residue inhibitory property, and rust prevention property, and will be described later. It is more preferable to contain the compound represented by the formula (M) and an ethylenically unsaturated compound having an acid group.
  • the ethylenically unsaturated compound is a compound represented by the following formula (M) (simply also referred to as "Compound M”) from the viewpoint of developing residue inhibitory property, rust preventive property, and bending resistance of the obtained cured film. It is preferable to include it.
  • Q 2 -R 1 -Q 1 formula (M) In formula (M), Q 1 and Q 2 each independently represent a (meth) acryloyloxy group, and R 1 represents a divalent linking group having a chain structure.
  • Q 1 and Q 2 in the formula (M) have the same group as Q 1 and Q 2 from the viewpoint of easiness of synthesis. Further, Q 1 and Q 2 in the formula (M) are preferably acryloyloxy groups from the viewpoint of reactivity.
  • R 1 in the formula (M) from the viewpoint of bending resistance of the obtained cured film, an alkylene group, an alkylene oxyalkylene group (-L 1 -O-L 1 - ), or, polyalkylene oxyalkylene group (- (L 1- O) p- L 1- ) is preferable, and a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferable, and an alkylene group having 4 to 20 carbon atoms is used. It is more preferable, and it is particularly preferable that it is a linear alkylene group having 6 to 18 carbon atoms.
  • the hydrocarbon group may have a chain structure at least in part, and the portion other than the chain structure is not particularly limited, and is, for example, branched chain, cyclic, or having 1 to 5 carbon atoms. It may be any of a linear alkylene group, an arylene group, an ether bond, and a combination thereof, and from the viewpoint of bending resistance of the obtained cured film, an alkylene group or two or more alkylene groups and one or more. It is preferably a group in combination with an arylene group, more preferably an alkylene group, and particularly preferably a linear alkylene group.
  • Each of the above L 1 independently represents an alkylene group, preferably an ethylene group, a propylene group, or a butylene group, and more preferably an ethylene group or a 1,2-propylene group.
  • p represents an integer of 2 or more, and is preferably an integer of 2 to 10.
  • the atomic number of the connecting chain of the shortest for connecting the Q 1, Q 2 in the compound M, from the viewpoints of moisture permeability and bending resistance of the obtained cured film is preferably from 3 to 50, The number is more preferably 4 to 40, further preferably 6 to 20, and particularly preferably 8 to 12.
  • the term "Q 1, Q atoms linking chain shortest connecting between two" shortest connecting the atom in R 1 be linked to Q 1 to atom in R 1 be linked to Q 2 Is the number of atoms in.
  • the compound M examples include 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate.
  • the ester monomer can also be used as a mixture.
  • 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,10-decanediol di (meth) acrylate from the viewpoint of bending resistance of the obtained cured film. It is preferably at least one compound selected from the group consisting of acrylates and neopentyl glycol di (meth) acrylates, preferably 1,6-hexanediol di (meth) acrylates and 1,9-nonanediol di ().
  • it is at least one compound selected from the group consisting of meta) acrylate and 1,10-decanediol di (meth) acrylate, and 1,9-nonanediol di (meth) acrylate and It is particularly preferable that the compound is at least one selected from the group consisting of 1,10-decanediol di (meth) acrylate.
  • Compound M may be used alone or in combination of two or more.
  • the content of compound M is 10% by mass to 90% by mass with respect to the total mass of the ethylenically unsaturated compound of the negative photosensitive resin layer N from the viewpoint of moisture permeability and bending resistance of the obtained cured film. Is more preferable, 15% by mass to 70% by mass is more preferable, 20% by mass to 50% by mass is further preferable, and 25% by mass to 35% by mass is particularly preferable.
  • the ethylenically unsaturated compound in the present disclosure refers to a compound having an ethylenically unsaturated group having a (weight average) molecular weight of 10,000 or less.
  • the content of the compound M is preferably 1% by mass to 30% by mass with respect to the total mass of the negative photosensitive resin layer N from the viewpoint of moisture permeability and bending resistance of the obtained cured film. It is more preferably from mass% to 25% by mass, further preferably from 5% by mass to 20% by mass, and particularly preferably from 6% by mass to 14.5% by mass.
  • the ethylenically unsaturated compound preferably contains a bifunctional or higher functional ethylenically unsaturated compound.
  • the "bifunctional or higher functional ethylenically unsaturated compound” means a compound having two or more ethylenically unsaturated groups in one molecule.
  • a (meth) acryloyl group is preferable.
  • a (meth) acrylate compound is preferable.
  • the ethylenically unsaturated compound examples include a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth) acrylate compound) and a trifunctional or higher functional ethylenic compound from the viewpoint of the strength of the cured film after curing. It is particularly preferred to include unsaturated compounds (preferably trifunctional or higher functional (meth) acrylate compounds).
  • the negative photosensitive resin layer N preferably contains the polymerizable compound B.
  • the polymerizable compound B is a compound different from the polymer A.
  • As the bond involved in the polymerization reaction in the polymerizable compound B for example, an ethylenically unsaturated bond is preferably mentioned.
  • the polymerizable group in the polymerizable compound B is not limited as long as it is a group involved in the polymerization reaction.
  • Examples of the polymerizable group in the polymerizable compound B include a group containing an ethylenically unsaturated bond (for example, a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group), and a cationically polymerizable group (for example, a cationically polymerizable group).
  • Epoxide group and oxetane group Epoxide group and oxetane group).
  • the polymerizable group is preferably a group containing an ethylenically unsaturated bond (hereinafter, may be referred to as an "ethylenically unsaturated group”), and more preferably an acryloyl group or a metaacryloyl group.
  • the polymerizable compound B is preferably a compound having an ethylenically unsaturated bond in that the negative photosensitive resin layer N is more excellent in photosensitivity, and has one or more ethylenically unsaturated groups in one molecule. It is more preferably a compound having (ie, an ethylenically unsaturated compound), and particularly preferably a compound having two or more ethylenically unsaturated groups in one molecule (ie, a polyfunctional ethylenically unsaturated compound). preferable.
  • the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, and preferably 3 or less, in terms of being excellent in resolution and peelability. It is more preferable, and it is particularly preferable that the number is two or less.
  • the polymerizable compound B preferably contains a trifunctional or higher functional ethylenically unsaturated compound from the viewpoint of curability and the strength and durability of the obtained resin pattern 2 as a permanent film, and is pentafunctional or higher. More preferably, it contains an ethylenically unsaturated compound.
  • the ethylenically unsaturated compound is preferably a (meth) acrylate compound having one or more (meth) acryloyl groups in one molecule.
  • the polymerizable compound B is a compound having two ethylenically unsaturated groups in one molecule (that is, 2) from the viewpoint of having a better balance of photosensitivity, resolution, and peelability in the negative photosensitive resin layer N. It is preferable to contain at least one selected from the group consisting of a functional ethylenically unsaturated compound) and a compound having three ethylenically unsaturated groups in one molecule (that is, a trifunctional ethylenically unsaturated compound). It is more preferable to contain a compound having two ethylenically unsaturated groups in one molecule.
  • the polymerizable compound B preferably contains an ethylenically unsaturated compound having an aliphatic cyclic skeleton from the viewpoint of strength and dimensional stability after curing, and is a di (meth) acrylate having an aliphatic cyclic skeleton. It is more preferable to contain a compound, and it is particularly preferable to contain a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure. Further, the polymerizable compound B preferably contains an ethylenically unsaturated compound having a dicyclopentanyl structure or a dicyclopentenyl structure from the viewpoint of strength and dimensional stability after curing.
  • the ratio of the content of the bifunctional ethylenically unsaturated compound to the content of the polymerizable compound B is 40% by mass or more from the viewpoint of excellent peelability of the negative type photosensitive resin layer N. It is preferably 60% by mass or more, and particularly preferably more than 70% by mass.
  • the upper limit of the content ratio of the bifunctional ethylenically unsaturated compound to the content of the polymerizable compound B is not limited and may be 100% by mass. That is, all the polymerizable compounds B contained in the negative photosensitive resin layer N may be bifunctional ethylenically unsaturated compounds.
  • the negative photosensitive resin layer N preferably contains a polymerizable compound B1 having one or more aromatic rings and two ethylenically unsaturated groups in one molecule.
  • the polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-mentioned polymerizable compounds B.
  • the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is preferably 40% by mass or more, preferably 50% by mass or more, from the viewpoint of better resolution. It is more preferably 55% by mass or more, and particularly preferably 60% by mass or more.
  • the upper limit of the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is not limited.
  • the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is preferably 99% by mass or less, more preferably 95% by mass or less, and 90% by mass or less from the viewpoint of peelability. Is more preferable, and 85% by mass or less is particularly preferable.
  • Examples of the aromatic ring in the polymerizable compound B1 include an aromatic hydrocarbon ring (for example, a benzene ring, a naphthalene ring, and an anthracene ring) and an aromatic heterocycle (for example, a thiophene ring, a furan ring, a pyrrole ring, and an imidazole ring. Triazole ring and pyridine ring), and fused rings thereof.
  • the aromatic ring is preferably an aromatic hydrocarbon ring, more preferably a benzene ring.
  • the aromatic ring may have a substituent.
  • the polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing the swelling of the negative photosensitive resin layer N due to the developing solution.
  • the bisphenol structure include a bisphenol A structure derived from bisphenol A (that is, 2,2-bis (4-hydroxyphenyl) propane) and bisphenol F (that is, 2,2-bis (4-hydroxyphenyl) methane).
  • Examples include a bisphenol F structure derived from bisphenol B and a bisphenol B structure derived from bisphenol B (that is, 2,2-bis (4-hydroxyphenyl) butane).
  • the bisphenol structure is preferably a bisphenol A structure.
  • Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure. Each polymerizable group may be directly attached to the bisphenol structure. Each polymerizable group may be attached to the bisphenol structure via one or more alkyleneoxy groups.
  • the alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group.
  • the number of alkyleneoxy groups added to the bisphenol structure is not limited, but is preferably 4 to 16 per molecule, and more preferably 6 to 14.
  • the polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162. The contents of the above publication are incorporated herein by reference.
  • the polymerizable compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A structure, and more preferably 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane. ..
  • Examples of the 2,2-bis (4-((meth) acryloxipolyalkoxy) phenyl) propane include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324M, Hitachi Chemical Co., Ltd.).
  • Examples of the polymerizable compound B1 include a compound represented by the following general formula (I).
  • R 1 and R 2 independently represent a hydrogen atom or a methyl group
  • A represents C 2 H 4
  • B represents C 3 H 6
  • n. 1 and n 3 are independently integers from 1 to 39
  • n 1 + n 3 are integers from 2 to 40
  • n 2 and n 4 are independent integers from 0 to 29, respectively.
  • N 2 + n 4 is an integer of 0 to 30, and the sequence of repeating units of-(AO)-and-(BO)-is random or block. good.
  • ⁇ (A—O) ⁇ or ⁇ (BO) ⁇ may be on the bisphenyl group side.
  • n 2 + n 4 is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, further preferably an integer of 0 to 2, and particularly preferably 0.
  • n 1 + n 2 + n 3 + n 4 is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 12.
  • the negative type photosensitive resin layer N may contain one kind alone or two or more kinds of polymerizable compounds B1.
  • the content ratio of the polymerizable compound B1 in the negative photosensitive resin layer N is preferably 10% by mass or more with respect to the total mass of the negative photosensitive resin layer N from the viewpoint of better resolution. More preferably, it is 20% by mass or more.
  • the upper limit of the content ratio of the polymerizable compound B1 is not limited.
  • the content ratio of the polymerizable compound B1 in the negative photosensitive resin layer N shall be 70% by mass or less with respect to the total mass of the negative photosensitive resin layer N from the viewpoint of transferability and edge fuse resistance. Is preferable, and 60% by mass or less is more preferable.
  • the negative photosensitive resin layer N may contain a polymerizable compound B1 and a polymerizable compound B other than the polymerizable compound B1.
  • the polymerizable compound B other than the polymerizable compound B1 include a monofunctional ethylenically unsaturated compound (that is, a compound having one ethylenically unsaturated group in one molecule) and a bifunctional ethylenically having no aromatic ring.
  • Unsaturated compounds ie, compounds that do not have an aromatic ring in one molecule and have two ethylenically unsaturated groups
  • trifunctional or higher functional ethylenically unsaturated compounds ie, in one molecule. Compounds having 3 or more ethylenically unsaturated groups).
  • Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate. , And phenoxyethyl (meth) acrylate.
  • bifunctional ethylenically unsaturated compound having no aromatic ring examples include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.
  • alkylene glycol di (meth) acrylate examples include tricyclodecanedimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Industry Co., Ltd.) and tricyclodecanedimethanol dimethacrylate (DCP, Shin-Nakamura Chemical Industry Co., Ltd.).
  • 1,9-Nonandiol diacrylate (A-NOD-N, Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-Hexanediol diacrylate (A-HD-N, Shin-Nakamura Chemical Industry Co., Ltd.), Examples thereof include ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di (meth) acrylate.
  • polyalkylene glycol di (meth) acrylate examples include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di (meth) acrylate.
  • Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate.
  • Examples of commercially available products include 8UX-015A (Taisei Fine Chemical Co., Ltd.), UA-32P (Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (Shin-Nakamura Chemical Co., Ltd.).
  • Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth).
  • Examples thereof include acrylates, trimethylolpropane tetra (meth) acrylates, trimethylolethanetri (meth) acrylates, tri (meth) acrylates of isocyanurates, glycerintri (meth) acrylates, and alkylene oxide modified products thereof.
  • (tri / tetra / penta / hexa) (meth) acrylate is a concept that includes tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. be.
  • (tri / tetra) (meth) acrylate” is a concept including tri (meth) acrylate and tetra (meth) acrylate.
  • alkylene oxide-modified product of the trifunctional or higher functional ethylenically unsaturated compound examples include caprolactone-modified (meth) acrylate compound (for example, KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd.) and Shin Nakamura Chemical Industry Co., Ltd.
  • alkylene oxide-modified (meth) acrylate compound for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E manufactured by Shin Nakamura Chemical Industry Co., Ltd., Shin Nakamura A-9300 manufactured by Chemical Industry Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex, ethoxylated glycerin triacrylate (for example, A-GLY-9E manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Examples thereof include Aronix (registered trademark) TO-2349 (Toa Synthetic Co., Ltd.), Aronix M-520 (Toa Synthetic Co., Ltd.), and Aronix M-510 (Toa Synthetic Co., Ltd.).
  • Examples of the polymerizable compound B other than the polymerizable compound B1 include the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942.
  • the negative photosensitive resin layer N preferably contains a polymerizable compound B1 and a trifunctional or higher functional ethylenically unsaturated compound, preferably the polymerizable compound B1 and two or more trifunctional or higher ethylenes. It is more preferable to contain a sex unsaturated compound.
  • the mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compound ([total mass of the polymerizable compound B1]: [total mass of the trifunctional or higher ethylenically unsaturated compound] is It is preferably 1: 1 to 5: 1, more preferably 1.2: 1 to 4: 1, and particularly preferably 1.5: 1 to 3: 1.
  • the weight average molecular weight (Mw) of the polymerizable compound B is preferably 200 to 3,000, more preferably 280 to 2,200, and particularly preferably 300 to 2,200.
  • the negative type photosensitive resin layer N may contain one kind alone or two or more kinds of polymerizable compounds B.
  • the content ratio of the polymerizable compound B in the negative photosensitive resin layer N is preferably 10% by mass to 70% by mass, preferably 20% by mass to 60% by mass, based on the total mass of the negative photosensitive resin layer N. It is more preferably%, and particularly preferably 20% by mass to 50% by mass.
  • the negative photosensitive resin layer N preferably contains a polyfunctional epoxy resin from the viewpoint of strength and durability of the obtained pattern 2 as a permanent film, and preferably contains a polyfunctional epoxy resin, a hydroxy group-containing compound, and a photocation. It is more preferable to include a polymerization initiator.
  • the polyfunctional epoxy resin include an epoxy compound having at least two oxylan groups in one molecule, an epoxy compound containing at least two epoxy groups having an alkyl group at the ⁇ -position in one molecule, and the like.
  • Examples of the epoxy compound having at least two oxylan groups in one molecule include a bisphenol F type epoxy resin (Epototo YDF-170, manufactured by Toto Kasei Co., Ltd.), a bixilenol type or a biphenol type epoxy resin (“YX4000,” Japan Epoxy Resin Co., Ltd. ”, etc.) or a mixture thereof, a heterocyclic epoxy resin having an isocyanurate skeleton, etc.
  • a bisphenol F type epoxy resin Epoto YDF-170, manufactured by Toto Kasei Co., Ltd.
  • YX4000 Japan Epoxy Resin Co., Ltd.
  • a heterocyclic epoxy resin having an isocyanurate skeleton etc.
  • Bisphenol A type epoxy resin Novolak type epoxy resin, Bisphenol F type epoxy resin, Hydrogenated Bisphenol A type epoxy resin, Bisphenol S type epoxy resin, Phenol Novolak type epoxy resin, Cresole Novolak type epoxy resin, Halogenized epoxy resin ( For example, low brominated epoxy resin, high halogenated epoxy resin, brominated phenol novolac type epoxy resin, etc.), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy Resins, dicyclopentadiene type epoxy resins (“HP-7200, HP-7200H; manufactured by DIC Co., Ltd.”, etc.), glycidylamine type epoxy resins (diaminodiphenylmethane type epoxy resins, diglycidylani
  • Imid type alicyclic epoxy resin trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylol ethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy Resin (Naftor Aralkill type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional naphthalene type d Epoxy resin, commercially available products such as "ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.”, "HP-4032, EXA-4750, EXA-4700; manufactured by DIC Co., Ltd.”), phenol compounds and divinyl A reaction product of a polyphenol compound obtained by an addition reaction with a diolefin compound such as benzene or dicyclopentadiene and epichlorohydrin, or a ring-opened
  • Bisphenol A type epoxy resin octafunctional bisphenol A novolak type epoxy resin (eg, EPON SU-8 manufactured by Resolution Performance Products), epoxy obtained by reacting alcoholic hydroxy groups of bisphenol F type epoxy resin with epichlorohydrin Resin (eg, NER-7604 manufactured by Nippon Kayaku Co., Ltd.), epoxy resin obtained by reacting the alcoholic hydroxy group of bisphenol A type epoxy resin with epichlorohydrin (eg, NER-1302 manufactured by Nihon Kayaku Co., Ltd.) , O-cresol novolac type epoxy resin (eg, EOCN4400 manufactured by Nippon Kayaku Co., Ltd.), obtained by reacting the phenolic hydroxy group of the resin obtained by reacting di (methoxymethylphenyl) with phenol and epichlorohydrin.
  • epichlorohydrin Resin eg, NER-7604 manufactured by Nippon Kayaku Co., Ltd.
  • epichlorohydrin eg, NER-1302 manufactured by Ni
  • Biphenylphenol novolac type epoxy resin (eg NC-3000H manufactured by Nippon Kayaku Co., Ltd.), epoxy resin having a cyclic phosphorus-containing structure, ⁇ -methylstilben type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenyl Type liquid crystal epoxy resin, azomethinphenyl type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type epoxy resin, glycidyl methacrylate copolymer epoxy resin ("CP-50S, CP-50M; manufactured by Nippon Oil & Fats Co., Ltd.”, etc.) , Cyclohexyl maleimide and glycidyl methacrylate copolymer epoxy resin, bis (glycidyl oxyphenyl) fluorene type epoxy resin, bis (glycidyl oxyphenyl) adamantan type epoxy resin and the like. These may be used alone or in combination of two or more.
  • an epoxy compound containing at least two epoxy groups having an alkyl group at the ⁇ -position in one molecule can be used, and the ⁇ -position is an alkyl group.
  • Compounds containing an epoxy group substituted with are particularly preferable.
  • all of the two or more epoxy groups contained in one molecule may be ⁇ -alkyl substituted glycidyl groups, and at least one epoxy group. May be a ⁇ -alkyl substituted glycidyl group.
  • oxetane compound examples include an oxetane compound having at least two oxetanyl groups in one molecule. Specifically, for example, bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl-).
  • oxetans such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers or copolymers thereof, compounds having an oxetane group
  • examples include ether compounds such as novolak resin, poly (p-hydroxystyrene), cardo-type bisphenols, calix arrayes, calix resorcinarenes, resins having a hydroxyl group such as silsesquioxane, and the oxetane ring. Examples thereof include a copoly
  • any epoxy resin can be used as long as it has two or more epoxy groups in one molecule, but the epoxy equivalent of the epoxy resin is 100 g / g so that a sufficient curing rate can be obtained. Equivalent to 500 g / equivalent is preferable, and 100 g / equivalent to 300 g / equivalent is more preferable.
  • the epoxy equivalent referred to here means a value measured by a method based on JIS K-7236.
  • As the type of epoxy resin glycidyl ether type, glycidyl ester type, glycidyl amine type, alicyclic type and the like can be used, but glycidyl ether type and glycidyl ester type are preferable because of good liquid storage stability.
  • the ether type is most preferable.
  • the epoxy resin is preferably liquid at room temperature (25 ° C.), more preferably has a viscosity at 25 ° C. of 5,000 mPa ⁇ s or less, and is 1,000 mPa ⁇ s or less. More preferably. These epoxy resins can be used alone or in admixture of two or more.
  • epoxy resin examples include sorbitol polyglycidyl ether as a glycidyl ether type, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, and trimethylolpropane polyglycidyl ether.
  • the negative photosensitive resin layer N may contain one type alone or two or more types of polyfunctional epoxy resins.
  • the content ratio of the polyfunctional epoxy resin in the negative photosensitive resin layer N is preferably 10% by mass to 90% by mass, preferably 20% by mass to 70% by mass, based on the total mass of the negative photosensitive resin layer N. More preferably.
  • the negative photosensitive resin layer N preferably contains a hydroxy group-containing compound from the viewpoint of strength and durability of the obtained pattern 2 as a permanent film.
  • a hydroxy group-containing compound a polyol compound or a phenolic compound can be appropriately used.
  • the polyol compound contains a hydroxy group that reacts with the epoxy group in the epoxy resin under the influence of an acid catalyst and acts as a reactive diluent.
  • the dry coating film obtained by drying the solvent component after coating the resin composition is softened, so that stress induction during the production of the laminate is avoided and shrinkage is reduced. , It is possible to prevent cracks in the resin pattern 2 which is a permanent film.
  • polyol compound a commercially available polyester polyol can be used. Specific examples include “Plaxel 205" having a molecular weight of 530 and an OH value (also referred to as "hydroxyl value") of 210 mgKOH / g, “Plaxel 210" having a molecular weight of 1,000 and an OH value of 110 mgKOH / g, and a molecular weight.
  • “Plaxel 220” with a molecular weight of 2,000 and an OH value of 56 mgKOH / g both trade names, manufactured by Daicel Co., Ltd.
  • Examples thereof include "Capa2100” having an OH value of 112 mgKOH / g and "Capa2200” having a molecular weight of 2,000 and an OH value of 56 mgKOH / g (both trade names, manufactured by Perstop).
  • phenol-based compound examples include phenol novolac resin, cresol novolak resin, polyfunctional bisphenol A novolak resin, biphenylphenol novolac resin, phenol resin having a trishydroxyphenylmethane skeleton, phenol resin having a terpendiphenol skeleton, and bisphenol.
  • examples thereof include phenol resins made from various phenols such as A and bisphenol F.
  • the hydroxyl value of the preferred hydroxyl group-containing compound of the hydroxy group-containing compound is preferably 90 mgKOH / g to 300 mgKOH / g, and more preferably 100 mgKOH / g to 250 mgKOH / g. This hydroxy group-containing compound may be used alone or in combination of two or more.
  • the negative photosensitive resin layer N may contain one kind alone or two or more kinds of hydroxy group-containing compounds.
  • the content ratio of the hydroxy group-containing compound in the negative photosensitive resin layer N is preferably 1% by mass to 35% by mass, and 5% by mass to 25% by mass, based on the total mass of the negative photosensitive resin layer N. More preferably.
  • the negative photosensitive resin layer N preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is a compound that receives active light (for example, ultraviolet rays, visible light, and X-rays) to initiate polymerization of a polymerizable compound (for example, polymerizable compound B).
  • active light for example, ultraviolet rays, visible light, and X-rays
  • the photopolymerization initiator is not limited, and a known photopolymerization initiator can be used.
  • the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable from the viewpoint of curability.
  • the negative type photosensitive resin layer N preferably contains a photocationic polymerization initiator from the viewpoint of the strength and durability of the obtained resin pattern 2 as a permanent film.
  • Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an ⁇ -aminoalkylphenone structure, a photopolymerization initiator having an ⁇ -hydroxyalkylphenone structure, and an acylphosphine oxide. Examples thereof include a photopolymerization initiator having a structure and a photopolymerization initiator having an N-phenylglycine structure.
  • the negative photosensitive resin layer N contains 2,4,5-triarylimidazole dimer as a photoradical polymerization initiator from the viewpoints of photosensitivity, visibility of exposed parts, visibility of unexposed parts, and resolution. It preferably contains at least one selected from the group consisting of a mer and a derivative of the 2,4,5-triarylimidazole dimer.
  • the two 2,4,5-triarylimidazole dimers and their derivatives may have the same or different structures.
  • Derivatives of the 2,4,5-triarylimidazole dimer include, for example, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di. (Methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, and 2- (P-methoxyphenyl) -4,5-diphenylimidazole dimer can be mentioned.
  • photoradical polymerization initiator examples include the polymerization initiators described in paragraphs 0031 to 0042 of JP2011-95716A and paragraphs 0064 to 0081 of JP2015-14783A.
  • photoradical polymerization initiator examples include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), and benzophenone.
  • DBE ethyl dimethylaminobenzoate
  • benzoin methyl ether examples include benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), and benzophenone.
  • photoradical polymerization initiators include, for example, TAZ-110 (Midori Chemical Co., Ltd.), TAZ-111 (Midori Chemical Co., Ltd.), 1- [4- (Phenylthio)] phenyl-1,2-.
  • Octandion-2- (O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, BASF), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-3 Il] Etanon-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, BASF), IRGACURE OXE-03 (BASF), IRGACURE OXE-04 (BASF), 2- (dimethylamino)- 2-[(4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: Omnirad 379EG, IGM Resins BV), 2-methyl-1- (4-Methylthiophenyl) -2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins BV), 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2) -Met
  • the photoradical polymerization initiator includes at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and derivatives of 2,4,5-triarylimidazole dimer. Is preferable.
  • the photocationic polymerization initiator (that is, a photoacid generator) generates a cation by being irradiated with ultraviolet rays, far ultraviolet rays, excimer lasers such as KrF and ArF, X-rays, electron beams, etc., and the cations are polymerized. It is a compound that can be an initiator.
  • a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm and generates an acid is preferable.
  • the chemical structure of the photocationic polymerization initiator is not limited.
  • a photocationic polymerization initiator that is not directly sensitive to active light with a wavelength of 300 nm or more is also a sensitizer if it is a compound that is sensitive to active light with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. Can be preferably used in combination with.
  • Examples of the photocationic polymerization initiator include aromatic iodonium complex salts and aromatic sulfonium complex salts.
  • aromatic iodonium complex salts include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and trilucmil iodonium tetrakis.
  • Examples thereof include (pentafluorophenyl) borate (manufactured by Rhodia, trade name Rhodesyl PI2074), di (4-tershaributyl) iodonium tris (trifluoromethanesulfonyl) metanide (manufactured by BASF, trade name CGI BBI-C1) and the like.
  • Specific examples of the aromatic sulfonium complex salt include 4-thiophenyldiphenylsulfonium hexafluoroantimonate (manufactured by San Apro, trade name CPI-101A) and thiophenyldiphenyl sulfonium tris (pentafluoroethyl) trifluoro.
  • Phenyl phosphate (manufactured by San Apro, trade name CPI-210S), 4- ⁇ 4- (2-chlorobenzoyl) phenylthio ⁇ phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate (manufactured by ADEKA, trade name SP-172) , 4-Phenyl Diphenyl Sulfonium Hexafluoro Antimonate-Containing Aromatic Sulfonium Hexafluoro Antimonate Mixture (ACETO Corporate USA, Trade Name CPI-6996) and Triphenyl Sulfonium Tris (Trifluoromethanesulfonyl) Metanide (BASF, trade name CGI TPS-C1), Tris [4- (4-acetylphenyl) sulfonylphenyl] sulfonium tris (trifluoromethylsulfonyl) methide (BASF,
  • aromatic sulfonium complex salts are preferable from the viewpoint of vertical rectangular processability and thermal stability, and 4- ⁇ 4- (2-chlorobenzoyl) phenylthio ⁇ phenylbis (4-fluoro) is preferable.
  • Phenyl Sulfonium hexafluoroantimonate, a mixture of aromatic sulfonium hexafluoroantimonates containing 4-thiophenyldiphenyl sulfonium hexafluoroantimonate, or tris [4- (4-acetylphenyl) sulfonylphenyl] Sulfonium tetrakis (2,3,4,5,6-pentafluorophenyl) borate is particularly preferred.
  • the photocationic polymerization initiator is preferably a photocationic polymerization initiator that generates an acid having a pKa of 4 or less, and more preferably a photocationic polymerization initiator that generates an acid having a pKa of 3 or less.
  • a photocationic polymerization initiator that generates an acid having a pKa of 2 or less is particularly preferable.
  • the lower limit of pKa is not limited.
  • the pKa of the acid generated from the photocationic polymerization initiator is preferably -10.0 or more, for example.
  • photocationic polymerization initiator examples include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.
  • ionic photocationic polymerization initiator examples include onium salt compounds (for example, diaryliodonium salt compounds and triarylsulfonium salt compounds), and quaternary ammonium salt compounds.
  • Examples of the ionic photocationic polymerization initiator include the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-85643.
  • nonionic photocationic polymerization initiator examples include trichloromethyl-s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.
  • examples of the trichloromethyl-s-triazine compound, the diazomethane compound, and the imide sulfonate compound include the compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Laid-Open No. 2011-22149.
  • examples of the oxime sulfonate compound include the compounds described in paragraphs 0084 to 0088 of International Publication No. 2018/179640.
  • the negative type photosensitive resin layer N may contain one kind alone or two or more kinds of photopolymerization initiators.
  • the content ratio of the photopolymerization initiator in the negative photosensitive resin layer N is preferably 0.01% by mass or more, preferably 0.1% by mass or more, based on the total mass of the negative photosensitive resin layer N. It is more preferable to have it, and it is particularly preferable that it is 1.0% by mass or more.
  • the upper limit of the content ratio of the photopolymerization initiator is not limited.
  • the content ratio of the photopolymerization initiator is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the negative photosensitive resin layer N.
  • the negative photosensitive resin layer N preferably contains a metal oxidation inhibitor.
  • the metal oxidation inhibitor is preferably a compound having an aromatic ring containing a nitrogen atom in the molecule. Further, as the metal oxidation inhibitor, at least the aromatic ring containing a nitrogen atom is selected from the group consisting of an imidazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, and a fused ring between them and another aromatic ring. It is preferably one ring, and more preferably the aromatic ring containing a nitrogen atom is an imidazole ring or a fused ring of an imidazole ring and another aromatic ring.
  • the other aromatic ring may be a mono-prime ring or a heterocyclic ring, but a mono-prime ring is preferable, a benzene ring or a naphthalene ring is more preferable, and a benzene ring is further preferable.
  • Preferred metal oxidation inhibitors are preferably imidazole, benzimidazole, tetrazole, mercaptothiazazole, and benzotriazole, with imidazole, benzimidazole, and benzotriazole being more preferred.
  • the metal oxidation inhibitor a commercially available product may be used, and for example, Johoku Chemical Industry Co., Ltd., BT120, etc. containing benzotriazole can be preferably used.
  • a benzotriazole compound or a carboxybenzotriazole compound is preferably mentioned.
  • the benzotriazole compound include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, and the like. Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.
  • Examples of the carboxybenzotriazole compound include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole. Examples of commercially available products of the carboxybenzotriazole compound include CBT-1 (Johoku Chemical Industry Co., Ltd.).
  • the negative photosensitive resin layer N may contain one kind alone or two or more kinds of metal oxidation inhibitors.
  • the content of the metal oxidation inhibitor is preferably 0.1% by mass to 20% by mass, preferably 0.5% by mass to 10% by mass, based on the total mass of the negative photosensitive resin layer N. More preferably, it is more preferably 1% by mass to 5% by mass.
  • the negative photosensitive resin layer N may contain components other than the above-mentioned components (hereinafter, may be referred to as “arbitrary components”).
  • Optional components include, for example, dyes, surfactants, and additives other than the above components.
  • the negative photosensitive resin layer N has a maximum absorption in the wavelength range of 400 nm to 780 nm at the time of color development from the viewpoints of the visibility of the exposed portion, the visibility of the non-exposed portion, the pattern visibility after development, and the resolution. It is preferable to contain a dye having a wavelength of 450 nm or more and whose maximum absorption wavelength is changed by an acid, a base, or a radical (hereinafter, may be referred to as “dye NC”). Although the detailed mechanism is unknown, the inclusion of the dye NC in the negative photosensitive resin layer N improves the adhesion with the layer adjacent to the negative photosensitive resin layer N, and is more excellent in resolution.
  • the term "maximum absorption wavelength changes by acid, base, or radical" used with respect to a dye is a mode in which a dye in a color-developing state is decolorized by an acid, base, or radical. It may mean any aspect of a mode in which the dye in the above color is developed by an acid, a base or a radical, and a mode in which the dye in a color-developing state changes to a color-developing state of another hue.
  • the dye NC may be a compound that changes from the decolorized state by exposure to develop a color, or may be a compound that changes from the decolorized state by exposure to decolorize.
  • the dye NC may be a dye whose color development or decolorization state is changed by the action of an acid, a base, or a radical generated by exposure.
  • the dye NC is a dye whose color development or decolorization state changes by changing the state (for example, pH) in the negative photosensitive resin layer N by an acid, a base, or a radical generated by exposure. There may be.
  • the dye NC may be a dye whose color development or decolorization state changes by directly receiving an acid, a base, or a radical as a stimulus without exposure.
  • the dye NC is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical from the viewpoint of visibility of an exposed portion, visibility of a non-exposed portion, and resolution, and the maximum absorption wavelength is changed by a radical. It is more preferable that the dye is a dye.
  • the negative photosensitive resin layer N is a dye NC whose maximum absorption wavelength is changed by radicals and a photoradical polymerization initiator from the viewpoints of visibility of exposed parts, visibility of non-exposed parts, and resolution. It is preferable to include both of the above.
  • the dye NC is preferably a dye that develops color with an acid, a base, or a radical from the viewpoint of visibility of the exposed part and visibility of the non-exposed part.
  • An example of the color-developing mechanism of dye NC is by exposing a negative photosensitive resin layer N containing a photoradical polymerization initiator, a photocationic polymerization initiator (that is, a photoacid generator), or a photobase generator.
  • a photoradical polymerization initiator that is, a photoacid generator
  • a photobase generator that is, a photoacid generator
  • Radical-reactive dyes, acid-reactive dyes, or base-reactive dyes are produced by radicals, acids, or bases generated from photoradical polymerization initiators, photocationic polymerization initiators, or photobase generators.
  • An aspect of developing color can be mentioned.
  • the maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development is preferably 550 nm or more, preferably 550 nm to 700 nm, from the viewpoint of the visibility of the exposed portion and the visibility of the non-exposed portion. More preferably, it is particularly preferably 550 to 650 nm.
  • the dye NC may have one or two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm at the time of color development.
  • the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.
  • the maximum absorption wavelength of the dye NC is the transmission spectrum of the solution containing the dye NC (liquid temperature 25 ° C.) in the range of 400 nm to 780 nm using a spectrophotometer (UV3100, Shimadzu Corporation) in an atmospheric atmosphere. It is measured and then measured by detecting the wavelength at which the intensity of light is minimized (maximum absorption wavelength).
  • Examples of the dye that develops or decolorizes by exposure include leuco compounds.
  • Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.
  • the dye NC is preferably a leuco compound from the viewpoint of the visibility of the exposed portion and the visibility of the non-exposed portion.
  • the leuco compound examples include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropylan skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and a diarylmethane skeleton.
  • triarylmethane dye a leuco compound having a triarylmethane skeleton
  • spiropylan dye a leuco compound having a spiropylan skeleton
  • fluorane dye fluorane dye
  • diarylmethane skeleton examples include a diarylmethane skeleton having a diarylmethane skeleton.
  • leuco compound (diarylmethane dye) having a rhodamine lactam skeleton, a rhodamine lactam skeleton (rhodamine lactam dye), a leuco compound having an indrill phthalide skeleton (indolyl phthalide dye), and a leuco auramine skeleton.
  • Leuco compounds (leuco auramine dyes) can be mentioned.
  • the leuco compound is preferably a triarylmethane dye or a fluorane dye, and more preferably a leuco compound having a triphenylmethane skeleton (triphenylmethane dye) or a fluorane dye.
  • the leuco compound preferably has a lactone ring, a surujin ring, or a sultone ring from the viewpoint of visibility of the exposed portion and visibility of the non-exposed portion.
  • a radical generated from the photoradical polymerization initiator or an acid generated from the photocationic polymerization initiator By reacting the lactone ring, sultin ring, or sulton ring contained in the leuco compound with a radical generated from the photoradical polymerization initiator or an acid generated from the photocationic polymerization initiator, the leuco compound is changed to a closed ring state.
  • the color can be decolorized, or the radical compound can be changed to a ring-opened state to develop a color.
  • the leuco compound is preferably a compound having a lactone ring, a sultone ring, or a sultone ring, and the lactone ring, the sultone ring, or the sultone ring is opened by a radical or an acid to develop a color. It is more preferable that the compound has, and the lactone ring is opened by a radical or an acid to develop a color.
  • leuco compounds include p, p', p "-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (Ciba Geigy), crystal violet lactone, malakite green lactone, benzoyl leucomethylene blue, 2 -(N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) aminofluorane, 2-anilino-3-methyl-6- (N-ethyl-p-toluizino) fluorane, 3,6-dimethoxyfluorane, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluorane, 3- (N-cyclohexyl-N-methylamino) -6- Methyl-7-anilinofluorane, 3- (N, N-diethylamino) -6
  • Examples of the dye NC include a dye.
  • Specific examples of dyes include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuxin, Methyl Violet 2B, Kinaldine Red, Rose Bengal, Metanyl Yellow, Timor Sulfophthalene, Xylenol Blue, Methyl Orange, Paramethyl.
  • the dye NC is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoints of visibility of exposed parts, visibility of non-exposed parts, pattern visibility after development, and resolution, and color is developed by radicals. It is more preferable that the dye is a radical.
  • the dye NC is preferably leuco crystal violet, crystal violet lactone, brilliant green, or Victoria pure blue-naphthalene sulfonate.
  • the negative type photosensitive resin layer N may contain one kind alone or two or more kinds of dyes.
  • the content ratio of the dye is 0.1 with respect to the total mass of the negative photosensitive resin layer N from the viewpoints of the visibility of the exposed portion, the visibility of the non-exposed portion, the pattern visibility after development, and the resolution. It is preferably 0% by mass or more, more preferably 0.1% by mass to 10% by mass, further preferably 0.1% by mass to 5% by mass, and 0.1% by mass to 1% by mass. Is particularly preferable.
  • the content ratio of the dye NC means the content ratio of the dye when all of the dye NC contained in the negative type photosensitive resin layer N is in a colored state.
  • a method for quantifying the content ratio of dye NC will be described by taking a dye that develops color by radicals as an example. Two solutions are prepared by dissolving the dye (0.001 g) and the dye (0.01 g) in methyl ethyl ketone (100 mL). IRGACURE OXE-01 (BASF) is added to each of the obtained solutions as a photoradical polymerization initiator, and then radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state.
  • BASF methyl ethyl ketone
  • the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve is prepared.
  • the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that the negative photosensitive resin layer N (3 g) is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the negative photosensitive resin layer N, the content of the dye contained in the negative photosensitive resin layer N is calculated based on the calibration curve.
  • the negative photosensitive resin layer N preferably contains a surfactant from the viewpoint of thickness uniformity.
  • the surfactant include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, and nonionic surfactants are preferable.
  • nonionic surfactant examples include a polyoxyethylene higher alkyl ether compound, a polyoxyethylene higher alkylphenyl ether compound, a higher fatty acid diester compound of polyoxyethylene glycol, a silicone-based nonionic surfactant, and a fluorine-based nonionic property.
  • Surfactants can be mentioned.
  • the negative photosensitive resin layer N preferably contains a fluorine-based nonionic surfactant from the viewpoint of being more excellent in resolution. It is considered that the negative type photosensitive resin layer N contains a fluorine-based nonionic surfactant to suppress the penetration of the etching solution into the negative type photosensitive resin layer N and reduce the side etching.
  • Commercially available products of the fluorine-based nonionic surfactant include, for example, Megafvck (registered trademark) F-551, F-552 (DIC Corporation), and Megafvck F-554 (DIC Corporation). ..
  • surfactant examples include the surfactant described in paragraphs 0120 to 0125 of International Publication No. 2018/179640, the surfactant described in paragraph 0017 of Japanese Patent No. 45027884, and JP-A-2009-237362.
  • the surfactants described in paragraphs 0060 to 0071 of the publication are also mentioned.
  • the negative type photosensitive resin layer N may contain one type alone or two or more types of surfactants.
  • the content ratio of the surfactant is preferably 0.001% by mass to 10% by mass, and preferably 0.01% by mass to 3% by mass, based on the total mass of the negative photosensitive resin layer N. More preferred.
  • Additives examples include a radical polymerization inhibitor, a sensitizer, a plasticizer, a heterocyclic compound, a resin other than those described above, and a solvent.
  • the negative type photosensitive resin layer N may contain one kind alone or two or more kinds of additives.
  • the negative type photosensitive resin layer N may contain a radical polymerization inhibitor.
  • the radical polymerization inhibitor include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784.
  • the radical polymerization inhibitor is preferably phenothiazine, phenoxazine, or 4-methoxyphenol.
  • the radical polymerization inhibitor other than the above include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. It is preferable to use a nitrosophenylhydroxyamine aluminum salt as a radical polymerization inhibitor so as not to impair the sensitivity of the negative photosensitive resin layer N.
  • the ratio of the total content of the radical polymerization inhibitor, the benzotriazol compound, and the carboxybenzotriazol compound is 0.01% by mass to 3% by mass with respect to the total mass of the negative photosensitive resin layer N. It is preferably 0.05% by mass to 1% by mass, and more preferably 0.05% by mass to 1% by mass. It is preferable that the ratio of the total content of each of the above components is 0.01% by mass or more from the viewpoint of imparting storage stability to the negative photosensitive resin layer N. On the other hand, it is preferable that the ratio of the total content of each of the above-mentioned components is 3% by mass or less from the viewpoint of maintaining the sensitivity and suppressing the decolorization of the dye.
  • the negative type photosensitive resin layer N may contain a sensitizer.
  • the sensitizer is not limited, and a known sensitizer can be used.
  • dyes and pigments can also be used as the sensitizer.
  • the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, and triazole compounds (for example, 1,2,4-triazole), stillben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoaclysin compounds.
  • the negative type photosensitive resin layer N may contain one type alone or two or more types of sensitizers.
  • the content ratio of the sensitizer can be appropriately selected depending on the purpose, but the sensitivity to the light source is improved and the curing rate is improved by the balance between the polymerization rate and the chain transfer. From the viewpoint, it is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 1% by mass with respect to the total mass of the negative type photosensitive resin layer N.
  • the negative photosensitive resin layer N may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound.
  • a plasticizer and a heterocyclic compound include the compounds described in paragraphs 097 to 0103 and 0111 to 0118 of International Publication No. 2018/179640.
  • the negative photosensitive resin layer N may contain a resin other than those described above.
  • Resins other than those described above include acrylic resins, styrene-acrylic copolymers (however, limited to copolymers having a styrene content of 40% by mass or less), polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, and polyesters. Examples thereof include resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.
  • the negative type photosensitive resin layer N may contain a solvent.
  • the solvent may remain in the negative type photosensitive resin layer N. The solvent will be described later.
  • the negative photosensitive resin layer N has, as an additive, for example, a metal oxide particle, an antioxidant, a dispersant, an acid growth agent, a development accelerator, a conductive fiber, a thermal radical polymerization initiator, a thermal acid generator, and the like. It may contain at least one selected from the group consisting of UV absorbers, thickeners, cross-linking agents, organic precipitation inhibitors, and inorganic precipitation inhibitors. Additives are described, for example, in paragraphs 0165 to 0184 of JP2014-85643A. The contents of the above publication are incorporated herein by reference.
  • the negative photosensitive resin layer N may contain a predetermined amount of impurities.
  • impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof.
  • halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the content is preferably as follows.
  • the content of impurities in the negative photosensitive resin layer N is preferably 80 ppm or less, more preferably 10 ppm or less, and further preferably 2 ppm or less on a mass basis.
  • the content of impurities in the negative photosensitive resin layer N can be 1 ppb or more or 0.1 ppm or more on a mass basis.
  • a raw material having a low impurity content is selected as the raw material of the negative photosensitive resin layer N, prevention of contamination of impurities during the formation of the negative photosensitive resin layer N, and Cleaning the manufacturing equipment to remove impurities.
  • the amount of impurities can be kept within the above range.
  • Impurities can be quantified by a known method, for example, ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, or ion chromatography.
  • ICP Inductively Coupled Plasma
  • the content of benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the negative photosensitive resin layer N is low. Is preferable.
  • the content of the above compound in the negative photosensitive resin layer N is preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 4 ppm or less on a mass basis.
  • the content of the above compound in the negative photosensitive resin layer N can be 10 ppb or more or 100 ppb or more on a mass basis.
  • the content of the above-mentioned compound can be suppressed in the same manner as the above-mentioned metal impurities. Moreover, it can be quantified by a known measurement method.
  • the water content in the negative photosensitive resin layer N is preferably 0.01% by mass to 1.0% by mass, preferably 0.05% by mass to 0% by mass, from the viewpoint of improving reliability and laminateability. More preferably, it is 5% by mass.
  • the thickness of the negative photosensitive resin layer N may be determined, for example, according to the thickness of the resin pattern 2 formed in the developing step described later.
  • the thickness of the negative photosensitive resin layer N may be determined, for example, in the range of 1 ⁇ m to 100 ⁇ m.
  • the transmittance of light having a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and more preferably 50% or more from the viewpoint of being more excellent in adhesion. Is particularly preferable.
  • the upper limit of transmittance is not limited.
  • the transmittance of light having a wavelength of 365 nm is preferably 99.9% or less.
  • the preparation step includes a step of preparing a laminated precursor having a transparent base material and a light-shielding pattern 1 on the transparent base material, and a negative type photosensitive on the transparent base material and the light-shielding pattern 1. It is preferable to include a step of forming the sex resin layer N. In the step of forming the negative type photosensitive resin layer N, it is preferable to form the negative type photosensitive resin layer N by using a photosensitive transfer material (also referred to as “dry film”). That is, the negative type photosensitive resin layer N is preferably a layer formed of a photosensitive transfer material.
  • the preparation steps include a step of preparing a transparent base material, a step of forming a light-shielding pattern 1 on the transparent base material, and a negative type photosensitive resin layer N on the transparent base material and the light-shielding pattern 1. It is preferable to include a step of forming the above.
  • the steps of forming the light-shielding pattern 1 include a step of forming a light-shielding layer on the transparent base material, a step of forming a photosensitive resin layer on the light-shielding layer, and a step of forming the photosensitive resin layer. It is preferable to include a step of forming a resist pattern by exposure and development, and a step of removing the light-shielding layer not covered by the resist pattern.
  • the negative type photosensitive resin layer N it is preferable to form the negative type photosensitive resin layer N by using a photosensitive transfer material.
  • the preparation steps include, for example, a step of preparing a transparent base material, a step of forming a light-shielding pattern 1 on the transparent base material, and a negative photosensitive resin on the transparent base material and the light-shielding pattern 1. Examples thereof include a step of forming the layer N and the like.
  • the preparation steps include, for example, a step of preparing a laminated precursor having a transparent base material and a light-shielding layer on the transparent base material, and a step of forming a light-shielding pattern 1 from the light-shielding layer.
  • An embodiment including a step of forming a negative type photosensitive resin layer N on the transparent base material and the light-shielding pattern 1 can be mentioned.
  • the light-shielding layer is a layer that is a material for the light-shielding pattern 1.
  • Examples of the method for producing a laminated precursor having a transparent base material and a light-shielding layer include a method of forming a light-shielding layer on the transparent base material.
  • the preparatory steps include, for example, a step of forming a light-shielding layer on one surface of the transparent substrate, a step of forming a photoresist layer on the light-shielding layer, and exposing and developing the photoresist layer to form a resist pattern. Examples thereof include a step of forming and a step of etching the light-shielding layer to form the light-shielding pattern 1.
  • the method for forming the photoresist layer is not particularly limited, and known photoresist compositions and photosensitive transfer materials can be used.
  • Examples of the method of forming the light-shielding pattern 1 include a method of forming a light-shielding layer on a transparent base material and then processing the light-shielding layer into a pattern.
  • Examples of the method for forming the light-shielding layer include sputtering and plating.
  • sputtering for example, a layer containing Cu, Ti, or Ni (light-shielding layer) can be formed on a transparent substrate.
  • Cu which has low electrical resistance and is inexpensive, is preferable.
  • the component of the layer (light-shielding layer) formed by sputtering may be Ni, Al, Nb, W, Ni-P, or Ni-B.
  • Examples of plating include electroless plating.
  • a method of electroless plating a known method can be used.
  • electroless copper plating copper can be deposited on a transparent substrate by the reaction of copper ions and a reducing agent.
  • the catalyst used in electroless plating is preferably a palladium-tin mixed catalyst.
  • the primary particle size of the catalyst is preferably 10 nm or less.
  • the plating solution used for electroless plating preferably contains hypophosphorous acid as a reducing agent. Examples of the plating include the plating described in the section "Pattern 3 forming step" below.
  • the structure of the light-shielding layer may be a single-layer structure or a multi-layer structure. By forming the light-shielding layer having a multi-layer structure, a conductive pattern having a multi-layer structure can be formed. Examples of the method for forming each layer included in the light-shielding layer having a multi-layer structure include electroless plating, sputtering, vapor deposition, and coating of a coupling agent.
  • photolithography As a method of processing the light-shielding layer into a pattern, for example, photolithography can be mentioned.
  • photolithography a known photolithography can be used. For example, a photosensitive resin layer is formed on the light-shielding layer, then a resist pattern is formed by exposure and development of the photosensitive resin layer, and then the light-shielding layer not covered by the resist pattern is removed. As a result, a light-shielding pattern can be formed.
  • the type of the photosensitive resin layer formed on the light-shielding layer is not limited.
  • the photosensitive resin layer may be a positive type photosensitive resin layer or a negative type photosensitive resin layer.
  • Examples of the negative photosensitive resin layer include the negative photosensitive resin layer described in the above section “Negative photosensitive resin layer N”.
  • Examples of the method for forming the photosensitive resin layer include a method using a photosensitive resin composition and a method using a photosensitive transfer material.
  • Examples of the method using the photosensitive resin composition include a method of applying the photosensitive resin composition on the light-shielding layer and then drying the photosensitive resin composition.
  • the photosensitive resin composition is a composition containing a material for a photosensitive resin layer.
  • Examples of the method using the photosensitive transfer material include a method of arranging the photosensitive resin layer on the light-shielding layer by laminating the photosensitive transfer material having the photosensitive resin layer and the light-shielding layer. ..
  • Method of forming the negative type photosensitive resin layer the following section "Method of forming the negative type photosensitive resin layer N" can be referred to.
  • the exposure method of the photosensitive resin layer is not limited as long as it is a method capable of forming an exposed portion and a non-exposed portion in the photosensitive resin layer.
  • As the exposure method a known method can be used.
  • the region of the photosensitive resin layer to be exposed may be determined according to the shape of the target light-shielding pattern. For the exposure conditions, the section "Exposure step" below can be referred to.
  • the method for developing the photosensitive resin layer is not limited as long as the photosensitive resin layer can be processed into a pattern by removing the exposed portion or the non-exposed portion of the photosensitive resin layer.
  • the unexposed portion of the negative photosensitive resin layer is removed.
  • the development of the positive photosensitive resin layer the exposed portion of the positive photosensitive resin layer is removed.
  • a developing method a known method can be used. For the development conditions, the section "Development process" below can be referred to.
  • a known method can be used as a method for removing the light-shielding layer (that is, the exposed light-shielding layer) that is not covered by the resist pattern.
  • the light-shielding layer contains metal
  • the light-shielding layer that is not covered by the resist pattern can be removed by etching.
  • the etching include wet etching and dry etching.
  • the etching is preferably wet etching.
  • Wet etching is etching using a chemical called an etching solution.
  • the etching solution include a sulfuric acid-hydrogen peroxide aqueous solution.
  • the composition of the sulfuric acid-hydrogen peroxide aqueous solution is not limited.
  • Examples of the sulfuric acid-hydrogen acid aqueous solution include a sulfuric acid-hydrogen acid aqueous solution in which the concentration of sulfuric acid is 1% by volume to 10% by volume and the concentration of hydrogen peroxide is 1% by volume to 10% by volume. Be done.
  • the temperature of the sulfuric acid-hydrogen peroxide aqueous solution can be set, for example, in the range of 20 ° C. to 35 ° C.
  • the immersion time in the sulfuric acid-hydrogen peroxide aqueous solution can be set, for example, in the range of 1 minute to 10 minutes.
  • the sulfuric acid-hydrogen peroxide aqueous solution can be used until the concentration of copper dissolved in the sulfuric acid-hydrogen peroxide aqueous solution becomes, for example, 50 g / L.
  • the etching solution include a cupric chloride solution.
  • the composition of the cupric chloride solution is not limited.
  • the cupric chloride solution for example, a solution containing 20% by mass to 35% by mass of cupric chloride and 1% by mass to 7% by mass of chlorine can be preferably used.
  • the etching conditions are not limited to the above conditions.
  • the temperature of the etching solution and the immersion time in the etching solution may be determined according to the composition of the light-shielding layer, the thickness of the light-shielding layer, and the type of the etching solution.
  • the laminated body may have an adhesion layer between the transparent base material and the light-shielding pattern 1.
  • the adhesion layer may be formed, for example, by forming the adhesion layer on the transparent base material before forming the light-shielding pattern 1.
  • Examples of the method for forming the adhesion layer include electroless plating, sputtering, and thin film deposition.
  • Examples of the method for forming the adhesion layer include a method including application, drying, and sintering of a metal particle dispersion liquid in which metal particles are dispersed.
  • the surface of the transparent base material may be roughened by desmear treatment, if necessary, before forming the adhesion layer and the light-shielding pattern.
  • desmear treatment liquid oxidizing roughening liquid
  • examples of the desmear treatment liquid include chromium / sulfuric acid roughening liquid, alkaline permanganate roughening liquid (for example, sodium permanganate roughening liquid), and sodium fluoride / chromium / sulfuric acid crude liquid. Examples include chemicals.
  • Photosensitive resin composition examples include a method of applying the photosensitive resin composition on a transparent base material and a light-shielding pattern, and then drying the photosensitive resin composition.
  • the components of the photosensitive resin composition may be determined according to the components of the target negative photosensitive resin layer N.
  • Preferred components of the photosensitive resin composition include, for example, the components described in the above section "Negative type photosensitive resin layer N".
  • Examples of the photosensitive resin composition include a composition containing a polymer A, a polymerizable compound B, and a photopolymerization initiator.
  • the photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive resin layer.
  • the solvent is not limited as long as it can dissolve or disperse the components of the photosensitive resin composition (for example, the polymer A, the polymerizable compound B, and the polymerization initiator), and a known solvent can be used.
  • a known solvent can be used.
  • the solvent include an alkylene glycol ether solvent, an alkylene glycol ether acetate solvent, an alcohol solvent (for example, methanol and ethanol), a ketone solvent (for example, acetone and methyl ethyl ketone), and an aromatic hydrocarbon solvent (for example, toluene).
  • Examples include aprotonic polar solvents (eg, N, N-dimethylformamide), cyclic ether solvents (eg, tetrahydrofuran), ester solvents, amide solvents, and lactone solvents.
  • the photosensitive resin composition preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent.
  • the photosensitive resin composition comprises at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent. It is more preferable to include it. It is particularly preferable that the photosensitive resin composition contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent.
  • alkylene glycol ether solvent examples include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether. Be done.
  • alkylene glycol ether acetate solvent examples include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.
  • the solvent described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvent described in paragraph 0014 of JP-A-2018-177789 may be used. These contents are incorporated herein by reference.
  • the photosensitive resin composition may contain one kind of solvent alone or two or more kinds of solvents.
  • the content ratio of the solvent in the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. It is more preferable that it is a part.
  • the method for preparing the photosensitive resin composition is not limited.
  • a method for preparing the photosensitive resin composition for example, a method of preparing a photosensitive resin composition by preparing a solution in which each component is dissolved in a solvent in advance and mixing the obtained solutions in a predetermined ratio. Can be mentioned.
  • the photosensitive resin composition is preferably filtered using a filter having a pore size of 0.2 ⁇ m to 30 ⁇ m before forming the negative photosensitive resin layer.
  • the method for applying the photosensitive resin composition is not limited, and a known method can be used.
  • Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.
  • a photosensitive transfer material having a negative photosensitive resin layer N and a transparent base material having a light-shielding pattern are bonded to each other to form a transparent base material and a light-shielding pattern.
  • a method of arranging the negative type photosensitive resin layer N on the surface can be mentioned.
  • the photosensitive transfer material and the transparent base material are superposed on each other, and a roll or the like is used. It is preferable to pressurize and heat by means.
  • a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.
  • the components of the photosensitive transfer material will be described.
  • the photosensitive transfer material has a negative photosensitive resin layer N.
  • the negative type photosensitive resin layer N is as described in the above section “Negative type photosensitive resin layer N”.
  • the photosensitive transfer material preferably has a temporary support.
  • the temporary support is a support that can be peeled off from the photosensitive transfer material.
  • the temporary support can support at least the negative photosensitive resin layer N.
  • the temporary support may be peeled off before the exposure step. After irradiating light without peeling the temporary support in the exposure step, the temporary support may be peeled off. By irradiating light without peeling off the temporary support in the exposure process, the influence of dust and dirt in the exposure environment can be avoided.
  • a temporary support having light transmission can be used.
  • “having light transmittance” means that the transmittance of light having a wavelength used for pattern exposure is 50% or more.
  • the transmittance of light having a wavelength (preferably a wavelength of 365 nm) used for pattern exposure is preferably 60% or more from the viewpoint of improving the exposure sensitivity of the negative photosensitive resin layer N, which is 70. % Or more is more preferable.
  • Examples of the temporary support include a glass substrate, a resin film, and paper.
  • the temporary support is preferably a resin film from the viewpoint of strength, flexibility, and light transmission.
  • the resin film examples include polyethylene terephthalate film (that is, PET film), cellulose triacetate film, polystyrene film, and polycarbonate film.
  • the resin film is preferably a PET film, more preferably a biaxially stretched PET film.
  • the thickness of the temporary support is not limited.
  • the average thickness of the temporary support may be determined, for example, according to the strength of the temporary support, the light transmittance, the material, and the flexibility required for bonding the photosensitive transfer material and the transparent base material. ..
  • the average thickness of the temporary support is preferably 5 ⁇ m to 100 ⁇ m. Further, the average thickness of the temporary support is preferably 5 ⁇ m to 50 ⁇ m, more preferably 5 ⁇ m to 20 ⁇ m, and further preferably 10 ⁇ m to 20 ⁇ m from the viewpoint of ease of handling and versatility. It is particularly preferably 10 ⁇ m to 16 ⁇ m.
  • the arithmetic mean roughness Ra of the surface of the temporary support on the side on which the negative photosensitive resin layer N is arranged is preferably 0.1 ⁇ m or less, more preferably 0.05 ⁇ m or less, and 0.02 ⁇ m. The following is particularly preferable.
  • the lower limit of the arithmetic mean roughness Ra is not limited.
  • the arithmetic mean roughness Ra of the surface of the temporary support on the side on which the negative photosensitive resin layer N is arranged may be determined, for example, in the range of 0 ⁇ m or more.
  • Arithmetic mean roughness Ra is measured by the following method. Using a three-dimensional optical profiler (New View7300, manufactured by Zygo), a surface profile of the object to be measured is obtained under the following conditions. As the measurement and analysis software, Microscope Application of MetroPro ver 8.3.2 is used. Next, the Surface Map screen is displayed using the above software, and histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness Ra of the surface of the object to be measured is obtained. When the surface of the object to be measured is in contact with the surface of another layer, the arithmetic mean roughness Ra of the surface of the exposed object to be measured may be measured by peeling the object to be measured from the other layer. ..
  • the temporary support (particularly the resin film) is free from, for example, deformation (for example, wrinkles), scratches, and defects. From the viewpoint of transparency of the temporary support, it is preferable that the number of fine particles, foreign substances, defects, and precipitates contained in the temporary support is small.
  • the number of fine particles, foreign substances, and defects having a diameter of 1 ⁇ m or more is preferably 50 pieces / 10 mm 2 or less, more preferably 10 pieces / 10 mm 2 or less, and 3 pieces / It is more preferably 10 mm 2 or less, and particularly preferably 0/10 mm 2.
  • the photosensitive transfer material may have a cover film (also referred to as a protective film). According to the cover film, the surface of the layer in contact with the cover film (for example, the negative photosensitive resin layer N) can be protected.
  • the photosensitive transfer material preferably includes a temporary support, a negative photosensitive resin layer N, and a cover film in this order.
  • the photosensitive transfer material preferably has a cover film in contact with the surface of the negative photosensitive resin layer N opposite to the side on which the temporary support is arranged.
  • cover film examples include a resin film and paper.
  • the cover film is preferably a resin film from the viewpoint of strength and flexibility.
  • the resin film examples include polyethylene film, polypropylene film, polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film.
  • the resin film is preferably a polyethylene film, a polypropylene film, or a polyethylene terephthalate film.
  • the thickness of the cover film is not limited.
  • the average thickness of the cover film is preferably 5 ⁇ m to 100 ⁇ m, more preferably 10 ⁇ m to 50 ⁇ m, and particularly preferably 10 ⁇ m to 20 ⁇ m.
  • the arithmetic mean roughness Ra of the surface of the cover film on the side on which the negative photosensitive resin layer N is arranged is preferably 0.3 ⁇ m or less, preferably 0.1 ⁇ m or less, from the viewpoint of excellent resolution. Is more preferable, and 0.05 ⁇ m or less is particularly preferable.
  • the arithmetic mean roughness of the surface on the side where the negative photosensitive resin layer N of the cover film is arranged is within the above range, the thickness of the negative photosensitive resin layer and the formed resin pattern can be made uniform. improves.
  • the lower limit of the arithmetic mean roughness Ra is not limited.
  • the arithmetic average roughness Ra of the surface of the cover film on the side on which the negative photosensitive resin layer N is arranged is preferably 0.001 ⁇ m or more.
  • the arithmetic mean roughness Ra of the surface of the cover film on the side on which the negative photosensitive resin layer N is arranged is measured by a method according to the method for measuring the arithmetic mean roughness Ra described in the above section "Temporary Support”. ..
  • the photosensitive transfer material according to the present disclosure may have a thermoplastic resin layer N.
  • the photosensitive transfer material preferably has a thermoplastic resin layer between the temporary support and the negative type photosensitive resin layer N.
  • the followability to the adherend is improved, and the space between the adherend and the photosensitive transfer material is improved. This is because, as a result of suppressing the mixing of air bubbles, the adhesion between layers is improved.
  • the thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.
  • alkali-soluble resin examples include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, and polyimide resin.
  • alkali-soluble resin examples include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, and polyimide resin.
  • examples thereof include polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.
  • the alkali-soluble resin is preferably an acrylic resin from the viewpoint of developability and adhesion to a layer adjacent to the thermoplastic resin layer.
  • the "acrylic resin” is selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylic acid amide. It means a resin having at least one kind.
  • the ratio of the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylic acid amide is the ratio of the total content of the acrylic resin. It is preferably 50% by mass or more with respect to the total mass.
  • the ratio of the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester is 30% by mass to 100% by mass with respect to the total mass of the acrylic resin. %, More preferably 50% by mass to 100% by mass.
  • the alkali-soluble resin is preferably a polymer having an acid group.
  • the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, and a carboxy group is preferable.
  • the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and more preferably a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more.
  • the upper limit of acid value is not limited.
  • the acid value of the alkali-soluble resin is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.
  • the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not limited and can be appropriately selected from known resins and used.
  • Examples of the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more include carboxy group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP-A-2011-95716. Described in paragraphs 0033 to 0052 of Japanese Patent Application Laid-Open No. 2010-237589, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more, and paragraphs 0053 to 0068 of JP-A-2016-224162.
  • a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be mentioned.
  • the content ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, preferably 10% by mass to 40% by mass, based on the total mass of the carboxy group-containing acrylic resin. It is more preferable, and it is particularly preferable that it is 12% by mass to 30% by mass.
  • the alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth) acrylic acid from the viewpoint of developability and adhesion to a layer adjacent to the thermoplastic resin layer.
  • the alkali-soluble resin may have a reactive group.
  • the reactive group may be, for example, a group capable of addition polymerization.
  • Reactive groups include, for example, ethylenically unsaturated groups, polycondensable groups (eg, hydroxy and carboxy groups), and polyaddition reactive groups (eg, epoxy groups and (blocking) isocyanate groups). Be done.
  • the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and particularly preferably 20,000 to 50,000.
  • the thermoplastic resin layer may contain one type alone or two or more types of alkali-soluble resins.
  • the content ratio of the alkali-soluble resin is 10% by mass to 99% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of developability and adhesion to the layer adjacent to the thermoplastic resin layer. It is more preferably 20% by mass to 90% by mass, further preferably 40% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass.
  • the thermoplastic resin layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development, and the maximum absorption wavelength is changed by an acid, a base, or a radical (hereinafter referred to as “dye B”). In some cases), it is preferable to include.
  • the preferred embodiment of the dye B is the same as the preferred embodiment of the dye NC described above, except for the points described later.
  • the dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical from the viewpoint of visibility of the exposed part, visibility of the non-exposed part, and resolution, and the maximum absorption wavelength is changed by the acid. It is more preferable that the dye is a radical.
  • the thermoplastic resin layer is composed of a dye whose maximum absorption wavelength is changed by an acid as dye B and a compound which generates an acid by light, which will be described later, from the viewpoints of visibility of an exposed part, visibility of a non-exposed part, and resolution. And, preferably.
  • the thermoplastic resin layer may contain one type alone or two or more types of dye B.
  • the content ratio of the dye B is preferably 0.2% by mass or more, preferably 0.2% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of the visibility of the exposed portion and the visibility of the non-exposed portion. It is more preferably% to 6% by mass, further preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass.
  • the content ratio of the dye B means the content ratio of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored state.
  • a method for quantifying the content ratio of dye B will be described by taking a dye that develops color by radicals as an example. Two solutions are prepared by dissolving the dye (0.001 g) and the dye (0.01 g) in methyl ethyl ketone (100 mL). IRGACURE OXE-01 (BASF) is added to each of the obtained solutions as a photoradical polymerization initiator, and then radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state.
  • IRGACURE OXE-01 BASF
  • the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve is prepared.
  • the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that the thermoplastic resin layer (0.1 g) is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of the dye contained in the thermoplastic resin layer is calculated based on the calibration curve.
  • the thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (hereinafter, may be referred to as "compound C").
  • Compound C is preferably a compound that receives active rays (for example, ultraviolet rays and visible rays) to generate acids, bases, or radicals.
  • active rays for example, ultraviolet rays and visible rays
  • Examples of compound C include known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators).
  • Compound C is preferably a photoacid generator.
  • the thermoplastic resin layer preferably contains a photoacid generator from the viewpoint of resolution.
  • the photoacid generator include a photocationic polymerization initiator that may be contained in the negative-type photosensitive resin layer described above, and the same preferred embodiments are used except for the points described below.
  • the photoacid generator preferably contains at least one selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and has sensitivity, resolution and adhesion. From the viewpoint, it is more preferable to contain an oxime sulfonate compound.
  • the photoacid generator is a photoacid generator having the following structure.
  • the thermoplastic resin layer may contain a photobase generator.
  • the photobase generator include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, and bis [ [(2-Nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoetan, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane , N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaammine cobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,6 -Dimethyl
  • the thermoplastic resin layer may contain a photoradical polymerization initiator.
  • the photoradical polymerization initiator include a photoradical polymerization initiator that may be contained in the negative photosensitive resin layer described above, and the preferred embodiment is also the same.
  • the thermoplastic resin layer may contain one kind alone or two or more kinds of compound C.
  • the content ratio of the compound C is 0.1% by mass to 10% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of the visibility of the exposed portion, the visibility of the non-exposed portion, and the resolution. It is preferable, and it is more preferable that it is 0.5% by mass to 5% by mass.
  • the thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to a layer adjacent to the thermoplastic resin layer, and developability.
  • the molecular weight of the plasticizer (the molecular weight of the oligomer or polymer is the weight average molecular weight (Mw); the same applies hereinafter in this paragraph) is preferably smaller than the molecular weight of the alkali-soluble resin.
  • the molecular weight of the plasticizer is preferably 200 to 2,000.
  • the plasticizer is not limited as long as it is a compound that develops plasticity by being compatible with an alkali-soluble resin. From the viewpoint of imparting plasticity, the plasticizer is preferably a compound having an alkyleneoxy group in the molecule, and more preferably a polyalkylene glycol compound.
  • the alkyleneoxy group contained in the plasticizer preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.
  • the plasticizer preferably contains a (meth) acrylate compound from the viewpoint of resolution and storage stability. From the viewpoint of compatibility, resolution, and adhesion to the layer adjacent to the thermoplastic resin layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound.
  • thermoplastic resin layer and the negative type photosensitive resin layer are arranged in direct contact with each other, the thermoplastic resin layer and the negative type photosensitive resin layer are each the same (meth) acrylate compound. Is preferably included. This is because the thermoplastic resin layer and the negative photosensitive resin layer N each contain the same (meth) acrylate compound, so that the diffusion of components between the layers is suppressed and the storage stability is improved.
  • the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer
  • the (meth) acrylate compound may not polymerize even in the exposed portion after exposure from the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer. preferable.
  • the (meth) acrylate compound used as a plasticizer is composed of two or more (meth) acrylate compounds in one molecule from the viewpoints of resolution, adhesion to a layer adjacent to a thermoplastic resin layer, and developability. It is preferably a (meth) acrylate compound having a meta) acryloyl group.
  • the (meth) acrylate compound used as a plasticizer is preferably a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound.
  • thermoplastic resin layer may contain one type alone or two or more types of plasticizers.
  • the content ratio of the plasticizer is 1% by mass to 70% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoints of resolution, adhesion to the layer adjacent to the thermoplastic resin layer, and developability. It is preferably 10% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass.
  • the thermoplastic resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.
  • the surfactant include a surfactant that may be contained in the negative photosensitive resin layer N described above, and the preferred embodiment is also the same.
  • thermoplastic resin layer may contain one type alone or two or more types of surfactants.
  • the content ratio of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the thermoplastic resin layer.
  • the thermoplastic resin layer may contain a sensitizer.
  • the sensitizer include the sensitizer that may be contained in the negative photosensitive resin layer described above.
  • thermoplastic resin layer may contain one type alone or two or more types of sensitizers.
  • the content ratio of the sensitizer is 0.01% by mass to 5% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of improving the sensitivity to the light source, the visibility of the exposed part, and the visibility of the non-exposed part. %, More preferably 0.05% by mass to 1% by mass.
  • thermoplastic resin layer may contain known additives in addition to the above components, if necessary.
  • thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Laid-Open No. 2014-85643. The contents of the above publication are incorporated herein by reference.
  • the thickness of the thermoplastic resin layer is not limited.
  • the average thickness of the thermoplastic resin layer is preferably 1 ⁇ m or more, and more preferably 2 ⁇ m or more, from the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer.
  • the upper limit of the average thickness of the thermoplastic resin layer is not limited. From the viewpoint of developability and resolvability, the average thickness of the thermoplastic resin layer is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
  • the method for forming the thermoplastic resin layer is not limited as long as it is a method capable of forming a layer containing the above components.
  • Examples of the method for forming the thermoplastic resin layer include a method in which the thermoplastic resin composition is applied to the surface of the temporary support and the coating film of the thermoplastic resin composition is dried.
  • thermoplastic resin composition examples include a composition containing the above components.
  • the thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.
  • the solvent contained in the thermoplastic resin composition is not limited as long as it is a solvent capable of dissolving or dispersing the components contained in the thermoplastic resin layer.
  • the solvent include a solvent that may be contained in the above-mentioned photosensitive resin composition, and the preferred embodiment is also the same.
  • thermoplastic resin composition may contain one kind alone or two or more kinds of solvents.
  • the content ratio of the solvent in the thermoplastic resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the thermoplastic resin composition. It is more preferable that it is a part.
  • thermoplastic resin composition The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out according to the above-mentioned method for preparing the photosensitive resin composition and the method for forming the negative type photosensitive resin layer N.
  • a thermoplastic resin composition was prepared by preparing a solution in which each component contained in the thermoplastic resin layer was dissolved in a solvent in advance and mixing the obtained solutions in a predetermined ratio, and then obtained.
  • the thermoplastic resin layer can be formed by applying the thermoplastic resin composition to the surface of the temporary support and drying the coating film of the thermoplastic resin composition. Further, after forming the negative type photosensitive resin layer N on the cover film, the thermoplastic resin layer may be formed on the surface of the negative type photosensitive resin layer N.
  • the photosensitive transfer material preferably has an intermediate layer between the thermoplastic resin layer and the negative photosensitive resin layer N. According to the intermediate layer, it is possible to suppress the mixing of components when forming a plurality of layers and during storage.
  • the intermediate layer is preferably a water-soluble layer from the viewpoint of developability and suppressing mixing of components during application of the plurality of layers and storage after application.
  • water-soluble means that the solubility in 100 g of water having a liquid temperature of 22 ° C. and a pH of 7.0 is 0.1 g or more.
  • the intermediate layer examples include an oxygen blocking layer having an oxygen blocking function, which is described as a “separation layer” in JP-A-5-72724. Since the intermediate layer is an oxygen blocking layer, the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and as a result, the productivity is improved.
  • the oxygen blocking layer used as the intermediate layer may be appropriately selected from known layers.
  • the oxygen blocking layer used as the intermediate layer is preferably an oxygen blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22 ° C.).
  • the intermediate layer preferably contains a resin.
  • the resin contained in the intermediate layer include polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, acrylamide-based resin, polyethylene oxide-based resin, gelatin, vinyl ether-based resin, polyamide resin, and copolymers thereof. Can be mentioned.
  • the resin contained in the intermediate layer is preferably a water-soluble resin.
  • the resin contained in the intermediate layer is a polymer A contained in the negative photosensitive resin layer N and a thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer from the viewpoint of suppressing mixing of components between a plurality of layers. ), It is preferable that the resin is different from any of the above.
  • the intermediate layer preferably contains polyvinyl alcohol, and preferably contains polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of oxygen blocking property and suppressing mixing of components during application of the plurality of layers and storage after application. Is more preferable.
  • the intermediate layer may contain one kind of resin alone or two or more kinds of resins.
  • the content ratio of the resin in the intermediate layer is 50% by mass with respect to the total mass of the intermediate layer from the viewpoint of oxygen blocking property and suppressing mixing of components during application of the plurality of layers and storage after application. It is preferably ⁇ 100% by mass, more preferably 70% by mass to 100% by mass, further preferably 80% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass. preferable.
  • the intermediate layer may contain an additive if necessary.
  • the additive include a surfactant.
  • the thickness of the intermediate layer is not limited.
  • the average thickness of the intermediate layer is preferably 0.1 ⁇ m to 5 ⁇ m, more preferably 0.5 ⁇ m to 3 ⁇ m.
  • the oxygen blocking property is not deteriorated, the mixing of the components at the time of forming a plurality of layers and at the time of storage can be suppressed, and the intermediate layer at the time of development can be suppressed. The increase in removal time can be suppressed.
  • the method of forming the intermediate layer is not limited as long as it is a method capable of forming a layer containing the above components.
  • a method for forming the intermediate layer for example, a method of applying the composition for the intermediate layer to the surface of the thermoplastic resin layer or the negative photosensitive resin layer N and then drying the coating film of the composition for the intermediate layer is used. Can be mentioned.
  • compositions for the intermediate layer include a composition containing a resin and an optional additive.
  • the composition for the intermediate layer preferably contains a solvent in order to adjust the viscosity of the composition for the intermediate layer and facilitate the formation of the intermediate layer.
  • the solvent is not limited as long as it is a solvent that can dissolve or disperse the resin.
  • the solvent is preferably at least one selected from the group consisting of water and a water-miscible organic solvent, and more preferably water or a mixed solvent of water and a water-miscible organic solvent.
  • the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin.
  • the water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, and more preferably methanol or ethanol.
  • the photosensitive transfer material may further have another layer such as a refractive index adjusting layer.
  • the refractive index adjusting layer is not particularly limited, and a known refractive index adjusting layer can be used.
  • the refractive index of the refractive index adjusting layer is preferably higher than that of the photosensitive layer from the viewpoint of suppressing the visibility of wiring.
  • the refractive index of the refractive index adjusting layer is preferably 1.50 or more, more preferably 1.55 or more, further preferably 1.60 or more, and particularly preferably 1.70 or more. preferable.
  • the upper limit of the refractive index of the refractive index adjusting layer is not particularly limited, but is preferably 2.10 or less, more preferably 1.85 or less, still more preferably 1.78 or less.
  • the thickness of the refractive index adjusting layer is not particularly limited.
  • the thickness of the refractive index adjusting layer is preferably 50 nm or more and 500 nm or less, more preferably 55 nm or more and 110 nm or less, and further preferably 60 nm or more and 100 nm or less.
  • the method of controlling the refractive index of the refractive index adjusting layer is not particularly limited, and for example, a method of using a resin having a predetermined refractive index alone, a method of using a resin and metal oxide particles or metal particles, a metal salt and a resin. A method using a complex with and the like can be mentioned.
  • the type of the metal oxide particles is not particularly limited, and known metal oxide particles can be used.
  • the metal oxide particles are selected from the group consisting of zirconium oxide particles (ZrO 2 particles), Nb 2 O 5 particles, titanium oxide particles (TiO 2 particles), and silicon dioxide particles (SiO 2 particles). At least one kind is preferable.
  • the metal oxide particles for example, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles from the viewpoint that the refractive index of the second resin layer can be easily adjusted to 1.6 or more. Is more preferable.
  • the average thickness of the photosensitive transfer material is preferably 5 ⁇ m to 55 ⁇ m, more preferably 10 ⁇ m to 50 ⁇ m, and particularly preferably 20 ⁇ m to 40 ⁇ m.
  • the average thickness of the photosensitive transfer material is measured by a method according to the method for measuring the average thickness of the transparent substrate.
  • the shape of the photosensitive transfer material is not limited.
  • the shape of the photosensitive transfer material is preferably roll-shaped from the viewpoint of versatility and transportability. By winding the photosensitive transfer material, the shape of the photosensitive transfer material can be made into a roll.
  • the method for producing the photosensitive transfer material is not limited.
  • Examples of the method for producing the photosensitive transfer material include a step of forming a negative photosensitive resin layer N by applying a photosensitive resin composition on a temporary support, and the above-mentioned negative photosensitive resin layer N.
  • a method including a step of arranging a cover film on the surface and a method including the step of placing the cover film on the surface can be mentioned.
  • the photosensitive resin composition applied on the temporary support may be dried, if necessary.
  • the drying method is not limited, and a known drying method can be used.
  • Examples of the method of arranging the cover film on the negative type photosensitive resin layer N include a method of crimping the cover film to the negative type photosensitive resin layer N.
  • a part of the negative photosensitive resin layer N is irradiated with light from a surface of the transparent base material opposite to the surface on which the light-shielding pattern 1 is provided. Includes process (exposure process).
  • exposure process light is irradiated from the surface of the transparent substrate opposite to the surface on which the light-shielding pattern 1 is provided.
  • the "surface provided with the light-shielding pattern 1 of the transparent base material” means the surface of the transparent base material on the side having the light-shielding pattern 1. For example, in FIG.
  • the “surface provided with the light-shielding pattern 1 of the transparent base material” refers to the surface of the transparent base material 10 in contact with the light-shielding pattern 20, that is, the surface to be exposed 10a. Refers to the side facing the other side.
  • the negative-type photosensitive resin layer N is formed by the light-shielding pattern. By blocking a part of the reaching light, a part of the negative photosensitive resin layer N can be selectively exposed. The exposed portion of the negative photosensitive resin layer N has reduced solubility in a developing solution.
  • the surface of the transparent substrate is irradiated with light on the surface opposite to the surface facing the light-shielding pattern. This makes it possible to accelerate the curing of the negative photosensitive resin layer N in the vicinity of the transparent substrate. As a result, the resolution of the resin pattern can be improved in the developing process described later. Further, it is possible to form a resin pattern having a side wall having high linearity.
  • the light source used in the exposure step may be a light source that irradiates the negative photosensitive resin layer N with light having a wavelength that allows exposure (for example, 365 nm or 405 nm).
  • Specific examples of the light source include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).
  • the light irradiated in the exposure step preferably contains a wavelength included in the wavelength range of 200 nm to 1,500 nm, more preferably contains a wavelength included in the wavelength range of 250 nm to 450 nm, and has a wavelength range of 300 nm to 410 nm. It is preferable to include the wavelength contained in, and it is more preferable to include the wavelength of 365 nm.
  • the exposure amount is preferably 5 mJ / cm 2 to 200 mJ / cm 2 , and more preferably 10 mJ / cm 2 to 100 mJ / cm 2 .
  • a part of the negative photosensitive resin layer N can be selectively exposed by the light-shielding pattern, so that the surface of the transparent base material is opposite to the surface on which the light-shielding pattern 1 is provided. You may irradiate the whole area of.
  • the method for producing a structure according to the present disclosure includes a step (development step) of forming a resin pattern 2 on the transparent substrate by developing the negative photosensitive resin layer N irradiated with light.
  • the developing step the negative type photosensitive resin layer N is developed to form the resin pattern 2 in the region defined by the transparent base material and the light-shielding pattern.
  • the non-exposed portion of the negative photosensitive resin layer N is removed to correspond to the shape of the exposed portion of the negative photosensitive resin layer N.
  • a resin pattern having a shape is formed.
  • the negative photosensitive resin layer N can be developed using, for example, a developing solution.
  • the type of developer is not limited as long as the non-exposed portion of the negative photosensitive resin layer N can be removed.
  • a known developing solution for example, the developing solution described in JP-A-5-72724
  • JP-A-5-72724 a known developing solution
  • the developer is preferably an alkaline aqueous solution-based developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L.
  • the developer may contain a water-soluble organic solvent and / or a surfactant.
  • the developing solution the developing solution described in paragraph 0194 of International Publication No. 2015/093271 is also preferable.
  • the development method is not particularly limited, and may be any of paddle development, shower development, shower and spin development, and dip development.
  • shower development is a development process in which an exposed portion or a non-exposed portion is removed by spraying a developing solution onto the photosensitive resin layer after exposure by a shower.
  • the cleaning agent After the developing step, it is preferable to spray the cleaning agent with a shower and rub with a brush to remove the developing residue.
  • the temperature of the developer is not limited.
  • the liquid temperature of the developing solution is preferably 20 ° C. to 40 ° C.
  • the average thickness of the resin pattern 2 is preferably larger than the average thickness of the light-shielding pattern 1.
  • a thick light-shielding pattern 1 can be formed.
  • the ratio of the average thickness of the resin pattern 2 to the average thickness of the light-shielding pattern 1 ([average thickness of the resin pattern 2] / [average thickness of the light-shielding pattern 1]) must be 1.1 or more. It is preferably 1.5 or more, and particularly preferably 3 or more.
  • the ratio of the average thickness of the resin pattern 2 to the average thickness of the light-shielding pattern 1 may be 4, 5, or 10.
  • the average thickness of the resin pattern 2 is assumed by a method according to the method for measuring the average thickness of the transparent base material.
  • the average thickness of the resin pattern 2 is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and particularly preferably more than 2 ⁇ m. Further, the average thickness of the resin pattern is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and particularly preferably 10 ⁇ m or more. The upper limit of the thickness of the resin pattern 2 is not limited. The average thickness of the resin pattern may be determined, for example, in the range of 100 ⁇ m or less.
  • the average width of the resin pattern 2 is preferably 50 ⁇ m or less, and more preferably 5 ⁇ m or less.
  • the average width of the resin pattern 2 is preferably 0.3 ⁇ m or more, and more preferably 0.5 ⁇ m or more.
  • the average width of the resin pattern 2 is measured by a method according to the method for measuring the average width of the light-shielding pattern 1.
  • the method for producing a structure according to the present disclosure includes a step of forming a pattern 3 in a region defined by the light-shielding pattern 1 and the resin pattern 2 (pattern 3 forming step).
  • the pattern 3 is formed on the light-shielding pattern 1.
  • the pattern 3 is formed in the region defined by the light-shielding pattern 1 and the resin pattern 2.
  • Pattern 3 is preferably conductive from the viewpoint of more exerting the effects in the present disclosure. Further, from the viewpoint of pattern formability and dimensional stability of the obtained pattern 3, it is preferable that the average thickness of the pattern 3 is thicker than the average thickness of the light-shielding pattern 1.
  • the conductive pattern 3 material preferably contains Cu or an alloy of Cu.
  • the alloy of Cu is preferably an alloy of Cu and at least one selected from the group consisting of Ni, Mo, Ta, Ti, V, Cr, Fe, Mn, Co, and W.
  • the pattern 3 formed by using the above-mentioned material contains the above-mentioned metal element.
  • the pattern 3 obtained in the pattern 3 forming step may be a conductive pattern made of Cu.
  • the light-shielding pattern 1 and the pattern 3 contain the same kind of material.
  • the pattern 3 is preferably a pattern formed by a plating method.
  • known plating can be used. Examples of plating include electroplating and electroless plating.
  • the plating is preferably electroplating, more preferably electrocopper plating.
  • a light-shielding pattern 1 that can function as a seed layer is used as a cathode, and a metal is stacked on the light-shielding pattern to form a conductive pattern 3 on the light-shielding pattern 1. can do.
  • Examples of the components of the plating solution used in electroplating include water-soluble copper salts.
  • a water-soluble copper salt usually used as a component of a plating solution can be used.
  • the water-soluble copper salt is preferably at least one selected from the group consisting of, for example, an inorganic copper salt, an alkane sulfonic acid copper salt, an alkanol sulfonic acid copper salt, and an organic acid copper salt.
  • Examples of the inorganic copper salt include copper sulfate, copper oxide, copper chloride, and copper carbonate.
  • Examples of the alkane sulfonic acid copper salt include copper methane sulfonate and copper propane sulfonate.
  • Examples of the alkanol sulfonate copper salt include copper isethionic acid and copper propanol sulfonate.
  • the organic acid copper salt include copper acetate, copper citrate, and copper tartrate.
  • the plating solution may contain sulfuric acid. Since the plating solution contains sulfuric acid, the pH of the plating solution and the sulfate ion concentration can be adjusted.
  • the electroplating method and conditions are not limited. For example, by supplying the transparent base material after the developing step to the plating tank to which the plating solution is added, the pattern 3 having conductivity can be formed on the light-shielding pattern 1. In electroplating, for example, by controlling the current density and the transport speed of the transparent substrate, the pattern 3 having conductivity can be formed.
  • the temperature of the plating solution used for electroplating is generally 70 ° C. or lower, preferably 10 ° C. to 40 ° C.
  • the current density in electroplating is generally 0.1 A / dm 2 to 100 A / dm 2 , preferably 0.5 A / dm 2 to 20 A / dm 2.
  • a plurality of metals may be continuously plated.
  • a metal such as copper
  • deterioration of visibility or aesthetics may be a problem due to reflection.
  • the method for reducing the reflectance of the surface of the pattern 3 include oxidation treatment, sulfurization treatment, nitriding treatment, chlorination treatment, formation of a blackened layer film, and black plating.
  • a layer containing a black material can be formed on the surface of the pattern 3.
  • the method for reducing the reflectance of the surface of the pattern 3 is preferably an oxidation treatment or a sulfurization treatment.
  • the oxidation treatment can obtain a more excellent antiglare effect, and is also preferable from the viewpoint of simplicity of waste liquid treatment and environmental safety.
  • the post-baking process may be performed.
  • the insulation reliability, the curing property, or the plating adhesion can be improved by completely heat-curing the unreacted thermosetting component.
  • the heating temperature is preferably 80 ° C. to 240 ° C.
  • the heating time is preferably 5 minutes to 120 minutes.
  • the surface of the pattern 3 may be protected by a resin layer.
  • the surface of the pattern 3 can be protected by forming a resin layer on the conductive pattern.
  • the components of the resin layer include an acrylic resin, a polyester resin, a polyvinyl acetal resin layer, a polyimide resin, and an epoxy resin.
  • the method for forming the resin layer include coating and thermocompression bonding.
  • the structure of pattern 3 may be a single-layer structure or a multi-layer structure.
  • the components of each layer of the pattern 3 having a multi-layer structure may be the same or different.
  • the thickness of pattern 3 is not limited.
  • the thickness of the pattern 3 may be determined, for example, according to the application.
  • the average thickness of the pattern 3 may be determined according to, for example, the magnitude of the current supplied to the wiring and the wiring width.
  • the average thickness of the pattern 3 is preferably 0.5 ⁇ m or more, more preferably 1 ⁇ m or more, and particularly preferably 2 ⁇ m or more.
  • the average thickness of the pattern 3 is preferably 3 ⁇ m or more, more preferably 5 ⁇ m or more, and particularly preferably 10 ⁇ m or more.
  • the average thickness of the pattern 3 is measured by a method according to the method for measuring the average thickness of the transparent substrate.
  • the width of pattern 3 is preferably narrow.
  • the average width of the pattern 3 is preferably 50 ⁇ m or less, more preferably 10 ⁇ m or less, further preferably 5 ⁇ m or less, and particularly preferably 2 ⁇ m or less.
  • the average width of the pattern 3 is 5 ⁇ m or less, the visibility of the pattern 3 in a device sensitive to visibility such as a touch panel can be reduced.
  • the average width of the pattern 3 is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, and particularly preferably 0.8 ⁇ m or more.
  • the average width of the pattern 3 is measured by a method according to the method for measuring the average width of the light-shielding pattern 1.
  • the surface resistance value of the conductive pattern 3 is preferably less than 0.2 ⁇ / ⁇ , and more preferably less than 0.15 ⁇ / ⁇ .
  • the surface resistance value of the conductive pattern 3 is measured by the 4-probe method. When the pattern size is fine and difficult to measure, the surface resistance value of the conductive layer having the same composition and thickness may be measured.
  • the interface between the pattern 3 and the light-shielding pattern 1 may not be clearly observed.
  • the interface between the light-shielding pattern 1 and the pattern 3 may not be clearly observed.
  • the fact that the interface between the pattern 3 and the light-shielding pattern 1 is not clearly observed does not preclude the object of the present disclosure.
  • the method for producing a structure according to the present disclosure further includes a step of performing at least one of post-exposure and post-heating on the resin pattern 2 from the viewpoint of improving the strength and durability of the resin pattern 2 which is a permanent film. Is preferable.
  • the method for producing a structure according to the present disclosure preferably includes a step of post-exposure the resin pattern 2 (also referred to as a “post-exposure step”) after the development step, and after the pattern 3 forming step, It is more preferable to include a step of post-exposing the resin pattern 2.
  • the method for producing a structure according to the present disclosure may further include a step of heating (post-heating) the resin pattern 2 (also referred to as a “post-heating step”), if necessary. Since the resin pattern 2 is an exposed portion of the negative photosensitive resin layer N, by performing the post-exposure or the post-heating, the remaining polymerization initiator, the polymerizable compound, and the like further cause a polymerization reaction and the like. The strength of the resin pattern 2 and the durability such as heat resistance, light resistance, and moisture resistance are improved.
  • the light source used for exposure in the post-exposure step is not particularly limited, and a known exposure light source can be used. From the viewpoint of removability, it is preferable to use a light source containing light having the same wavelength as that in the resin pattern forming step.
  • the exposure amount in the post-exposure step is preferably 5mJ / cm 2 ⁇ 5,000mJ / cm 2, more preferably 10mJ / cm 2 ⁇ 3,000mJ / cm 2, and particularly preferably 100mJ / cm 2 ⁇ 1,500mJ / cm 2.
  • the exposure amount in the post-exposure step is preferably equal to or more than the exposure amount in the resin pattern forming step, and more preferably larger than the exposure amount in the resin pattern forming step.
  • the method for producing a structure according to the present disclosure may include a post-heating step a plurality of times.
  • the heating temperature and heating time in the post-heating step are not particularly limited and can be appropriately selected.
  • the method of post-heating is not particularly limited, and a known method can be used.
  • the method may be performed by means provided in the exposure apparatus and the developing apparatus, or may be performed by using a hot plate or the like.
  • the method for producing a structure according to the present disclosure may include any steps (other steps) other than those described above.
  • the other steps are not particularly limited, and examples thereof include known steps.
  • the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be preferably used in the present disclosure.
  • the method for producing a structure according to the present disclosure may include a step of polishing the obtained pattern, a step of cleaning the obtained pattern, and the like.
  • the method for manufacturing a structure according to the present disclosure may include a step of providing a member according to each application, which will be described later.
  • the structure obtained by the method for producing a structure according to the present disclosure can be applied to various uses.
  • Applications of the structure obtained by the method for manufacturing the structure according to the present disclosure include, for example, a touch sensor, an electromagnetic wave shield, an antenna, a wiring substrate, and a conductive heating element.
  • the structure obtained by the method for producing a structure according to the present disclosure can function as, for example, an electric conductor.
  • the structure obtained by the method for producing a structure according to the present disclosure can exhibit various functions depending on the characteristics of the formed patterns (resin pattern 2, pattern 3, etc.). ..
  • the touch sensor according to the present disclosure has a structure obtained by the method for manufacturing the structure according to the present disclosure.
  • the conductive pattern of the structure (for example, the light-shielding pattern 1 and the conductive pattern 3, etc., the same applies hereinafter) can be used as, for example, a transparent electrode or a frame wiring.
  • the components of the touch sensor according to the present disclosure are not limited except that the structure obtained by the method for manufacturing the structure according to the present disclosure is included.
  • a component included in a known touch sensor can be used.
  • the touch sensor is described in, for example, Japanese Patent No. 6486341 and Japanese Patent Application Laid-Open No. 2016-155978.
  • the above publications are incorporated herein by reference.
  • the method for manufacturing a touch sensor according to the present disclosure is not limited as long as it is a method for manufacturing a touch sensor having a structure obtained by the method for manufacturing a structure according to the present disclosure.
  • the electromagnetic wave shield according to the present disclosure has a structure obtained by the method for manufacturing the structure according to the present disclosure.
  • the conductive pattern of the structure can be used as, for example, an electromagnetic wave shield body.
  • the components of the electromagnetic wave shield according to the present disclosure are not limited except that the structure obtained by the method for manufacturing the structure according to the present disclosure is included.
  • a component included in a known electromagnetic wave shield can be used.
  • the electromagnetic wave shield is described in, for example, Japanese Patent No. 6486382 and Japanese Patent Application Laid-Open No. 2012-163951. The above publications are incorporated herein by reference.
  • the method for manufacturing an electromagnetic wave shield according to the present disclosure is not limited as long as it is a method for manufacturing an electromagnetic wave shield having a structure obtained by the method for manufacturing a structure according to the present disclosure.
  • the antenna according to the present disclosure is an antenna having a structure obtained by the method for manufacturing the structure according to the present disclosure.
  • the conductive pattern of the structure can be used as, for example, a transmission / reception unit or a transmission line unit.
  • the components of the antenna according to the present disclosure are not limited except that the structure obtained by the method for manufacturing the structure according to the present disclosure is included.
  • a component included in a known antenna can be used.
  • the antenna is described in, for example, Japanese Patent Application Laid-Open No. 2016-219999. The above publications are incorporated herein by reference.
  • the method for manufacturing an antenna according to the present disclosure is not limited as long as it is a method for manufacturing an antenna having a structure obtained by the method for manufacturing a structure according to the present disclosure.
  • the wiring board according to the present disclosure has a structure obtained by the method for manufacturing the structure according to the present disclosure.
  • the conductive pattern of the structure can be used, for example, as wiring for a printed wiring board.
  • the components of the wiring board according to the present disclosure are not limited except that the components obtained by the method for manufacturing the structure according to the present disclosure are included.
  • a component included in a known wiring board can be used.
  • the wiring board is described in, for example, Japanese Patent No. 5774686 and Japanese Patent Application Laid-Open No. 2017-204538. The above publications are incorporated herein by reference.
  • the method for manufacturing a wiring board according to the present disclosure is not limited as long as it is a method for manufacturing a wiring board having a structure obtained by the method for manufacturing a structure according to the present disclosure.
  • the conductive heating element according to the present disclosure has a structure obtained by the method for producing the structure according to the present disclosure.
  • the conductive pattern of the structure can be used as a heating element, for example.
  • the components of the conductive heating element according to the present disclosure are not limited except that the structure obtained by the method for producing the structure according to the present disclosure is included.
  • a component included in a known conductive heating element can be used.
  • the conductive heating element is described in, for example, Japanese Patent Application Laid-Open No. 6486382. The above publications are incorporated herein by reference.
  • the method for manufacturing a conductive heating element according to the present disclosure is not limited as long as it is a method for manufacturing a conductive heating element having a structure obtained by the method for manufacturing a structure according to the present disclosure.
  • the structure according to the present disclosure is arranged adjacent to the transparent base material, the light-shielding pattern 1 arranged on the transparent base material, and the light-shielding pattern 1 on the transparent base material, and It has a resin pattern 2 in contact with the transparent substrate, a pattern 3 in a region defined by the light-shielding pattern 1 and the resin pattern 2, and the average thickness of the light-shielding pattern 1 is 2 ⁇ m or less.
  • the average thickness of the resin pattern 2 exceeds 2 ⁇ m, the average thickness of the pattern 3 is thicker than the average thickness of the light-shielding pattern 1, and the resin pattern 2 is a permanent film.
  • a structure having a conductive pattern in which the occurrence of morphological abnormalities is reduced is provided.
  • the structure according to the present disclosure is preferably a structure manufactured by the method for manufacturing the structure according to the present disclosure.
  • preferred embodiments of the transparent base material, the light-shielding pattern 1, the resin pattern 2, and the pattern 3 in the structure according to the present disclosure are the transparent base material and the light-shielding material in the above-described method for producing the structure according to the present disclosure. This is the same as the preferred embodiment of the sex pattern 1, the resin pattern 2, and the pattern 3.
  • FIG. 2 is a schematic cross-sectional view showing an example of the structure according to the present disclosure.
  • the structure 200 shown in FIG. 2 has a transparent base material 11, a pattern 21 (light-shielding pattern 1), a resin pattern 41 (resin pattern 2), and a pattern 51 (pattern 3).
  • the light-shielding pattern 21 is arranged on the transparent base material 11.
  • the light-shielding pattern 21 is in contact with the transparent base material 11. However, the light-shielding pattern 21 may come into contact with the transparent base material 11 via another layer (not shown).
  • the resin pattern 41 is arranged on the transparent base material 11 next to the light-shielding pattern 21 and is in contact with the transparent base material 11. Further, the pattern 51 is arranged on the light-shielding pattern 21 and between the resin patterns 41.
  • Table 1 shows the content of each structural unit in the polymer A-1.
  • the acid value of polymer A-1 is 15.6 mgKOH / g.
  • the above abbreviations represent the following compounds, respectively.
  • AA Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • CH Cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • EA Ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • MMA Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • PMEA Propylene glycol monomethyl ether acetate (manufactured by Showa Denko KK)
  • V-601 2,2'-azobis (2-methylpropionate) dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • Polymer A-3 is contained in the same manner as in polymer A-1, except that the monomers (styrene, methacrylic acid, and methyl methacrylate) used in the synthesis of polymer A-1 are changed to the following monomers.
  • a solution solid content concentration: 40.0% by mass
  • the weight average molecular weight of the polymer A-3 was 40,000.
  • Benzyl methacrylate 81.0 g
  • Methacrylic acid 19.0 g
  • negative type photosensitive resin compositions NR1 to NR6 solid content concentration: 25% by mass were prepared by adding methyl ethyl ketone.
  • BPE-500 ethoxylated bisphenol A dimethacrylate (addition of 10 mol of ethylene oxide), manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • BPE-200 ethoxylated bisphenol A dimethacrylate (addition of 4 mol of ethylene oxide), Shin-Nakamura Chemical Industry Co., Ltd.
  • M-270 Polypropylene glycol diacrylate, A-TMPT: Trimethylol propantriacrylate, SR-454: Trimethylol propantriacrylate ethoxylated (ethylene oxide 3) (Molar addition), SR-502 manufactured by Alchema: Trimethylol propantriacrylate ethoxylated (addition of 9 mol of ethylene oxide), A-9300-CL1: ⁇ -caprolactone-modified tris- (2-acryloxyethyl) isocyanurate manufactured by Alchema , Shin-Nakamura Chemical Industry Co., Ltd.
  • B-CIM Photoradical generator (photopolymerization initiator), Hampford, 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer SB-PI 701: Sensitizer, 4,4'-bis (diethylamino) benzophenone, manufactured by Sanyo Trading Co., Ltd.
  • CBT-1 rust preventive, carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd.
  • TDP-G polymerization inhibitor, phenothiazine, Irganox 245 manufactured by Kawaguchi Chemical Industry Co., Ltd .: polymerization inhibitor, hindered phenol compound, F-552 manufactured by BASF, fluorosurfactant, Megafuck F552, manufactured by DIC Co., Ltd.
  • ⁇ Preparation of positive photosensitive resin composition PR1> By mixing PGMEA with polymer A-1, photoacid generator B-1, surfactant C-1, and basic compound D-1, weighed according to the composition shown in Table 2 below, the solid content concentration A 10% by mass mixture was obtained. The above mixture was filtered using a filter made of polytetrafluoroethylene having a pore size of 0.2 ⁇ m to obtain a positive photosensitive resin composition PR1.
  • the photoacid generator B-1 is a compound having the following structure (the compound described in paragraph 0227 of JP2013-47765A, synthesized according to the method described in paragraph 0227).
  • Surfactant C-1 is a compound having the following structure.
  • Basic compound D-1 is a compound having the following structure.
  • Negative Photosensitive Resin Compositions N1 to N8 After mixing the components selected according to the description in Table 3 or Table 4, the negative photosensitive resin compositions N1 to are added by adding a 1: 1 (mass ratio) mixed solvent of 1-methoxy-2-propyl acetate and methyl ethyl ketone. N8 (solid content concentration: 29% by mass) was prepared.
  • Thermal crosslinkable compound- E-1 Duranate WT32-B75P (blocked isocyanate compound, manufactured by Asahi Kasei Chemicals Co., Ltd.): 12.50 parts
  • AD-1 Hydrogen donating compound (N-phenylglycine, manufactured by Junsei Chemical Co., Ltd.)
  • AD-3 Fluorosurfactant (Mega Fvck F551A, manufactured by DIC Corporation)
  • AD-4 Sensitizer (4,5'-bis (diethylamino) benzophenone, SB-PI 701, manufactured by Sanyo Trading Co., Ltd.)
  • AD-6 Polymerization inhibitor (phenothiazine, TDP-G manufactured by Kawaguchi Chemical Industry Co., Ltd.)
  • AD-7 Rust inhibitor (carboxybenzotriazole, CBT-1 manufactured by Johoku
  • Example 1 ⁇ Preparation of photosensitive transfer material (dry film) 1>
  • a PET film Limirror 16KS40 manufactured by Toray Industries, Inc., thickness: 16 ⁇ m: arithmetic average roughness Ra: 0.02 ⁇ m
  • a negative photosensitive resin composition NR1 was applied to the surface of the temporary support using a slit-shaped nozzle so that the coating width was 1.0 m and the thickness after drying was the value shown in Table 5. It was applied.
  • a resist layer was formed by drying the coating film of the formed negative photosensitive resin composition NR1 at 90 ° C. for 100 seconds.
  • a photosensitive transfer material 1 was prepared by pressure-bonding a polyethylene film (Tamapoli Co., Ltd., GF-818, thickness: 19 ⁇ m) as a cover film on the surface of the formed resist layer. By winding the obtained photosensitive transfer material 1, a roll-shaped photosensitive transfer material 1 was produced.
  • a PET film with a copper layer was produced by forming a copper layer having a thickness of 0.05 ⁇ m on a polyethylene terephthalate (PET) film having a thickness of 100 ⁇ m by sputtering. After peeling the cover film from the photosensitive transfer material 1, the photosensitive transfer material 1 was attached to the PET film with a copper layer.
  • the bonding step was performed under the conditions that the roll temperature was 100 ° C., the linear pressure was 1.0 MPa, and the linear velocity was 1.0 m / min.
  • the resist layer was exposed by irradiating light with a high-pressure mercury lamp exposure machine (MAP-1200L manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm) via a photomask.
  • a high-pressure mercury lamp exposure machine MA-1200L manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm
  • the copper layer not covered with the resin pattern was etched with an etching solution (Cu-02 manufactured by Kanto Chemical Co., Inc.).
  • the residual resin pattern was removed using a stripping solution (10 mass% sodium hydroxide aqueous solution).
  • a PET film (Lumirror 16KS40 manufactured by Toray Industries, Inc., thickness: 16 ⁇ m: arithmetic average roughness Ra: 0.02 ⁇ m) was prepared.
  • a negative photosensitive resin composition N1 was applied to the surface of the temporary support using a slit-shaped nozzle so that the coating width was 1.0 m and the thickness after drying was the value shown in Table 5. It was applied.
  • the coating film of the formed negative photosensitive resin composition N1 was dried at 90 ° C. for 100 seconds.
  • a polyethylene film (Tamapoli Co., Ltd., GF-818, thickness: 19 ⁇ m) was pressure-bonded as a cover film to prepare a photosensitive transfer material 2.
  • a photosensitive transfer material 2 By winding up the obtained photosensitive transfer material 2, a roll-shaped photosensitive transfer material 2 was produced.
  • Light is emitted to the surface of the PET film opposite to the surface facing the copper pattern (light-shielding pattern 1) using a high-pressure mercury lamp exposure machine (MAP-1200L manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm). Irradiated. The exposure amount was 70 mJ / cm 2 .
  • the negative type photosensitive resin layer N was shower-developed for 30 seconds with an aqueous sodium carbonate solution having a liquid temperature of 25 ° C. to form a resin pattern 2.
  • the space portion (that is, the groove) of the copper pattern (light-shielding pattern 1) was filled with the resin pattern 2.
  • Table 2 shows the average thickness of the resin pattern 2.
  • Copper was deposited by electrolytic copper plating on a copper pattern (light-shielding pattern 1) not covered by the resin pattern 2 to form a conductive pattern 3.
  • the current density in electrolytic copper plating was 1.8 ASD.
  • the processing time in electrolytic copper plating was 6 minutes.
  • the PET film after electrolytic copper plating was heated at 130 ° C. for 30 minutes.
  • Table 5 shows the average thickness of the copper pattern (conducting pattern 3) precipitated by electrolytic copper plating.
  • Example 2 to 13 Type and thickness of base material, thickness of light-shielding pattern 1 (average thickness), type of photosensitive resin composition forming light-shielding pattern 1, dry coating thickness of photosensitive resin composition (thickness of resist layer), The shape of the light-shielding pattern 1, the exposure method at the time of forming the photosensitive pattern 1 (including the presence or absence of peeling of the temporary support), the method of forming the negative photosensitive resin layer N, the negative photosensitive composition used, and the like.
  • a structure having a copper pattern was prepared by the same procedure as in Example 1 except that the type of the layer, the thickness (average thickness) of the pattern 3, and the presence or absence of the curing treatment were appropriately changed according to the description in Table 5. Made. The average thickness of copper deposited by electrolytic copper plating can be increased by extending the treatment time.
  • Example 2 a polyimide (PI) film having a thickness of 100 ⁇ m was used as the base material to be used, and after pattern 3 was formed, a high-pressure mercury lamp exposure machine (MAP-1200L manufactured by Dainippon Kaken Co., Ltd.) was used. , Main wavelength: 365 nm) was used to irradiate light with an exposure amount of 1,000 mJ / cm 2 to perform post-exposure.
  • PI polyimide
  • Example 3 as the base material to be used, a base material (COP) in which an indium tin oxide (ITO) film having a thickness of 0.1 ⁇ m is formed by a sputtering method on a polycycloolefin (COP) film having a thickness of 100 ⁇ m.
  • a base material with a copper layer was prepared by forming a copper layer having a thickness of 0.03 ⁇ m on / ITO) by a sputtering method.
  • N10 instead of the negative photosensitive resin composition N1, N10 in which a high refractive index layer was laminated was formed on the following negative photosensitive resin composition N1.
  • a PET film (Lumirror 16KS40 manufactured by Toray Industries, Inc., thickness: 16 ⁇ m: arithmetic average roughness Ra: 0.02 ⁇ m) was prepared.
  • the negative photosensitive resin composition N1 was applied to the surface of the temporary support using a slit-shaped nozzle so that the coating width was 1.0 m and the thickness after drying was 3 ⁇ m.
  • the negative-type photosensitive resin layer N was formed by drying the coating film of the formed negative-type photosensitive resin composition N1 at 90 ° C. for 100 seconds.
  • a coating liquid (composition N9) for an overcoat layer composed of the following formulation 201 was applied using a slit-shaped nozzle to a thickness of 0.2 ⁇ m after drying.
  • the overcoat layer (OC) is arranged so that it has a thickness, is applied, dried with a hot air convection dryer having a temperature gradient of 40 ° C. to 95 ° C. to remove the solvent, and is arranged in direct contact with the photosensitive layer. Layer) was formed.
  • the refractive index of the overcoat layer was 1.68 at a wavelength of 550 nm at 25 ° C.
  • Formulation 201 is prepared using a resin having an acid group and an aqueous ammonia solution.
  • the resin having an acid group is neutralized with the aqueous ammonia solution, and an aqueous resin composition containing an ammonium salt of the resin having an acid group.
  • Formulation 201 water-based resin composition
  • aqueous ammonia 4.92 parts, polyfunctional ethylenically unsaturated compound having a carboxylic acid group (Aronix TO-2349, manufactured by Toa Synthetic Co., Ltd.): 0.04 parts, ZrO 2 particles (Nano Teen OZ- S30M, solid content 30.5%, methanol 69.5%, refractive acid 2.2, average particle size: about 12 nm, manufactured by Nissan Chemical Industry Co., Ltd .: 4.34 parts, rust preventive (benzotriazole derivative) , BT-LX, manufactured by Johoku Chemical Industry Co., Ltd.): 0.03 parts ⁇ Surfactant (fluorine-based surfactant, Megafuck F444, manufactured by DIC Co., Ltd.): 0.01 parts ⁇ Distilled water: 24. 83 parts, methanol: 65.83 parts
  • a photosensitive transfer material 2 was prepared by pressure-bonding a polyethylene film (manufactured by Tamapoli Co., Ltd., GF-818, thickness: 19 ⁇ m) as a cover film on the surface of the formed overcoat layer. By winding up the obtained photosensitive transfer material 2, a roll-shaped photosensitive transfer material 2 was produced.
  • a polyethylene film manufactured by Tamapoli Co., Ltd., GF-818, thickness: 19 ⁇ m
  • Example 4 exposure was performed by a direct drawing exposure (DI exposure) method using a direct drawing exposure apparatus (manufactured by Via Mechanics, Ltd., DE-1DH, main wavelength 405 nm). Further, in Example 7, a base material laminated with a photosensitive transfer material is fixed on a 4-inch silicon wafer with a tape, and then reduced projection exposure is performed using an i-wire stepper (NSR-2009i9C) manufactured by Nikon Corporation. After forming the pattern 3, heating was performed at 145 ° C. for 20 minutes. Further, in Examples 9 and 10, the positive photosensitive resin composition PR1 shown in Table 5 was applied without using the photosensitive transfer material 1, dried at 90 ° C. for 100 seconds, and shown in Table 5.
  • DI exposure direct drawing exposure
  • a resist layer having the same thickness was formed. Further, in Examples 8 and 11, the negative photosensitive resin composition shown in Table 5 was applied without using the photosensitive transfer material 2, dried at 90 ° C. for 100 seconds, and shown in Table 5. A negative photosensitive resin layer N having a thickness was formed.
  • the light-shielding pattern 1 was formed as follows.
  • a PET film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd., thickness: 75 ⁇ m) was prepared.
  • a printer was prepared in which the ink in the ink cartridge of the monochrome inkjet printer PX-K100 (manufactured by Seiko Epson Corporation) was transferred to silver nano ink (DryCure Ag-J manufactured by C-INK Co., Ltd.).
  • a wiring pattern was formed by performing a printing operation on this printer via a printer driver, and then the printer was heated at 60 ° C. for 2 minutes.
  • the copper pattern 3 was formed as shown below.
  • An electroless copper plating solution (ARG copper manufactured by Okuno Pharmaceutical Industry Co., Ltd.) was prepared in a Cu plating bath according to the procedure described in the instruction manual, and then placed in a constant temperature bath at 45 ° C. for temperature control.
  • a copper pattern was formed by electroless plating by impregnating the plating bath with a substrate.
  • the light-shielding pattern 1 was formed as follows. After peeling the cover film from the photosensitive transfer material 1 on a polyimide (PI) film having a thickness of 100 ⁇ m, the photosensitive transfer material 1 was attached to a PET film with a copper layer. The above bonding was performed under the conditions that the roll temperature was 100 ° C., the linear pressure was 1.0 MPa, and the linear velocity was 1.0 m / min. Next, the resist layer was exposed by irradiating light with a maskless drawing apparatus (DWL66 + manufactured by Heidelberg, main wavelength: 405 nm). After peeling off the temporary support, the resist layer was shower-developed for 30 seconds with an aqueous sodium carbonate solution having a liquid temperature of 25 ° C.
  • PI polyimide
  • the abnormal portion refers to a portion in which morphological abnormalities such as cracking, peeling, and chipping are observed in the pattern 3.
  • the evaluation results are shown in Table 5.
  • N9 in the negative type photosensitive composition column used in Example 3 of Table 5 indicates an overcoat coating liquid (composition N9). From the results shown in Table 5, it can be seen that the method for producing the structure of Examples 1 to 13 can form a pattern in which the occurrence of morphological abnormalities is reduced as compared with the method for producing the structure of Comparative Example 1. ..

Landscapes

  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Physics & Mathematics (AREA)
  • General Engineering & Computer Science (AREA)
  • Theoretical Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Human Computer Interaction (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)

Abstract

Provided are a method for manufacturing a structure, and a structure, the method comprising: a step for preparing a laminate that has a transparent base material, a light-shielding pattern 1 disposed on the transparent base material, and a negative photosensitive resin layer N that is disposed on the transparent substrate and the light-shielding pattern and is in contact with the transparent base material; a step for irradiating a portion of the negative photosensitive resin layer N with light from a surface of the transparent substrate on a side opposite from a surface on which the light-shielding pattern 1 is provided; a step for forming a resin pattern 2 on the transparent base material by developing the negative photosensitive resin layer N irradiated with light; and a step for forming a pattern 3 in a region defined by the light-shielding pattern 1 and the resin pattern 2, wherein the obtained structure has the resin pattern 2 as a permanent film.

Description

構造体の製造方法、及び、構造体Structure manufacturing method and structure
　本開示は、構造体の製造方法、及び、構造体に関する。 This disclosure relates to a method for manufacturing a structure and the structure.
　金属細線のような導電性パターンは、種々の用途に使用されている。導電性パターンの用途としては、例えば、タッチパネルのタッチセンサー、アンテナ、指紋認証部、フォルダブルデバイス、及び透明ＦＰＣ（Ｆｌｅｘｉｂｌｅ　Ｐｒｉｎｔｅｄ　Ｃｉｒｃｕｉｔｓ）が挙げられる。例えば、半導体パッケージ、プリント配線基板、及びインターポーザーの再配線層の製造においては、基材上に微細な導電性パターンが形成されている。基材として、例えば、フィルム、シート、金属基板、セラミック基板、又はガラスが用いられている。 Conductive patterns such as thin metal wires are used for various purposes. Applications of the conductive pattern include, for example, a touch sensor of a touch panel, an antenna, a fingerprint authentication unit, a foldable device, and a transparent FPC (Flexible Printed Circuits). For example, in the manufacture of a semiconductor package, a printed wiring board, and a rewiring layer of an interposer, a fine conductive pattern is formed on the base material. As the base material, for example, a film, a sheet, a metal substrate, a ceramic substrate, or glass is used.
　一般的な導電性パターンの形成方法として、例えば、サブトラクティブ法、及びセミアディティブ法が知られている（例えば、特許文献１、及び特許文献２）。サブトラクティブ法では、例えば、基材上の導電性層をレジストパターンで保護した後、レジストパターンで保護されていない導電性層をエッチングにより除去することで、導電性パターンを形成することができる。一方、セミアディティブ法では、例えば、基材上にシード層といわれる無電解銅めっき層を設けた後、無電解銅めっき層上にレジストパターンを更に設ける。次に、レジストパターンが設けられていない無電解銅めっき層上に、めっきによって導電性パターンを形成した後、不要なレジストパターン、及び無電解銅めっき層（シード層）を除去する。 As a general method for forming a conductive pattern, for example, a subtractive method and a semi-additive method are known (for example, Patent Document 1 and Patent Document 2). In the subtractive method, for example, a conductive pattern can be formed by protecting the conductive layer on the base material with a resist pattern and then removing the conductive layer not protected by the resist pattern by etching. On the other hand, in the semi-additive method, for example, an electroless copper plating layer called a seed layer is provided on the base material, and then a resist pattern is further provided on the electroless copper plating layer. Next, after forming a conductive pattern by plating on the electroless copper plating layer on which the resist pattern is not provided, the unnecessary resist pattern and the electroless copper plating layer (seed layer) are removed.
　　特許文献１：特開２０１５－２２５６５０号公報
　　特許文献２：特開２０１５－０６５３７６号公報 Patent Document 1: Japanese Patent Application Laid-Open No. 2015-225650 Patent Document 2: Japanese Patent Application Laid-Open No. 2015-065376
　例えば導電性パターンの電気抵抗を小さくするために、厚みのある導電性パターンを形成することがある。しかしながら、サブトラクティブ法では、導電性層が配置された基材の面内方向にも等方的にエッチングが進行する現象（例えば、「サイドエッチング」と称される。）によってレジストパターンで保護された導電性層も薬液に浸食されることがある。サイドエッチングの発生は、エッチングを経て形成される導電性パターンの形態（例えば、形状、及び寸法）に影響を及ぼすため、例えば、矩形状の導電性パターンを形成することは困難になる場合がある。セミアディティブ法では、シード層とレジストパターンとの密着性に起因して導電性パターンの形成が不安定化することが課題となる。また、不要なシード層を除去する際に導電性パターンの一部が除去されることがあるため、セミアディティブ法においてもサブトラクティブ法と同様の課題がある。 For example, in order to reduce the electrical resistance of the conductive pattern, a thick conductive pattern may be formed. However, in the subtractive method, the resist pattern is protected by a phenomenon in which etching proceeds isotropically in the in-plane direction of the base material on which the conductive layer is arranged (for example, referred to as "side etching"). The conductive layer may also be eroded by the chemical solution. Since the occurrence of side etching affects the morphology (eg, shape and dimensions) of the conductive pattern formed through etching, it may be difficult to form, for example, a rectangular conductive pattern. .. In the semi-additive method, it is a problem that the formation of the conductive pattern becomes unstable due to the adhesion between the seed layer and the resist pattern. Further, since a part of the conductive pattern may be removed when the unnecessary seed layer is removed, the semi-additive method has the same problems as the subtractive method.
　本開示は、上記の事情に鑑みてなされたものである。
　本開示の一実施形態が解決しようとする課題は、形態異常の発生（割れ、剥がれ、欠け若しくはサイドエッチングに起因したテーパー形状の発生、又は、エッチングのバラツキに起因した寸法の変動。以下同じ。）が低減されたパターンを有する構造体の製造方法を提供することである。
　また、本開示の他の実施形態が解決しようとする課題は、形態異常の発生が低減されたパターンを有する構造体を提供することである。 This disclosure has been made in view of the above circumstances.
The problem to be solved by one embodiment of the present disclosure is the occurrence of morphological abnormalities (generation of tapered shape due to cracking, peeling, chipping or side etching, or dimensional fluctuation due to etching variation. The same shall apply hereinafter. ) Is to provide a method of manufacturing a structure having a reduced pattern.
Another problem to be solved by other embodiments of the present disclosure is to provide a structure having a pattern in which the occurrence of morphological abnormalities is reduced.
　上記課題を解決するための手段には、以下の態様が含まれる。
＜１＞　透明基材と、上記透明基材の上に配置された遮光性パターン１と、上記透明基材及び上記遮光性パターン１の上に配置され、かつ、上記透明基材に接するネガ型感光性樹脂層Ｎと、を有する積層体を準備する工程、上記透明基材の上記遮光性パターン１が設けられている面とは反対側の面から上記ネガ型感光性樹脂層Ｎの一部に光を照射する工程、光を照射された上記ネガ型感光性樹脂層Ｎを現像することで、上記透明基材上に樹脂パターン２を形成する工程、並びに、上記遮光性パターン１と上記樹脂パターン２とによって画定される領域にパターン３を形成する工程を含み、得られる構造体が、上記樹脂パターン２を永久膜として有する構造体の製造方法。
＜２＞　上記遮光性パターン１が、金属を含む＜１＞に記載の構造体の製造方法。
＜３＞　上記パターン３が、導電性を有する＜１＞又は＜２＞に記載の構造体の製造方法。
＜４＞　上記パターン３が、めっき法によって形成されてなるパターンである＜１＞～＜３＞のいずれか１つに記載の構造体の製造方法。
＜５＞　上記遮光性パターン１及び上記パターン３が、同種の材料を含む＜１＞～＜４＞のいずれか１つに記載の構造体の製造方法。
＜６＞　上記ネガ型感光性樹脂層Ｎが、アルカリ可溶性高分子、エチレン性不飽和化合物、及び、光重合開始剤を含む＜１＞～＜５＞のいずれか１つに記載の構造体の製造方法。
＜７＞　上記エチレン性不飽和化合物が、３官能以上のエチレン性不飽和化合物を含む＜６＞に記載の構造体の製造方法。
＜８＞　上記エチレン性不飽和化合物が、ジシクロペンタニル構造又はジシクロペンテニル構造を有するジ（メタ）アクリレート化合物を含む＜６＞又は＜７＞に記載の構造体の製造方法。
＜９＞　上記ネガ型感光性樹脂層Ｎが、多官能エポキシ樹脂、ヒドロキシ基含有化合物、及び、光カチオン重合開始剤を含む＜１＞～＜５＞のいずれか１つに記載の構造体の製造方法。
＜１０＞　上記ネガ型感光性樹脂層Ｎが、金属酸化抑制剤を含む＜１＞～＜９＞のいずれか１つに記載の構造体の製造方法。
＜１１＞　透明基材の一方の面に遮光性層を形成する工程、遮光性層上にフォトレジスト層を形成する工程、上記フォトレジスト層を露光及び現像してレジストパターンを形成する工程、並びに、上記遮光性層をエッチングし上記遮光性パターン１を形成する工程を更に含む＜１＞～＜１０＞のいずれか１つに記載の構造体の製造方法。
＜１２＞　上記遮光性パターン１の平均厚さよりも上記パターン３の平均厚さのほうが厚い＜１＞～＜１１＞のいずれか１つに記載の構造体の製造方法。
＜１３＞　上記透明基材が、透明フィルム基材である＜１＞～＜１２＞のいずれか１つに記載の構造体の製造方法。
＜１４＞　上記樹脂パターン２に対し後露光及び後加熱の少なくともいずれかを行う工程を更に含む＜１＞～＜１３＞のいずれか１つに記載の構造体の製造方法。
＜１５＞　上記ネガ型感光性樹脂層Ｎが、感光性転写材料により形成されてなる層である＜１＞～＜１４＞のいずれか１つに記載の構造体の製造方法。
＜１６＞　得られる構造体が、タッチセンサー、電磁波シールド、アンテナ、配線基板、導電性加熱素子、及び、視野角制御フィルムよりなる群から選ばれる１種の構造体である＜１＞～＜１５＞のいずれか１つに記載の構造体の製造方法。
＜１７＞　透明基材と、上記透明基材の上に配置された遮光性パターン１と、上記透明基材の上で上記遮光性パターン１に隣接して配置され、かつ、上記透明基材に接する樹脂パターン２と、上記遮光性パターン１と上記樹脂パターン２とによって画定される領域にパターン３とを有し、上記遮光性パターン１の平均厚さが、２μｍ以下であり、上記樹脂パターン２の平均厚さが、２μｍを超え、上記遮光性パターン１の平均厚さよりも上記パターン３の平均厚さのほうが厚く、上記樹脂パターン２を永久膜として有する構造体。 Means for solving the above problems include the following aspects.
<1> A negative type that is arranged on the transparent base material, the light-shielding pattern 1 arranged on the transparent base material, the transparent base material, and the light-shielding pattern 1 and is in contact with the transparent base material. A part of the negative type photosensitive resin layer N from a surface opposite to the surface of the transparent base material provided with the light-shielding pattern 1 in the step of preparing a laminate having the photosensitive resin layer N. The step of irradiating the transparent substrate with light, the step of forming the resin pattern 2 on the transparent substrate by developing the negative type photosensitive resin layer N irradiated with light, and the light-shielding pattern 1 and the resin. A method for producing a structure comprising the step of forming a pattern 3 in a region defined by the pattern 2 and the obtained structure having the resin pattern 2 as a permanent film.
<2> The method for producing a structure according to <1>, wherein the light-shielding pattern 1 contains a metal.
<3> The method for producing a structure according to <1> or <2>, wherein the pattern 3 has conductivity.
<4> The method for manufacturing a structure according to any one of <1> to <3>, wherein the pattern 3 is a pattern formed by a plating method.
<5> The method for producing a structure according to any one of <1> to <4>, wherein the light-shielding pattern 1 and the pattern 3 contain the same kind of material.
<6> The structure according to any one of <1> to <5>, wherein the negative photosensitive resin layer N contains an alkali-soluble polymer, an ethylenically unsaturated compound, and a photopolymerization initiator. Production method.
<7> The method for producing a structure according to <6>, wherein the ethylenically unsaturated compound contains a trifunctional or higher functional ethylenically unsaturated compound.
<8> The method for producing a structure according to <6> or <7>, wherein the ethylenically unsaturated compound contains a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure.
<9> The structure according to any one of <1> to <5>, wherein the negative photosensitive resin layer N contains a polyfunctional epoxy resin, a hydroxy group-containing compound, and a photocationic polymerization initiator. Production method.
<10> The method for producing a structure according to any one of <1> to <9>, wherein the negative photosensitive resin layer N contains a metal oxidation inhibitor.
<11> A step of forming a light-shielding layer on one surface of a transparent substrate, a step of forming a photoresist layer on the light-shielding layer, a step of exposing and developing the photoresist layer to form a resist pattern, and a step of forming a resist pattern. The method for producing a structure according to any one of <1> to <10>, further comprising a step of etching the light-shielding layer to form the light-shielding pattern 1.
<12> The method for producing a structure according to any one of <1> to <11>, wherein the average thickness of the pattern 3 is thicker than the average thickness of the light-shielding pattern 1.
<13> The method for producing a structure according to any one of <1> to <12>, wherein the transparent base material is a transparent film base material.
<14> The method for producing a structure according to any one of <1> to <13>, further comprising a step of performing at least one of post-exposure and post-heating on the resin pattern 2.
<15> The method for producing a structure according to any one of <1> to <14>, wherein the negative photosensitive resin layer N is a layer formed of a photosensitive transfer material.
<16> The obtained structure is one type of structure selected from the group consisting of a touch sensor, an electromagnetic wave shield, an antenna, a wiring substrate, a conductive heating element, and a viewing angle control film <1> to <15. > The method for manufacturing a structure according to any one of.
<17> The transparent base material, the light-shielding pattern 1 arranged on the transparent base material, and the transparent base material arranged adjacent to the light-shielding pattern 1 on the transparent base material and on the transparent base material. The resin pattern 2 in contact with the light-shielding pattern 1 and the pattern 3 in the region defined by the light-shielding pattern 1 and the resin pattern 2 are provided, and the average thickness of the light-shielding pattern 1 is 2 μm or less, and the resin pattern 2 The average thickness of the pattern 3 exceeds 2 μm, the average thickness of the pattern 3 is thicker than the average thickness of the light-shielding pattern 1, and the structure has the resin pattern 2 as a permanent film.
　本開示の一実施形態によれば、形態異常の発生が低減されたパターンを有する構造体の製造方法を提供することができる。
　また、本開示の他の実施形態によれば、形態異常の発生が低減されたパターンを有する構造体を提供することができる。 According to one embodiment of the present disclosure, it is possible to provide a method for manufacturing a structure having a pattern in which the occurrence of morphological abnormalities is reduced.
Further, according to another embodiment of the present disclosure, it is possible to provide a structure having a pattern in which the occurrence of morphological abnormalities is reduced.
本開示に係る構造体の製造方法の一例を示す概略断面図である。It is a schematic cross-sectional view which shows an example of the manufacturing method of the structure which concerns on this disclosure. 本開示に係る構造体の一例を示す概略断面図である。It is a schematic cross-sectional view which shows an example of the structure which concerns on this disclosure.
　以下、本開示の内容について説明する。なお、添付の図面を参照しながら説明するが、符号は省略する場合がある。
　また、本明細書において「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
　また、本明細書において、「（メタ）アクリル」はアクリル及びメタクリルの双方、又は、いずれかを表し、「（メタ）アクリレート」はアクリレート及びメタクリレートの双方、又は、いずれかを表す。
　更に、本明細書において組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する該当する複数の物質の合計量を意味する。
　本明細書において「工程」との語は、独立した工程だけでなく、他の工程と明確に区別できない場合であっても工程の所期の目的が達成されれば、本用語に含まれる。
　本明細書における基（原子団）の表記において、置換及び無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も含む。また、露光に用いられる光としては、一般的に、水銀灯の輝線スペクトル、エキシマレーザに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等の活性光線（活性エネルギー線）が挙げられる。
　また、本明細書における化学構造式は、水素原子を省略した簡略構造式で記載する場合もある。
　本開示において、「質量％」と「重量％」とは同義であり、「質量部」と「重量部」とは同義である。
　また、本開示において、２以上の好ましい態様の組み合わせは、より好ましい態様である。
　また、本開示における重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、特に断りのない限り、ＴＳＫｇｅｌ　ＧＭＨｘＬ、ＴＳＫｇｅｌ　Ｇ４０００ＨｘＬ、ＴＳＫｇｅｌ　Ｇ２０００ＨｘＬ（何れも東ソー（株）製の商品名）のカラムを使用したゲルパーミエーションクロマトグラフィ（ＧＰＣ）分析装置により、溶剤ＴＨＦ（テトラヒドロフラン）、示差屈折計により検出し、標準物質としてポリスチレンを用いて換算した分子量である。
　本開示において、「アルカリ可溶性」とは、２２℃の液温において、炭酸ナトリウムの水溶液（１００ｇ、炭酸ナトリウムの濃度：１質量％）への溶解度が０．１ｇ以上である性質を意味する。
　本開示において、「導電性」とは、電流が流れやすい性質を意味する。要求される電流の流れやすさは、制限されず、目的、及び用途において必要な程度であればよい。導電性を体積抵抗率で表す場合、体積抵抗率は、１×１０６Ωｃｍ未満であることが好ましく、１×１０４Ωｃｍ未満であることがより好ましい。
　本開示において、「光」とは、紫外線、可視光線、及び赤外線を含む電磁波を意味する。光は、波長２００ｎｍ～１，５００ｎｍの範囲内の光であることが好ましく、波長２５０ｎｍ～４５０ｎｍの範囲内の光であることがより好ましく、波長３００ｎｍ～４１０ｎｍの範囲内の光であることが特に好ましい。
　本開示において、「固形分」とは、対象物の全成分から溶剤を除いた成分を意味する。 The contents of the present disclosure will be described below. Although the description will be given with reference to the attached drawings, the reference numerals may be omitted.
In addition, the numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
Further, in the present specification, "(meth) acrylic" represents both acrylic and methacrylic, or either, and "(meth) acrylate" represents both acrylate and methacrylate, or either.
Further, in the present specification, the amount of each component in the composition is the sum of the plurality of applicable substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Means quantity.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Unless otherwise specified, the term "exposure" as used herein includes not only exposure using light but also drawing using particle beams such as an electron beam and an ion beam. In addition, as the light used for exposure, generally, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams (active energy rays) are used. Can be mentioned.
Further, the chemical structural formula in the present specification may be described by a simplified structural formula in which a hydrogen atom is omitted.
In the present disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Further, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
Unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Toso Co., Ltd.). It is a molecular weight converted by detecting with a solvent THF (tetrahydrofuran) and a differential refractometer by a gel permeation chromatography (GPC) analyzer and using polystyrene as a standard substance.
In the present disclosure, "alkali-soluble" means the property that the solubility of sodium carbonate in an aqueous solution (100 g, sodium carbonate concentration: 1% by mass) is 0.1 g or more at a liquid temperature of 22 ° C.
In the present disclosure, "conductive" means a property in which an electric current easily flows. The required current flowability is not limited and may be as long as it is necessary for the purpose and application. When the conductivity is expressed by the volume resistivity, the volume resistivity is preferably less than 1 × 10 6 Ωcm, and more preferably less than 1 × 10 4 Ωcm.
In the present disclosure, "light" means electromagnetic waves including ultraviolet rays, visible rays, and infrared rays. The light is preferably light having a wavelength in the range of 200 nm to 1,500 nm, more preferably light having a wavelength in the range of 250 nm to 450 nm, and particularly preferably light having a wavelength in the range of 300 nm to 410 nm. preferable.
In the present disclosure, the "solid content" means a component obtained by removing a solvent from all the components of an object.
（構造体の製造方法）
　本開示に係る構造体の製造方法は、透明基材と、上記透明基材の上に配置された遮光性パターン１と、上記透明基材及び上記遮光性パターン１の上に配置され、かつ、上記透明基材に接するネガ型感光性樹脂層Ｎと、を有する積層体を準備する工程（以下、「準備工程」ともいう。）、上記透明基材の上記遮光性パターン１が設けられている面とは反対側の面から上記ネガ型感光性樹脂層Ｎの一部に光を照射する工程（以下、「露光工程」ともいう。）、光を照射された上記ネガ型感光性樹脂層Ｎを現像することで、上記透明基材上に樹脂パターン２を形成する工程（以下、「現像工程」ともいう。）、並びに、上記遮光性パターン１と上記樹脂パターン２とによって画定される領域にパターン３を形成する工程（以下、「パターン３形成工程」ともいう。）を含み、得られる構造体が、上記樹脂パターン２を永久膜として有する。 (Manufacturing method of structure)
The method for producing a structure according to the present disclosure includes a transparent base material, a light-shielding pattern 1 arranged on the transparent base material, a transparent base material, and a light-shielding pattern 1 arranged on the transparent base material and the light-shielding pattern 1. A step of preparing a laminate having a negative type photosensitive resin layer N in contact with the transparent base material (hereinafter, also referred to as a “preparation step”) and the light-shielding pattern 1 of the transparent base material are provided. A step of irradiating a part of the negative type photosensitive resin layer N with light from a surface opposite to the surface (hereinafter, also referred to as “exposure step”), the negative type photosensitive resin layer N irradiated with light. By developing the above, a step of forming the resin pattern 2 on the transparent substrate (hereinafter, also referred to as “development step”), and a region defined by the light-shielding pattern 1 and the resin pattern 2 The structure including the step of forming the pattern 3 (hereinafter, also referred to as “pattern 3 forming step”) has the resin pattern 2 as a permanent film.
　本開示に係る構造体の製造方法が上記効果を奏する理由は、以下のように推察される。
　上記したように従来の構造体の製造方法（例えば、サブトラクティブ法、及びセミアディティブ法）では、パターンの形状、及び寸法の制御性が十分でない場合があることを本発明者は見出した。
　一方、本開示に係る構造体の製造方法では、上記の各工程を含むことで、例えば、サイドエッチング又はシード層の除去に伴うパターンの形態異常の発生を低減することができる。
　ここで、本開示に係る構造体の製造方法について図１を参照して説明する。
　図１は、本開示に係る構造体の製造方法の一例を示す概略断面図である。図１（ａ）は、準備工程の一例を示す。図１（ｂ）は、露光工程の一例を示す。図１（ｃ）は、現像工程の一例を示す。図１（ｄ）は、パターン３形成工程の一例を示す。
　図１（ａ）に示される積層体１００は、透明基材１０と、遮光性パターン２０（遮光性パターン１）と、ネガ型感光性樹脂層３０（ネガ型感光性樹脂層Ｎ）と、を有する。図１（ｂ）に示されるように、透明基材１０の遮光性パターン２０に対向する面とは反対側の面（すなわち、被露光面１０ａ）に対して光を照射する。遮光性パターン２０を通過する光の割合が小さいため、透明基材１０の被露光面１０ａに入射した光は、透明基材１０を経てネガ型感光性樹脂層３０の露光部３０ａを通過する。この結果、ネガ型感光性樹脂層３０の露光部３０ａが選択的に露光する。図１（ｃ）に示されるように、ネガ型感光性樹脂層３０を現像することでネガ型感光性樹脂層３０の露光部３０ａ以外の部分を除去し、透明基材１０と遮光性パターン２０とによって画定される領域（すなわち、溝）に樹脂パターン４０（樹脂パターン２）を形成する。図１（ｄ）に示されるように、遮光性パターン２０の上にパターン５０（パターン３）を形成する。図１（ｄ）において、パターン５０は、鋳型のように機能する遮光性パターン２０と樹脂パターン４０とによって画定される領域（すなわち、溝）に形成される。上記のような工程を経ることで、パターン５０を容易に形成することができる。
　よって、本開示に係る構造体の製造方法によれば、形態異常の発生が低減されたパターン（好ましくは、導電性パターン）が形成される。 The reason why the method for producing the structure according to the present disclosure exerts the above effect is presumed as follows.
As described above, the present inventor has found that the controllability of the shape and dimensions of the pattern may not be sufficient in the conventional method for manufacturing a structure (for example, the subtractive method and the semi-additive method).
On the other hand, in the method for producing a structure according to the present disclosure, by including each of the above steps, it is possible to reduce the occurrence of pattern morphological abnormality due to, for example, side etching or removal of the seed layer.
Here, a method for manufacturing the structure according to the present disclosure will be described with reference to FIG.
FIG. 1 is a schematic cross-sectional view showing an example of a method for manufacturing a structure according to the present disclosure. FIG. 1A shows an example of the preparation step. FIG. 1B shows an example of the exposure process. FIG. 1C shows an example of the developing process. FIG. 1D shows an example of the pattern 3 forming step.
The laminate 100 shown in FIG. 1A has a transparent base material 10, a light-shielding pattern 20 (light-shielding pattern 1), and a negative-type photosensitive resin layer 30 (negative-type photosensitive resin layer N). Have. As shown in FIG. 1 (b), the surface of the transparent base material 10 opposite to the surface facing the light-shielding pattern 20 (that is, the surface to be exposed 10a) is irradiated with light. Since the proportion of light passing through the light-shielding pattern 20 is small, the light incident on the exposed surface 10a of the transparent base material 10 passes through the exposed portion 30a of the negative photosensitive resin layer 30 via the transparent base material 10. As a result, the exposed portion 30a of the negative type photosensitive resin layer 30 is selectively exposed. As shown in FIG. 1 (c), the negative type photosensitive resin layer 30 is developed to remove the portion of the negative type photosensitive resin layer 30 other than the exposed portion 30a, and the transparent base material 10 and the light-shielding pattern 20 are removed. The resin pattern 40 (resin pattern 2) is formed in the region (that is, the groove) defined by. As shown in FIG. 1 (d), a pattern 50 (pattern 3) is formed on the light-shielding pattern 20. In FIG. 1D, the pattern 50 is formed in a region (ie, a groove) defined by a light-shielding pattern 20 that functions like a mold and a resin pattern 40. By going through the above steps, the pattern 50 can be easily formed.
Therefore, according to the method for manufacturing a structure according to the present disclosure, a pattern (preferably a conductive pattern) in which the occurrence of morphological abnormalities is reduced is formed.
　本開示に係る構造体の製造方法においては、得られる構造体が、上記樹脂パターン２を永久膜として有する。
　本開示において「永久膜」とは、上記構造体を有する物品（製品、また、上記構造体自体が物品である場合も含む。）の完成後にも残存している膜（層）である。永久膜として具体的には、例えば、絶縁膜、保護膜、スペーサー等が挙げられる。
　本開示に係る構造体の製造方法により得られる構造体は、例えば、タッチセンサー、電磁波シールド、アンテナ、配線基板、導電性加熱素子、及び、視野角制御フィルムよりなる群から選ばれる１種の構造体であることが好ましい。 In the method for producing a structure according to the present disclosure, the obtained structure has the above resin pattern 2 as a permanent film.
In the present disclosure, the "permanent film" is a film (layer) that remains even after the completion of an article having the above structure (including a product and the case where the structure itself is an article). Specific examples of the permanent film include an insulating film, a protective film, a spacer, and the like.
The structure obtained by the method for manufacturing a structure according to the present disclosure is one type of structure selected from the group consisting of, for example, a touch sensor, an electromagnetic wave shield, an antenna, a wiring substrate, a conductive heating element, and a viewing angle control film. It is preferably a body.
＜準備工程＞
　本開示に係る積層体の製造方法は、透明基材と、上記透明基材の上に配置された遮光性パターン１と、上記透明基材及び上記遮光性パターン１の上に配置され、かつ、上記透明基材に接するネガ型感光性樹脂層Ｎと、を有する積層体を準備する工程（準備工程）を含む。
　本開示において、「準備」とは、対象物を使用可能な状態にすることを意味する。積層体は、事前に製造された積層体であってもよい。積層体は、準備工程において製造された積層体であってもよい。すなわち、準備工程は、積層体を製造する工程を含んでもよい。 <Preparation process>
The method for producing a laminate according to the present disclosure is a transparent base material, a light-shielding pattern 1 arranged on the transparent base material, a transparent base material, and a light-shielding pattern 1 arranged on the transparent base material and the light-shielding pattern 1. The step (preparation step) of preparing a laminate having the negative type photosensitive resin layer N in contact with the transparent base material is included.
In the present disclosure, "preparation" means making an object ready for use. The laminated body may be a laminated body manufactured in advance. The laminate may be a laminate produced in the preparatory step. That is, the preparation step may include a step of manufacturing the laminate.
［透明基材］
　積層体は、透明基材を有する。本開示において、「透明」とは、上記露光工程における露光波長の透過率が５０％以上であることを意味する。「透明」との用語において規定される露光波長の透過率は、８０％以上であることが好ましく、９０％であることがより好ましく、９５％であることが特に好ましい。本開示において、「露光波長の透過率」とは、露光工程において対象物（例えば、透明基材）に到達する光に含まれる波長の透過率を意味する。例えば、露光工程において波長３６５ｎｍを含む光源を用いる場合、「露光波長の透過率」とは、波長３６５ｎｍの透過率をいう。本開示において、「透過率」とは、測定対象物の主面に垂直な方向（すなわち、厚さ方向）に光を入射させたときの入射光の強度に対する、測定対象物を通過して出射した出射光の強度の比率である。透過率は、大塚電子（株）製のＭＣＰＤ　Ｓｅｒｉｅｓを用いて測定する。
　また、透明基材は、波長４００ｎｍ～７００ｎｍの光の透過率が８０％以上であることが好ましい。 [Transparent substrate]
The laminate has a transparent substrate. In the present disclosure, "transparent" means that the transmittance of the exposure wavelength in the exposure step is 50% or more. The transmittance of the exposure wavelength defined by the term "transparent" is preferably 80% or more, more preferably 90%, and particularly preferably 95%. In the present disclosure, the "transmittance of an exposure wavelength" means the transmittance of a wavelength included in the light that reaches an object (for example, a transparent substrate) in the exposure process. For example, when a light source having a wavelength of 365 nm is used in the exposure step, the “transmittance of the exposure wavelength” means the transmittance of the wavelength of 365 nm. In the present disclosure, "transmittance" refers to the intensity of incident light when light is incident in a direction perpendicular to the main surface of the object to be measured (that is, in the thickness direction), and is emitted through the object to be measured. It is the ratio of the intensity of the emitted light. The transmittance is measured using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
Further, the transparent substrate preferably has a light transmittance of 80% or more at a wavelength of 400 nm to 700 nm.
　透明基材の形状は、制限されない。透明基材として、例えば、フィルム状、又は板状の透明基材が好ましく使用される。中でも、透明基材は、透明フィルム基材であることが好ましい。 The shape of the transparent base material is not limited. As the transparent base material, for example, a film-shaped or plate-shaped transparent base material is preferably used. Above all, the transparent base material is preferably a transparent film base material.
　透明基材としては、例えば、樹脂基板（例えば、樹脂フィルム）、及びガラス基板が挙げられる。樹脂基板は、可視光を透過する樹脂基板であることが好ましい。可視光を透過する樹脂基板の好ましい成分としては、例えば、ポリアミド系樹脂、ポリエチレンテレフタレート系樹脂、ポリエチレンナフタレート系樹脂、シクロオレフィン系樹脂、ポリイミド系樹脂、及びポリカーボネート系樹脂が挙げられる。可視光を透過する樹脂基板のより好ましい成分としては、例えば、ポリアミド、ポリエチレンテレフタレート（ＰＥＴ）、シクロオレフィンポリマー（ＣＯＰ）、ポリエチレンナフタレート（ＰＥＮ）、ポリイミド、及びポリカーボネートが挙げられる。透明基材は、ポリアミドフィルム、ポリエチレンテレフタレートフィルム、シクロオレフィンポリマー（ＣＯＰ）、ポリエチレンナフタレートフィルム、ポリイミドフィルム、又はポリカーボネートフィルムであることが好ましく、ポリエチレンテレフタレートフィルムであることがより好ましい。 Examples of the transparent substrate include a resin substrate (for example, a resin film) and a glass substrate. The resin substrate is preferably a resin substrate that transmits visible light. Preferred components of the resin substrate that transmits visible light include, for example, polyamide-based resin, polyethylene terephthalate-based resin, polyethylene naphthalate-based resin, cycloolefin-based resin, polyimide-based resin, and polycarbonate-based resin. More preferable components of the resin substrate that transmits visible light include, for example, polyamide, polyethylene terephthalate (PET), cycloolefin polymer (COP), polyethylene naphthalate (PEN), polyimide, and polycarbonate. The transparent substrate is preferably a polyamide film, a polyethylene terephthalate film, a cycloolefin polymer (COP), a polyethylene naphthalate film, a polyimide film, or a polycarbonate film, and more preferably a polyethylene terephthalate film.
　透明基材としては、例えば、紙フェノール、紙エポキシ、ガラスコンポジット、ガラスエポキシ、ポリテトラフルオロエチレン、硬質材料と軟質材料とを複合したリジッドフレキシブル材も挙げられる。透明基材は、多孔質の透明基材であってもよい。透明基材は、充填材、及び添加剤を含んでもよい。 Examples of the transparent base material include paper phenol, paper epoxy, glass composite, glass epoxy, polytetrafluoroethylene, and a rigid flexible material in which a hard material and a soft material are combined. The transparent base material may be a porous transparent base material. The transparent substrate may contain a filler and an additive.
　透明基材の表面は、例えば、アルカリ処理、又はエネルギー線照射によって改質されてもよい。 The surface of the transparent base material may be modified by, for example, alkali treatment or energy ray irradiation.
　透明基材の構造は、単層構造、又は多層構造であってもよい。透明基材は、例えば、機能層を含んでもよい。機能層としては、例えば、接着層、ハードコート層、及び屈折率調整層が挙げられる。 The structure of the transparent base material may be a single-layer structure or a multi-layer structure. The transparent substrate may include, for example, a functional layer. Examples of the functional layer include an adhesive layer, a hard coat layer, and a refractive index adjusting layer.
　透明基材の厚さは、制限されない。透明基材の厚さは、１０μｍ～２００μｍの範囲であることが好ましく、２０μｍ～１２０μｍの範囲であることがより好ましく、２０μｍ～１００μｍであることが特に好ましい。透明基材の厚さは、以下の方法によって測定する。走査型電子顕微鏡（ＳＥＭ）を用いて、透明基材の主面に対して垂直な方向（すなわち、厚さ方向）の断面を観察する。得られた観察画像に基づいて、透明基材の厚さを１０点測定する。測定値を算術平均することで、透明基材の平均厚さを求める。 The thickness of the transparent substrate is not limited. The thickness of the transparent substrate is preferably in the range of 10 μm to 200 μm, more preferably in the range of 20 μm to 120 μm, and particularly preferably in the range of 20 μm to 100 μm. The thickness of the transparent substrate is measured by the following method. A scanning electron microscope (SEM) is used to observe a cross section in a direction perpendicular to the main surface of the transparent substrate (ie, in the thickness direction). Based on the obtained observation image, the thickness of the transparent substrate is measured at 10 points. The average thickness of the transparent substrate is obtained by arithmetically averaging the measured values.
　透明基材の全光線透過率は、高いことが好ましい。透明基材の全光線透過率は、５０％以上であることが好ましく、８０％以上であることがより好ましく、９０％以上であることが更に好ましく、９５％以上であることが特に好ましい。透明基材の全光線透過率の上限は、制限されない。透明基材の全光線透過率は、１００％以下の範囲で決定すればよい。全光線透過率は、ＪＩＳ　Ｋ　７３６１－１（１９９７）に規定される方法により測定する。 The total light transmittance of the transparent substrate is preferably high. The total light transmittance of the transparent substrate is preferably 50% or more, more preferably 80% or more, further preferably 90% or more, and particularly preferably 95% or more. The upper limit of the total light transmittance of the transparent substrate is not limited. The total light transmittance of the transparent substrate may be determined in the range of 100% or less. The total light transmittance is measured by the method specified in JIS K 7361-1 (1997).
［遮光性パターン］
　積層体は、透明基材の上に遮光性パターン１を有する。例えば、図１（ｂ）に示されるように、積層体が遮光性パターン１を有することで、露光工程においてネガ型感光性樹脂層の一部を選択的に露光することができる。本開示において、「遮光」とは、露光波長の透過率が、５０％未満であることを意味する。「遮光」との用語において規定される露光波長の透過率は、３０％未満であることが好ましく、１０％未満であることがより好ましく、１％未満であることが特に好ましい。
　また、遮光性パターン１は、波長４００ｎｍ～７００ｎｍの光の透過率が３０％未満であることが好ましい。 [Light-shielding pattern]
The laminate has a light-shielding pattern 1 on a transparent substrate. For example, as shown in FIG. 1B, when the laminate has the light-shielding pattern 1, a part of the negative photosensitive resin layer can be selectively exposed in the exposure step. In the present disclosure, "light shielding" means that the transmittance of the exposure wavelength is less than 50%. The transmittance of the exposure wavelength defined by the term "light shielding" is preferably less than 30%, more preferably less than 10%, and particularly preferably less than 1%.
Further, the light-shielding pattern 1 preferably has a light transmittance of less than 30% at a wavelength of 400 nm to 700 nm.
　遮光性パターン１は、導電性を有することが好ましい。導電性を有する遮光性パターン１は、例えば、後述するパターン３形成工程においてめっきを行う際に電気伝導体（例えば、シード層）として機能することができる。シード層は、例えば、電気めっきにおいてカソードとして機能することができる。
　中でも、遮光性パターン１は、金属を含むことが好ましい。 The light-shielding pattern 1 preferably has conductivity. The conductive light-shielding pattern 1 can function as an electric conductor (for example, a seed layer) when plating is performed in the pattern 3 forming step described later, for example. The seed layer can function as a cathode in, for example, electroplating.
Above all, the light-shielding pattern 1 preferably contains a metal.
　遮光性パターン１の成分としては、例えば、金属が挙げられる。金属としては、例えば、Ｎｂ（ニオブ）、Ａｌ（アルミニウム）、Ｎｉ（ニッケル）、Ｚｎ（亜鉛）、Ｍｏ（モリブデン）、Ｔａ（タンタル）、Ｔｉ（チタン）、Ｖ（バナジウム）、Ｃｒ（クロム）、Ｆｅ（鉄）、Ｃｏ（コバルト）、Ｗ（タングステン）、Ｃｕ（銅）、Ｓｎ（スズ）、及びＭｎ（マンガン）が挙げられる。遮光性パターン１は、導電性の観点から、金属を含むことが好ましく、Ｎｂ、Ａｌ、Ｎｉ、Ｚｎ、Ｍｏ、Ｔａ、Ｔｉ、Ｖ、Ｃｒ、Ｆｅ、Ｃｏ、Ｗ、Ｃｕ、Ｓｎ及びＭｎよりなる群から選択される少なくとも１種の金属を含むことがより好ましく、Ｃｕを含むことが特に好ましい。Ｃｕは、電気抵抗が小さく、安価であるという観点から好ましい。遮光性パターン１は、１種単独、又は２種以上の金属を含んでもよい。遮光性パターン１に含まれる金属は、単体の金属、又は合金であってもよい。遮光性パターン１は、Ｃｕ、又はＣｕの合金を含むことが好ましい。遮光性パターン１が金属を含む場合、遮光性パターンに含まれる金属元素は、後述する導電性パターンに含まれる金属元素と同一であっても異なってもよい。遮光性パターン１は、導電性パターンに含まれる金属元素と同一の金属元素を含むことが好ましい。 Examples of the component of the light-shielding pattern 1 include metal. Examples of the metal include Nb (niobium), Al (aluminum), Ni (nickel), Zn (zinc), Mo (molybdenum), Ta (tantalum), Ti (titanium), V (vanadium), and Cr (chromium). , Fe (iron), Co (cobalt), W (tungsten), Cu (copper), Sn (tin), and Mn (manganese). The light-shielding pattern 1 preferably contains a metal from the viewpoint of conductivity, and is composed of Nb, Al, Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn and Mn. It is more preferable to contain at least one metal selected from the group, and it is particularly preferable to contain Cu. Cu is preferable from the viewpoint of low electrical resistance and low cost. The light-shielding pattern 1 may contain one kind alone or two or more kinds of metals. The metal contained in the light-shielding pattern 1 may be a single metal or an alloy. The light-shielding pattern 1 preferably contains Cu or an alloy of Cu. When the light-shielding pattern 1 contains a metal, the metal element contained in the light-shielding pattern may be the same as or different from the metal element contained in the conductive pattern described later. The light-shielding pattern 1 preferably contains the same metal element as the metal element contained in the conductive pattern.
　遮光性パターン１は、金属元素以外の元素を含んでもよい。金属元素以外の元素としては、例えば、Ｃ（炭素）、Ｐ（リン）、及びＢ（ホウ素）が挙げられる。金属元素以外の元素は、金属元素と合金を形成してもよい。 The light-shielding pattern 1 may contain an element other than a metal element. Examples of elements other than metal elements include C (carbon), P (phosphorus), and B (boron). Elements other than metal elements may form alloys with metal elements.
　遮光性パターン１の形状は、制限されない。遮光性パターン１の形状は、例えば、目的とする導電性パターンの形状に応じて決定すればよい。 The shape of the light-shielding pattern 1 is not limited. The shape of the light-shielding pattern 1 may be determined, for example, according to the shape of the target conductive pattern.
　遮光性パターン１の構造は、単層構造、又は多層構造であってもよい。多層構造を有する遮光性パターン１の各層の成分は、同一であっても異なってもよい。 The structure of the light-shielding pattern 1 may be a single-layer structure or a multi-layer structure. The components of each layer of the light-shielding pattern 1 having a multi-layer structure may be the same or different.
　遮光性パターン１の厚さは、制限されない。遮光性パターン１の平均厚さは、３μｍ以下であることが好ましく、２μｍ以下であることがより好ましく、１μｍ以下であることが更に好ましく、０．５μｍ以下であることが特に好ましい。遮光性パターン１の平均厚さが３μｍ以下であることで、遮光性パターンの成形性を向上させることができる。この結果、導電性パターンの形態異常の発生を更に低減することができる。遮光性パターン１の平均厚さは、０．０５μｍ以上であることが好ましく、０．１μｍ以上であることがより好ましく、０．３μｍ以上であることが特に好ましい。遮光性パターン１の平均厚さが０．０５μｍ以上であることで、露光波長の透過率を下げることができる。また、遮光性パターン１をシード層として使用する場合、導電性パターンの生産性を向上させることができる。遮光性パターン１の平均厚さは、上記透明基材の平均厚さの測定方法に準ずる方法によって測定する。 The thickness of the light-shielding pattern 1 is not limited. The average thickness of the light-shielding pattern 1 is preferably 3 μm or less, more preferably 2 μm or less, further preferably 1 μm or less, and particularly preferably 0.5 μm or less. When the average thickness of the light-shielding pattern 1 is 3 μm or less, the moldability of the light-shielding pattern can be improved. As a result, the occurrence of morphological abnormalities of the conductive pattern can be further reduced. The average thickness of the light-shielding pattern 1 is preferably 0.05 μm or more, more preferably 0.1 μm or more, and particularly preferably 0.3 μm or more. When the average thickness of the light-shielding pattern 1 is 0.05 μm or more, the transmittance of the exposure wavelength can be reduced. Further, when the light-shielding pattern 1 is used as the seed layer, the productivity of the conductive pattern can be improved. The average thickness of the light-shielding pattern 1 is measured by a method according to the method for measuring the average thickness of the transparent substrate.
　遮光性パターン１の幅は、制限されない。なお、遮光性パターン１の幅とは、透明基材の面方向において、遮光性パターン１の長手方向に対し垂直な方向における遮光性パターン１の長さである。例えば、遮光性パターン１がラインアンドスペースパターンであれば、遮光性パターン１の幅は、ラインパターンの短手方向の長さである。また、例えば、遮光性パターン１が、透明基材の面方向の断面形状が円形又は楕円形状であれば、遮光性パターン１の幅は、上記円形又は楕円形状における最小径である。
　遮光性パターン１の幅は、例えば、パターン３形成工程において形成する導電性パターンの幅に応じて決定すればよい。遮光性パターン１の平均幅は、５０μｍ以下であることが好ましく、１０μｍ以下であることがより好ましく、５μｍ以下であることが更に好ましく、２μｍ以下であることが特に好ましい。遮光性パターン１の平均幅は、０．１μｍ以上であることが好ましく、０．５μｍ以上であることがより好ましい。遮光性パターン１の平均幅は、５箇所で測定した遮光性パターンの幅の算術平均である。 The width of the light-shielding pattern 1 is not limited. The width of the light-shielding pattern 1 is the length of the light-shielding pattern 1 in the direction perpendicular to the longitudinal direction of the light-shielding pattern 1 in the surface direction of the transparent base material. For example, if the light-shielding pattern 1 is a line-and-space pattern, the width of the light-shielding pattern 1 is the length of the line pattern in the lateral direction. Further, for example, when the light-shielding pattern 1 has a circular or elliptical cross-sectional shape in the plane direction of the transparent base material, the width of the light-shielding pattern 1 is the minimum diameter in the circular or elliptical shape.
The width of the light-shielding pattern 1 may be determined, for example, according to the width of the conductive pattern formed in the pattern 3 forming step. The average width of the light-shielding pattern 1 is preferably 50 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, and particularly preferably 2 μm or less. The average width of the light-shielding pattern 1 is preferably 0.1 μm or more, and more preferably 0.5 μm or more. The average width of the light-shielding pattern 1 is an arithmetic mean of the width of the light-shielding pattern measured at five points.
　遮光性パターン１は、透明基材に直接又は他の層を介して接してもよい。他の層としては、例えば、密着層が挙げられる。例えば、積層体は、透明基材と遮光性パターン１との間に密着層を有してもよい。密着層の成分は、制限されない。密着層の成分は、例えば、透明基材と遮光性パターン１との密着力、及び本開示に係る構造体の製造方法によって得られる導電性パターンの使用環境（例えば、湿度、及び温度）における安定性に応じて決定すればよい。密着層は、Ｎｉ、Ｚｎ、Ｍｏ、Ｔａ、Ｔｉ、Ｖ、Ｃｒ、Ｆｅ、Ｃｏ、Ｗ、Ｃｕ、Ｓｎ、及びＭｎから選ばれる少なくとも１種を含むことが好ましい。密着層は、Ｃ（炭素原子）、Ｏ（酸素原子）、Ｈ（水素原子）、及びＮ（窒素原子）よりなる群から選択される少なくとも１種を更に含んでもよい。密着層は、黒化層であってもよい。黒化層は、露光工程において遮光性パターンによる光の反射を抑制することができる。密着層を黒化層として機能させる場合、密着層は、例えば、Ｎｉ－Ｃｕ合金を含むことが好ましい。黒化層として機能する密着層は、Ｃ、Ｏ、Ｈ、及びＮよりなる群から選択される少なくとも１種を更に含んでもよい。密着層の厚さは、制限されない。密着層の平均厚さは、３ｎｍ～５０ｎｍであることが好ましく、３ｎｍ～３５ｎｍであることがより好ましく、３ｎｍ～３３ｎｍであることが特に好ましい。 The light-shielding pattern 1 may be in contact with the transparent substrate directly or via another layer. Examples of the other layer include an adhesion layer. For example, the laminate may have an adhesion layer between the transparent substrate and the light-shielding pattern 1. The components of the adhesion layer are not limited. The components of the adhesion layer are, for example, the adhesion between the transparent base material and the light-shielding pattern 1, and the stability of the conductive pattern obtained by the method for producing the structure according to the present disclosure in the usage environment (for example, humidity and temperature). It may be decided according to the sex. The adhesion layer preferably contains at least one selected from Ni, Zn, Mo, Ta, Ti, V, Cr, Fe, Co, W, Cu, Sn, and Mn. The adhesion layer may further contain at least one selected from the group consisting of C (carbon atom), O (oxygen atom), H (hydrogen atom), and N (nitrogen atom). The adhesion layer may be a blackening layer. The blackened layer can suppress the reflection of light due to the light-shielding pattern in the exposure process. When the adhesion layer functions as a blackening layer, the adhesion layer preferably contains, for example, a Ni—Cu alloy. The adhesion layer that functions as a blackening layer may further contain at least one selected from the group consisting of C, O, H, and N. The thickness of the adhesion layer is not limited. The average thickness of the adhesion layer is preferably 3 nm to 50 nm, more preferably 3 nm to 35 nm, and particularly preferably 3 nm to 33 nm.
［ネガ型感光性樹脂層Ｎ］
　積層体は、透明基材及び遮光性パターン１の上に配置され、かつ、上記透明基材に接するネガ型感光性樹脂層Ｎを有する。ネガ型感光性樹脂層Ｎは、遮光性パターン１に直接又は他の層を介して接してもよい。ネガ型感光性樹脂層Ｎは、遮光性パターン１に接していることが好ましい。ネガ型感光性樹脂層Ｎとしては、公知のネガ型感光性樹脂層を利用することができる。 [Negative type photosensitive resin layer N]
The laminate has a negative photosensitive resin layer N that is arranged on the transparent base material and the light-shielding pattern 1 and is in contact with the transparent base material. The negative photosensitive resin layer N may be in contact with the light-shielding pattern 1 directly or via another layer. The negative photosensitive resin layer N is preferably in contact with the light-shielding pattern 1. As the negative type photosensitive resin layer N, a known negative type photosensitive resin layer can be used.
　ある実施形態において、ネガ型感光性樹脂層Ｎは、後述する重合体Ａと、後述する重合性化合物Ｂと、光重合開始剤と、を含むことが好ましい。ネガ型感光性樹脂層Ｎは、上記ネガ型感光性樹脂層Ｎの全質量に対して、１０質量％～９０質量％の重合体Ａ、５質量％～７０質量％の重合性化合物Ｂ、及び０．０１質量％～２０質量％の光重合開始剤を含むことが好ましい。ある実施形態において、ネガ型感光性樹脂層Ｎは、アルカリ可溶性高分子と、エチレン性不飽和化合物と、光重合開始剤と、を含むことが好ましい。 In a certain embodiment, the negative photosensitive resin layer N preferably contains a polymer A described later, a polymerizable compound B described later, and a photopolymerization initiator. The negative type photosensitive resin layer N includes 10% by mass to 90% by mass of the polymer A and 5% by mass to 70% by mass of the polymerizable compound B with respect to the total mass of the negative type photosensitive resin layer N. It is preferable to contain 0.01% by mass to 20% by mass of a photopolymerization initiator. In certain embodiments, the negative photosensitive resin layer N preferably contains an alkali-soluble polymer, an ethylenically unsaturated compound, and a photopolymerization initiator.
　また、ネガ型感光性樹脂層Ｎは、硬化性及び現像性の観点から、アルカリ可溶性高分子、エチレン性不飽和化合物、及び、光酸発生剤を含むことが好ましい。
　更に、ネガ型感光性樹脂層Ｎは、得られる樹脂パターン２の永久膜としての強度及び耐久性の観点から、多官能エポキシ樹脂、ヒドロキシ基含有化合物、及び、カチオン重合開始剤を含むことが好ましい。
　以下、ネガ型感光性樹脂層Ｎについて具体的に説明する。 Further, the negative photosensitive resin layer N preferably contains an alkali-soluble polymer, an ethylenically unsaturated compound, and a photoacid generator from the viewpoint of curability and developability.
Further, the negative photosensitive resin layer N preferably contains a polyfunctional epoxy resin, a hydroxy group-containing compound, and a cationic polymerization initiator from the viewpoint of strength and durability of the obtained resin pattern 2 as a permanent film. ..
Hereinafter, the negative type photosensitive resin layer N will be specifically described.
－アルカリ可溶性高分子－
　ネガ型感光性樹脂層Ｎは、アルカリ可溶性高分子を含むことが好ましい。
　なお、本開示において、「アルカリ可溶性」とは、２２℃において炭酸ナトリウムの１質量％水溶液１００ｇへの溶解度が０．１ｇ以上であることを意味する。
　アルカリ可溶性高分子は、例えば、現像性の観点から、酸価６０ｍｇＫＯＨ／ｇ以上であることが好ましい。
　また、アルカリ可溶性高分子は、例えば、加熱により架橋成分と熱架橋し、強固な膜を形成しやすいという観点から、酸価６０ｍｇＫＯＨ／ｇ以上のカルボキシ基を有する樹脂（いわゆる、カルボキシ基含有樹脂）であることが更に好ましく、酸価６０ｍｇＫＯＨ／ｇ以上のカルボキシ基を有するアクリル樹脂（いわゆる、カルボキシ基含有アクリル樹脂）であることが特に好ましい。
　なお、本開示において、アクリル樹脂とは、（メタ）アクリル化合物由来の構成単位を有する樹脂を指し、上記構成単位の含有量が、樹脂の全質量に対し、３０質量％以上であることが好ましく、５０質量％以上であることがより好ましい。
　アルカリ可溶性高分子がカルボキシ基を有する樹脂であると、例えば、ブロックイソシアネート化合物等の熱架橋性化合物を添加して熱架橋することで、３次元架橋密度を高めることができる。また、カルボキシ基を有する樹脂のカルボキシ基が無水化され、疎水化すると、湿熱耐性が改善し得る。 -Alkali-soluble polymer-
The negative photosensitive resin layer N preferably contains an alkali-soluble polymer.
In the present disclosure, "alkali-soluble" means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22 ° C. is 0.1 g or more.
The alkali-soluble polymer preferably has an acid value of 60 mgKOH / g or more from the viewpoint of developability, for example.
Further, the alkali-soluble polymer is, for example, a resin having a carboxy group having an acid value of 60 mgKOH / g or more (so-called carboxy group-containing resin) from the viewpoint that it is easily crosslinked with a crosslinked component by heating to form a strong film. Is more preferable, and an acrylic resin having a carboxy group having an acid value of 60 mgKOH / g or more (so-called carboxy group-containing acrylic resin) is particularly preferable.
In the present disclosure, the acrylic resin refers to a resin having a structural unit derived from a (meth) acrylic compound, and the content of the structural unit is preferably 30% by mass or more with respect to the total mass of the resin. , 50% by mass or more is more preferable.
When the alkali-soluble polymer is a resin having a carboxy group, the three-dimensional crosslink density can be increased by adding a heat-crosslinkable compound such as a blocked isocyanate compound and heat-crosslinking. Further, when the carboxy group of the resin having a carboxy group is anhydrous and hydrophobized, the wet heat resistance can be improved.
　酸価６０ｍｇＫＯＨ／ｇ以上のカルボキシ基含有アクリル樹脂としては、上記酸価の条件を満たす限りにおいて、特に制限はなく、公知のアクリル樹脂から適宜選択して用いることができる。
　例えば、特開２０１１－９５７１６号公報の段落００２５に記載のポリマーのうち、酸価６０ｍｇＫＯＨ／ｇ以上のカルボキシ基含有アクリル樹脂、特開２０１０－２３７５８９号公報の段落００３３～００５２に記載のポリマーのうち、酸価６０ｍｇＫＯＨ／ｇ以上のカルボキシ基含有アクリル樹脂等を好ましく用いることができる。 The carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not particularly limited as long as the above acid value conditions are satisfied, and can be appropriately selected from known acrylic resins and used.
For example, among the polymers described in paragraphs 0025 of JP2011-95716A, carboxy group-containing acrylic resins having an acid value of 60 mgKOH / g or more, and the polymers described in paragraphs 0033 to 0052 of JP2010-237589A. , A carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be preferably used.
　アルカリ可溶性高分子は、現像残渣抑制性、得られる硬化膜の透湿度、及び、得られる未硬化膜の粘着性の観点から、アクリル樹脂、又は、スチレン－アクリル共重合体であることが好ましく、スチレン－アクリル共重合体であることがより好ましい。
　なお、本開示において、スチレン－アクリル共重合体とは、スチレン化合物由来の構成単位と、（メタ）アクリル化合物由来の構成単位とを有する樹脂を指し、上記スチレン化合物由来の構成単位、上記（メタ）アクリル化合物由来の構成単位の合計含有量が、上記共重合体の全質量に対し、３０質量％以上であることが好ましく、５０質量％以上であることがより好ましい。
　また、スチレン化合物由来の構成単位の含有量は、上記共重合体の全質量に対し、１質量％以上であることが好ましく、５質量％以上であることがより好ましく、５質量％以上８０質量％以下であることが特に好ましい。
　また、上記（メタ）アクリル化合物由来の構成単位の含有量は、上記共重合体の全質量に対し、５質量％以上であることが好ましく、１０質量％以上であることがより好ましく、２０質量％以上９５質量％以下であることが特に好ましい。
　更に、上記（メタ）アクリル化合物としては、（メタ）アクリレート化合物、（メタ）アクリル酸、（メタ）アクリルアミド化合物、（メタ）アクリロニトリル等が挙げられる。中でも、（メタ）アクリレート化合物、及び、（メタ）アクリル酸よりなる群から選ばれた少なくとも１種の化合物が好ましい。 The alkali-soluble polymer is preferably an acrylic resin or a styrene-acrylic copolymer from the viewpoint of suppressing development residue, moisture permeability of the obtained cured film, and adhesiveness of the obtained uncured film. More preferably, it is a styrene-acrylic copolymer.
In the present disclosure, the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth) acrylic compound, and the structural unit derived from the styrene compound and the (meth) compound. ) The total content of the constituent units derived from the acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on the total mass of the copolymer.
The content of the structural unit derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and 5% by mass or more and 80% by mass with respect to the total mass of the copolymer. It is particularly preferable that it is% or less.
The content of the structural unit derived from the (meth) acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass, based on the total mass of the copolymer. It is particularly preferable that it is% or more and 95% by mass or less.
Further, examples of the (meth) acrylic compound include (meth) acrylate compound, (meth) acrylic acid, (meth) acrylamide compound, and (meth) acrylonitrile. Among them, at least one compound selected from the group consisting of (meth) acrylate compound and (meth) acrylic acid is preferable.
＜＜重合体Ａ＞＞
　ネガ型感光性樹脂層Ｎは、重合体Ａを含むことが好ましい。重合体Ａは、アルカリ可溶性高分子であることが好ましい。アルカリ可溶性高分子は、アルカリ物質に溶け易い高分子を包含する。なお、本開示において、「アルカリ可溶性」とは、２２℃において炭酸ナトリウムの１質量％水溶液１００ｇへの溶解度が０．１ｇ以上であることを意味する。 << Polymer A >>
The negative photosensitive resin layer N preferably contains the polymer A. The polymer A is preferably an alkali-soluble polymer. Alkali-soluble polymers include polymers that are easily soluble in alkaline substances. In the present disclosure, "alkali-soluble" means that the solubility of sodium carbonate in 100 g of a 1% by mass aqueous solution at 22 ° C. is 0.1 g or more.
　重合体Ａの酸価は、現像液によるネガ型感光性樹脂層Ｎの膨潤を抑制することで解像性がより優れる観点から、２２０ｍｇＫＯＨ／ｇ以下であることが好ましく、２００ｍｇＫＯＨ／ｇ未満であることがより好ましく、１９０ｍｇＫＯＨ／ｇ未満であることが特に好ましい。酸価の下限は、制限されない。重合体Ａの酸価は、現像性がより優れる観点から、６０ｍｇＫＯＨ／ｇ以上であることが好ましく、１２０ｍｇＫＯＨ／ｇ以上であることがより好ましく、１５０ｍｇＫＯＨ／ｇ以上であることが更に好ましく、１７０ｍｇＫＯＨ／ｇ以上であることが特に好ましい。重合体Ａの酸価は、例えば、重合体Ａを構成する構成単位の種類、及び酸基を含有する構成単位の含有量によって調整することができる。 The acid value of the polymer A is preferably 220 mgKOH / g or less, and less than 200 mgKOH / g, from the viewpoint of more excellent resolution by suppressing the swelling of the negative photosensitive resin layer N due to the developing solution. It is more preferable, and it is particularly preferable that it is less than 190 mgKOH / g. The lower limit of acid value is not limited. The acid value of the polymer A is preferably 60 mgKOH / g or more, more preferably 120 mgKOH / g or more, further preferably 150 mgKOH / g or more, and 170 mgKOH / g or more, from the viewpoint of more excellent developability. It is particularly preferable that it is g or more. The acid value of the polymer A can be adjusted, for example, by the type of the structural unit constituting the polymer A and the content of the structural unit containing an acid group.
　本開示において、酸価は、試料１ｇを中和するのに必要な水酸化カリウムの質量（ｍｇ）である。本開示においては、酸価の単位をｍｇＫＯＨ／ｇと記載する。酸価は、例えば、化合物中における酸基の平均含有量から算出できる。 In the present disclosure, the acid value is the mass (mg) of potassium hydroxide required to neutralize 1 g of the sample. In the present disclosure, the unit of acid value is described as mgKOH / g. The acid value can be calculated, for example, from the average content of acid groups in the compound.
　重合体Ａの重量平均分子量（Ｍｗ）は、５，０００～５００，０００であることが好ましい。重量平均分子量を５００，０００以下にすることは、解像性、及び現像性を向上させる観点から好ましい。重合体Ａの重量平均分子量は、１００，０００以下であることがより好ましく、６０，０００以下であることが更に好ましく、５０，０００以下であることが特に好ましい。一方、重量平均分子量を５，０００以上にすることは、現像凝集物の性状を制御する観点から好ましい。重合体Ａの重量平均分子量は、１０，０００以上であることがより好ましく、２０，０００以上であることが更に好ましく、３０，０００以上であることが特に好ましい。 The weight average molecular weight (Mw) of the polymer A is preferably 5,000 to 500,000. It is preferable that the weight average molecular weight is 500,000 or less from the viewpoint of improving the resolvability and the developability. The weight average molecular weight of the polymer A is more preferably 100,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, it is preferable to set the weight average molecular weight to 5,000 or more from the viewpoint of controlling the properties of the developed aggregate. The weight average molecular weight of the polymer A is more preferably 10,000 or more, further preferably 20,000 or more, and particularly preferably 30,000 or more.
　重合体Ａの分散度は、１．０～６．０であることが好ましく、１．０～５．０であることがより好ましく、１．０～４．０であることが更に好ましく、１．０～３．０であることが特に好ましい。本開示において、分散度は、数平均分子量に対する重量平均分子量の比（重量平均分子量／数平均分子量）である。 The dispersity of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, and even more preferably 1.0 to 4.0. It is particularly preferably 0.0 to 3.0. In the present disclosure, the degree of dispersion is the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).
　重合体Ａは、露光時の焦点位置がずれたときの線幅太り、及び解像度の悪化を抑制する観点から、芳香族炭化水素基を有する構成単位を有することが好ましく、芳香族炭化水素基を有する単量体に由来する構成単位を有することがより好ましい。 The polymer A preferably has a structural unit having an aromatic hydrocarbon group from the viewpoint of suppressing the line width thickening when the focal position is deviated during exposure and the deterioration of the resolution, and the polymer A preferably contains an aromatic hydrocarbon group. It is more preferable to have a structural unit derived from the monomer having.
　芳香族炭化水素基としては、例えば、置換又は非置換のフェニル基、及び置換又は非置換のアラルキル基が挙げられる。 Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group.
　重合体Ａにおける芳香族炭化水素基を有する単量体に由来する構成単位の含有割合は、重合体Ａの全質量に対して、２０質量％以上であることが好ましく、３０質量％以上であることがより好ましく、４０質量％以上であることが更に好ましく、４５質量％以上であることが特に好ましく、５０質量％以上であることが最も好ましい。芳香族炭化水素基を有する単量体に由来する構成単位の含有割合の上限は、制限されない。重合体Ａにおける芳香族炭化水素基を有する単量体に由来する構成単位の含有割合は、重合体Ａの全質量に対して、９５質量％以下であることが好ましく、８５質量％以下であることがより好ましい。なお、ネガ型感光性樹脂層が複数種の重合体Ａを含む場合、芳香族炭化水素基を有する単量体に由来する構成単位の含有割合は、重量平均値として求める。 The content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is preferably 20% by mass or more, preferably 30% by mass or more, based on the total mass of the polymer A. More preferably, it is more preferably 40% by mass or more, particularly preferably 45% by mass or more, and most preferably 50% by mass or more. The upper limit of the content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group is not limited. The content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is preferably 95% by mass or less, preferably 85% by mass or less, based on the total mass of the polymer A. Is more preferable. When the negative photosensitive resin layer contains a plurality of types of polymers A, the content ratio of the structural unit derived from the monomer having an aromatic hydrocarbon group is determined as a weight average value.
　芳香族炭化水素基を有する単量体としては、例えば、アラルキル基を有する単量体、スチレン、及び重合可能なスチレン誘導体（例えば、メチルスチレン、ビニルトルエン、ｔｅｒｔ－ブトキシスチレン、アセトキシスチレン、４－ビニル安息香酸、スチレンダイマー、及びスチレントリマー）が挙げられる。芳香族炭化水素基を有する単量体は、アラルキル基を有する単量体、又はスチレンであることが好ましい。 Examples of the monomer having an aromatic hydrocarbon group include a monomer having an aralkyl group, styrene, and a polymerizable styrene derivative (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-). Vinyl benzoic acid, styrene dimer, and styrene trimmer). The monomer having an aromatic hydrocarbon group is preferably a monomer having an aralkyl group or styrene.
　アラルキル基としては、置換又は非置換のフェニルアルキル基（ベンジル基を除く）、及び置換又は非置換のベンジル基が挙げられ、置換又は非置換のベンジル基が好ましい。 Examples of the aralkyl group include a substituted or unsubstituted phenylalkyl group (excluding a benzyl group) and a substituted or unsubstituted benzyl group, and a substituted or unsubstituted benzyl group is preferable.
　フェニルアルキル基を有する単量体としては、例えば、フェニルエチル（メタ）アクリレートが挙げられる。 Examples of the monomer having a phenylalkyl group include phenylethyl (meth) acrylate.
　ベンジル基を有する単量体としては、ベンジル基を有する（メタ）アクリレート（例えば、ベンジル（メタ）アクリレート、及びクロロベンジル（メタ）アクリレート）、ベンジル基を有するビニルモノマー（例えば、ビニルベンジルクロライド、及びビニルベンジルアルコール）が挙げられる。ベンジル基を有する単量体は、ベンジル（メタ）アクリレートであることが好ましい。 Examples of the monomer having a benzyl group include a (meth) acrylate having a benzyl group (for example, benzyl (meth) acrylate and a chlorobenzyl (meth) acrylate), a vinyl monomer having a benzyl group (for example, vinylbenzyl chloride, and the like). Vinyl benzyl alcohol). The monomer having a benzyl group is preferably a benzyl (meth) acrylate.
　ある実施形態において、重合体Ａにおける芳香族炭化水素基を有する単量体に由来する構成単位がベンジル（メタ）アクリレートに由来する構成単位である場合、重合体Ａにおけるベンジル（メタ）アクリレート単量体に由来する構成単位の含有割合は、重合体Ａの全質量に対して、５０質量％～９５質量％であることが好ましく、６０質量％～９０質量％であることがより好ましく、７０質量％～９０質量％であることが更に好ましく、７５質量％～９０質量％であることが特に好ましい。 In certain embodiments, when the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is the structural unit derived from the benzyl (meth) acrylate, the benzyl (meth) acrylate single amount in the polymer A is used. The content ratio of the structural unit derived from the body is preferably 50% by mass to 95% by mass, more preferably 60% by mass to 90% by mass, and 70% by mass, based on the total mass of the polymer A. It is more preferably% to 90% by mass, and particularly preferably 75% by mass to 90% by mass.
　ある実施形態において、重合体Ａにおける芳香族炭化水素基を有する単量体に由来する構成単位がスチレンに由来する構成単位である場合、重合体Ａにおけるスチレンに由来する構成単位の含有割合は、重合体Ａの全質量に対して、２０質量％～５５質量％であることが好ましく、２５～４５質量％であることがより好ましく、３０質量％～４０質量％であることが更に好ましく、３０質量％～３５質量％であることが特に好ましい。 In a certain embodiment, when the structural unit derived from the monomer having an aromatic hydrocarbon group in the polymer A is the structural unit derived from styrene, the content ratio of the structural unit derived from styrene in the polymer A is determined. It is preferably 20% by mass to 55% by mass, more preferably 25 to 45% by mass, further preferably 30% by mass to 40% by mass, and 30% by mass, based on the total mass of the polymer A. It is particularly preferably from mass% to 35% by mass.
　ある実施形態において、芳香族炭化水素基を有する単量体に由来する構成単位を有する重合体Ａは、芳香族炭化水素基を有する単量体と、後述する第一の単量体、及び後述する第二の単量体よりなる群から選択される少なくとも１種と、を重合することで得られる共重合体であることが好ましい。上記共重合体は、芳香族炭化水素基を有する単量体に由来する構成単位と、第一の単量体に由来する構成単位、及び第二の単量体に由来する構成単位よりなる群から選択される少なくとも１種と、を有する。 In a certain embodiment, the polymer A having a structural unit derived from a monomer having an aromatic hydrocarbon group includes a monomer having an aromatic hydrocarbon group, a first monomer described later, and a monomer described later. It is preferable that the copolymer is obtained by polymerizing at least one selected from the group consisting of the second monomer. The copolymer is a group consisting of a structural unit derived from a monomer having an aromatic hydrocarbon group, a structural unit derived from the first monomer, and a structural unit derived from the second monomer. It has at least one selected from.
　重合体Ａは、芳香族炭化水素基を有する単量体に由来する構成単位を有しない重合体であってもよい。芳香族炭化水素基を有する単量体に由来する構成単位を有しない重合体Ａは、後述する第一の単量体（芳香族炭化水素基を有する単量体を除く。）の少なくとも１種を重合することで得られる重合体であることが好ましく、後述する第一の単量体（芳香族炭化水素基を有する単量体を除く。）の少なくとも１種と、後述する第二の単量体（芳香族炭化水素基を有する単量体を除く。）の少なくとも１種と、を重合することにより得られる共重合体であることがより好ましい。 The polymer A may be a polymer having no structural unit derived from a monomer having an aromatic hydrocarbon group. The polymer A having no structural unit derived from the monomer having an aromatic hydrocarbon group is at least one kind of the first monomer (excluding the monomer having an aromatic hydrocarbon group) described later. It is preferable that the polymer is obtained by polymerizing the above, and at least one of the first monomer (excluding the monomer having an aromatic hydrocarbon group) described later and the second simpler described later. It is more preferable that it is a copolymer obtained by polymerizing at least one of a dimer (excluding a monomer having an aromatic hydrocarbon group).
　ある実施形態において、重合体Ａは、後述する第一の単量体の少なくとも１種を重合することで得られる重合体であることが好ましく、後述する第一の単量体の少なくとも１種と、後述する第二の単量体の少なくとも１種と、を重合することにより得られる共重合体であることがより好ましい。上記共重合体は、第一の単量体に由来する構成単位と、第二の単量体に由来する構成単位と、を有する。 In a certain embodiment, the polymer A is preferably a polymer obtained by polymerizing at least one of the first monomers described later, and is preferably the same as at least one of the first monomers described below. It is more preferable that the copolymer is obtained by polymerizing with at least one of the second monomers described later. The copolymer has a structural unit derived from the first monomer and a structural unit derived from the second monomer.
　第一の単量体は、分子中にカルボキシ基と重合性不飽和基とを有する単量体である。第一の単量体は、分子中に芳香族炭化水素基を有しない単量体であってもよい。第一の単量体としては、例えば、（メタ）アクリル酸、フマル酸、ケイ皮酸、クロトン酸、イタコン酸、４－ビニル安息香酸、マレイン酸無水物、及びマレイン酸半エステルが挙げられる。第一の単量体は、（メタ）アクリル酸であることが好ましい。 The first monomer is a monomer having a carboxy group and a polymerizable unsaturated group in the molecule. The first monomer may be a monomer having no aromatic hydrocarbon group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid semiester. The first monomer is preferably (meth) acrylic acid.
　重合体Ａにおける第一の単量体に由来する構成単位の含有割合は、重合体Ａの全質量に対して、５質量％～５０質量％であることが好ましく、１０質量％～４０質量％であることがより好ましく、１５質量％～３０質量％であることが特に好ましい。 The content ratio of the structural unit derived from the first monomer in the polymer A is preferably 5% by mass to 50% by mass, and 10% by mass to 40% by mass, based on the total mass of the polymer A. Is more preferable, and 15% by mass to 30% by mass is particularly preferable.
　第二の単量体は、非酸性であり、かつ、分子中に少なくとも１つの重合性不飽和基を有する単量体である。第二の単量体は、分子中に芳香族炭化水素基を有しない単量体であってもよい。第二の単量体としては、例えば、（メタ）アクリレート化合物、ビニルアルコールのエステル化合物、及び（メタ）アクリロニトリルが挙げられる。本開示において、「（メタ）アクリロニトリル」は、アクリロニトリル、メタクリロニトリル、又はアクリロニトリル及びメタクリロニトリルの両方を包含する。 The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. The second monomer may be a monomer having no aromatic hydrocarbon group in the molecule. Examples of the second monomer include a (meth) acrylate compound, an ester compound of vinyl alcohol, and (meth) acrylonitrile. In the present disclosure, "(meth) acrylonitrile" includes acrylonitrile, methacrylonitrile, or both acrylonitrile and methacrylonitrile.
　（メタ）アクリレート化合物としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、及び２－エチルヘキシル（メタ）アクリレートが挙げられる。
　（メタ）アクリレート化合物としては、脂環式アルキル基、直鎖状アルキル基、分岐状アルキル基を有するものが挙げられる。 Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. Examples thereof include tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
Examples of the (meth) acrylate compound include those having an alicyclic alkyl group, a linear alkyl group, and a branched alkyl group.
　ビニルアルコールのエステル化合物としては、例えば、酢酸ビニルが挙げられる。 Examples of the ester compound of vinyl alcohol include vinyl acetate.
　第二の単量体は、メチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、及びｎ－ブチル（メタ）アクリレートよりなる群から選択される少なくとも１種であることが好ましく、メチル（メタ）アクリレートであることがより好ましい。 The second monomer is preferably at least one selected from the group consisting of methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-butyl (meth) acrylate, and is preferably methyl (meth). More preferably, it is an acrylate.
　重合体Ａにおける第二の単量体に由来する構成単位の含有割合は、重合体Ａの全質量に対して、５質量％～６０質量％であることが好ましく、１５質量％～５０質量％であることがより好ましく、２０質量％～４５質量％であることが特に好ましい。 The content ratio of the structural unit derived from the second monomer in the polymer A is preferably 5% by mass to 60% by mass, and 15% by mass to 50% by mass, based on the total mass of the polymer A. Is more preferable, and 20% by mass to 45% by mass is particularly preferable.
　重合体Ａは、露光時の焦点位置がずれたときの線幅太り、及び解像度の悪化を抑制する観点から、アラルキル基を有する単量体に由来する構成単位、及びスチレンに由来する構成単位よりなる群から選択される少なくとも１種を含むことが好ましい。例えば、重合体Ａは、メタクリル酸に由来する構成単位と、ベンジルメタクリレートに由来する構成単位と、スチレンに由来する構成単位と、を含む共重合体、及びメタクリル酸に由来する構成単位と、メチルメタクリレートに由来する構成単位と、ベンジルメタクリレートに由来する構成単位と、スチレンに由来する構成単位と、を含む共重合体よりなる群から選択される少なくとも１種であることが好ましい。 The polymer A is composed of a structural unit derived from a monomer having an aralkyl group and a structural unit derived from styrene from the viewpoint of suppressing the line width thickening when the focal position is deviated during exposure and the deterioration of resolution. It is preferable to include at least one selected from the group. For example, the polymer A is a copolymer containing a structural unit derived from methacrylic acid, a structural unit derived from benzyl methacrylate, a structural unit derived from styrene, a structural unit derived from methacrylic acid, and methyl. It is preferably at least one selected from the group consisting of copolymers containing a structural unit derived from methacrylate, a structural unit derived from benzyl methacrylate, and a structural unit derived from styrene.
　ある実施形態において、重合体Ａは、芳香族炭化水素基を有する単量体に由来する構成単位を２５質量％～６０質量％、第一の単量体に由来する構成単位を２０質量％～５５質量％、及び第二の単量体に由来する構成単位を２０質量％～５５質量％含む重合体であることが好ましい。重合体Ａは、芳香族炭化水素基を有する単量体に由来する構成単位を２５質量％～４０質量％、第一の単量体に由来する構成単位を２０質量％～３５質量％、及び第二の単量体に由来する構成単位を３０質量％～４５質量％含む重合体であることがより好ましい。 In a certain embodiment, the polymer A contains 25% by mass to 60% by mass of a structural unit derived from a monomer having an aromatic hydrocarbon group and 20% by mass or more of a structural unit derived from a first monomer. A polymer containing 55% by mass and 20% by mass to 55% by mass of a structural unit derived from the second monomer is preferable. In the polymer A, the structural unit derived from the monomer having an aromatic hydrocarbon group is 25% by mass to 40% by mass, the structural unit derived from the first monomer is 20% by mass to 35% by mass, and the like. A polymer containing 30% by mass to 45% by mass of a structural unit derived from the second monomer is more preferable.
　ある実施形態において、重合体Ａは、芳香族炭化水素基を有する単量体に由来する構成単位を７０質量％～９０質量％、及び第一の単量体に由来する構成単位を１０質量％～２５質量％含む重合体であることが好ましい。 In certain embodiments, the polymer A contains 70% by mass to 90% by mass of structural units derived from a monomer having an aromatic hydrocarbon group, and 10% by mass of a structural unit derived from a first monomer. It is preferably a polymer containing up to 25% by mass.
　重合体Ａのガラス転移温度（Ｔｇ）は、３０℃～１３５℃であることが好ましい。ネガ型感光性樹脂層において、重合体ＡのＴｇが１３５℃以下であることで、露光時の焦点位置がずれたときの線幅太り、及び解像度の悪化を抑制することができる。上記の観点から、重合体ＡのＴｇは、１３０℃以下であることがより好ましく、１２０℃以下であることが更に好ましく、１１０℃以下であることが特に好ましい。また、重合体ＡのＴｇが３０℃以上であることは、耐エッジフューズ性を向上させる観点から好ましい。上記の観点から、重合体ＡのＴｇは、４０℃以上であることがより好ましく、５０℃以上であることが更に好ましく、６０℃以上であることが特に好ましく、７０℃以上であることが最も好ましい。 The glass transition temperature (Tg) of the polymer A is preferably 30 ° C to 135 ° C. When the Tg of the polymer A is 135 ° C. or lower in the negative photosensitive resin layer, it is possible to suppress the line width thickening and the deterioration of the resolution when the focal position is deviated during exposure. From the above viewpoint, the Tg of the polymer A is more preferably 130 ° C. or lower, further preferably 120 ° C. or lower, and particularly preferably 110 ° C. or lower. Further, it is preferable that the Tg of the polymer A is 30 ° C. or higher from the viewpoint of improving the edge fuse resistance. From the above viewpoint, the Tg of the polymer A is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, particularly preferably 60 ° C. or higher, and most preferably 70 ° C. or higher. preferable.
　重合体Ａは、市販品、又は合成品であってもよい。重合体Ａの合成は、例えば、上記した少なくとも１種の単量体を溶剤（例えば、アセトン、メチルエチルケトン、又はイソプロパノール）で希釈した溶液に、ラジカル重合開始剤（例えば、過酸化ベンゾイル、又はアゾイソブチロニトリル）を適量添加し、次いで、加熱撹拌することによって行われることが好ましい。また、混合物の一部を反応液に滴下しながら合成を行う場合もある。反応終了後、更に溶剤を加えて、所望の濃度に調整する場合もある。合成手段としては、溶液重合以外に、塊状重合、懸濁重合、又は乳化重合を用いてもよい。 The polymer A may be a commercially available product or a synthetic product. Polymer A is synthesized, for example, by diluting at least one of the above-mentioned monomers with a solvent (for example, acetone, methyl ethyl ketone, or isopropanol) and a radical polymerization initiator (for example, benzoyl peroxide or azoisobuty) in a solution. Butyronitrile) is preferably added in an appropriate amount, and then heated and stirred. In some cases, the synthesis is carried out while dropping a part of the mixture into the reaction solution. After completion of the reaction, a solvent may be further added to adjust the concentration to a desired level. As the synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.
　ネガ型感光性樹脂層Ｎは、１種単独、又は２種以上のアルカリ可溶性高分子を含んでもよい。 The negative type photosensitive resin layer N may contain one kind alone or two or more kinds of alkali-soluble polymers.
　アルカリ可溶性高分子の含有割合は、ネガ型感光性樹脂層Ｎの全質量に対して、１０質量％～９０質量％であることが好ましく、３０質量％～７０質量％であることがより好ましく、４０質量％～６０質量％であることが特に好ましい。ネガ型感光性樹脂層Ｎに対するアルカリ可溶性高分子の含有割合を９０質量％以下にすることは、現像時間を制御する観点から好ましい。一方で、ネガ型感光性樹脂層Ｎに対するアルカリ可溶性高分子の含有割合を１０質量％以上にすることは、耐エッジフューズ性を向上させる観点から好ましい。 The content ratio of the alkali-soluble polymer is preferably 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, based on the total mass of the negative photosensitive resin layer N. It is particularly preferably 40% by mass to 60% by mass. It is preferable that the content ratio of the alkali-soluble polymer to the negative photosensitive resin layer N is 90% by mass or less from the viewpoint of controlling the developing time. On the other hand, it is preferable that the content ratio of the alkali-soluble polymer with respect to the negative photosensitive resin layer N is 10% by mass or more from the viewpoint of improving the edge fuse resistance.
　ネガ型感光性樹脂層Ｎが２種以上のアルカリ可溶性高分子を含む場合、ネガ型感光性樹脂層Ｎは、芳香族炭化水素基を有する単量体に由来する構成単位を有する２種以上のアルカリ可溶性高分子を含むこと、又は芳香族炭化水素基を有する単量体に由来する構成単位を有するアルカリ可溶性高分子と、芳香族炭化水素基を有する単量体に由来する構成単位を有しないアルカリ可溶性高分子と、を含むことが好ましい。後者の場合、芳香族炭化水素基を有する単量体に由来する構成単位を有するアルカリ可溶性高分子の含有割合は、アルカリ可溶性高分子の全質量に対して、５０質量％以上であることが好ましく、７０質量％以上であることがより好ましく、８０質量％以上であることが更に好ましく、９０質量％以上であることが特に好ましい。 When the negative type photosensitive resin layer N contains two or more kinds of alkali-soluble polymers, the negative type photosensitive resin layer N has two or more kinds having a structural unit derived from a monomer having an aromatic hydrocarbon group. It does not have a structural unit derived from an alkali-soluble polymer or a monomer having an aromatic hydrocarbon group, and an alkali-soluble polymer having a structural unit derived from a monomer having an aromatic hydrocarbon group. It preferably contains an alkali-soluble polymer. In the latter case, the content ratio of the alkali-soluble polymer having a structural unit derived from the monomer having an aromatic hydrocarbon group is preferably 50% by mass or more with respect to the total mass of the alkali-soluble polymer. , 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
－重合性化合物－
　ネガ型感光性樹脂層Ｎは、重合性化合物を含むことが好ましい。
　本開示において、「重合性化合物」とは、重合反応に関与する結合、又は重合性基を有し、後述する重合開始剤の作用を受けて重合する化合物を意味する。
　また、本開示における重合性化合物は、上記アルカリ可溶性高分子とは異なる化合物であり、分子量５，０００未満であることが好ましい。
　重合性化合物としては、エチレン性不飽和化合物が好ましい。
　上記エチレン性不飽和化合物として、得られる硬化膜の強度、基板密着性、現像残渣抑制性、及び、防錆性の観点から、酸基を有するエチレン性不飽和化合物とを含むことが好ましく、後述する式（Ｍ）で表される化合物と、酸基を有するエチレン性不飽和化合物とを含むことがより好ましい。 -Polymerizable compound-
The negative photosensitive resin layer N preferably contains a polymerizable compound.
In the present disclosure, the "polymerizable compound" means a compound having a bond or a polymerizable group involved in a polymerization reaction and polymerizing under the action of a polymerization initiator described later.
Further, the polymerizable compound in the present disclosure is a compound different from the alkali-soluble polymer, and preferably has a molecular weight of less than 5,000.
As the polymerizable compound, an ethylenically unsaturated compound is preferable.
The ethylenically unsaturated compound preferably contains an ethylenically unsaturated compound having an acid group from the viewpoints of the strength of the obtained cured film, substrate adhesion, development residue inhibitory property, and rust prevention property, and will be described later. It is more preferable to contain the compound represented by the formula (M) and an ethylenically unsaturated compound having an acid group.
　上記エチレン性不飽和化合物は、現像残渣抑制性、防錆性、得られる硬化膜の曲げ耐性の観点から、下記式（Ｍ）で表される化合物（単に、「化合物Ｍ」ともいう。）を含むことが好ましい。
　　Ｑ２－Ｒ１－Ｑ１　　　式（Ｍ）
　式（Ｍ）中、Ｑ１及びＱ２はそれぞれ独立に、（メタ）アクリロイルオキシ基を表し、Ｒ１は鎖状構造を有する二価の連結基を表す。 The ethylenically unsaturated compound is a compound represented by the following formula (M) (simply also referred to as "Compound M") from the viewpoint of developing residue inhibitory property, rust preventive property, and bending resistance of the obtained cured film. It is preferable to include it.
Q 2 -R 1 -Q 1 formula (M)
In formula (M), Q 1 and Q 2 each independently represent a (meth) acryloyloxy group, and R 1 represents a divalent linking group having a chain structure.
　式（Ｍ）におけるＱ１及びＱ２は、合成容易性の観点から、Ｑ１及びＱ２は同じ基であることが好ましい。
　また、式（Ｍ）におけるＱ１及びＱ２は、反応性の観点から、アクリロイルオキシ基であることが好ましい。
　式（Ｍ）におけるＲ１は、得られる硬化膜の曲げ耐性の観点から、アルキレン基、アルキレンオキシアルキレン基（－Ｌ１－Ｏ－Ｌ１－）、又は、ポリアルキレンオキシアルキレン基（－（Ｌ１－Ｏ）ｐ－Ｌ１－）であることが好ましく、炭素数２～２０の炭化水素基、又は、ポリアルキレンオキシアルキレン基であることがより好ましく、炭素数４～２０のアルキレン基であることが更に好ましく、炭素数６～１８の直鎖アルキレン基であることが特に好ましい。上記炭化水素基は、少なくとも一部に鎖状構造を有していればよく、上記鎖状構造以外の部分としては、特に制限はなく、例えば、分岐鎖状、環状又は炭素数１～５の直鎖状アルキレン基、アリーレン基、エーテル結合、及び、それらの組み合わせのいずれであってもよく、得られる硬化膜の曲げ耐性の観点から、アルキレン基、又は、２以上のアルキレン基と１以上のアリーレン基とを組み合わせた基であることが好ましく、アルキレン基であることがより好ましく、直鎖アルキレン基であることが特に好ましい。
　なお、上記Ｌ１はそれぞれ独立に、アルキレン基を表し、エチレン基、プロピレン基、又は、ブチレン基であることが好ましく、エチレン基、又は、１，２－プロピレン基であることがより好ましい。ｐは２以上の整数を表し、２～１０の整数であることが好ましい。 It is preferable that Q 1 and Q 2 in the formula (M) have the same group as Q 1 and Q 2 from the viewpoint of easiness of synthesis.
Further, Q 1 and Q 2 in the formula (M) are preferably acryloyloxy groups from the viewpoint of reactivity.
R 1 in the formula (M), from the viewpoint of bending resistance of the obtained cured film, an alkylene group, an alkylene oxyalkylene group (-L 1 -O-L 1 - ), or, polyalkylene oxyalkylene group (- (L 1- O) p- L 1- ) is preferable, and a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferable, and an alkylene group having 4 to 20 carbon atoms is used. It is more preferable, and it is particularly preferable that it is a linear alkylene group having 6 to 18 carbon atoms. The hydrocarbon group may have a chain structure at least in part, and the portion other than the chain structure is not particularly limited, and is, for example, branched chain, cyclic, or having 1 to 5 carbon atoms. It may be any of a linear alkylene group, an arylene group, an ether bond, and a combination thereof, and from the viewpoint of bending resistance of the obtained cured film, an alkylene group or two or more alkylene groups and one or more. It is preferably a group in combination with an arylene group, more preferably an alkylene group, and particularly preferably a linear alkylene group.
Each of the above L 1 independently represents an alkylene group, preferably an ethylene group, a propylene group, or a butylene group, and more preferably an ethylene group or a 1,2-propylene group. p represents an integer of 2 or more, and is preferably an integer of 2 to 10.
　また、化合物ＭにおけるＱ１とＱ２との間を連結する最短の連結鎖の原子数は、得られる硬化膜の透湿度及び曲げ耐性の観点から、３個～５０個であることが好ましく、４個～４０個であることがより好ましく、６個～２０個であることが更に好ましく、８個～１２個であることが特に好ましい。
　本開示において、「Ｑ１とＱ２の間を連結する最短の連結鎖の原子数」とは、Ｑ１に連結するＲ１における原子からＱ２に連結するＲ１における原子までを連結する最短の原子数である。 The atomic number of the connecting chain of the shortest for connecting the Q 1, Q 2 in the compound M, from the viewpoints of moisture permeability and bending resistance of the obtained cured film is preferably from 3 to 50, The number is more preferably 4 to 40, further preferably 6 to 20, and particularly preferably 8 to 12.
In this disclosure, the term "Q 1, Q atoms linking chain shortest connecting between two" shortest connecting the atom in R 1 be linked to Q 1 to atom in R 1 be linked to Q 2 Is the number of atoms in.
　化合物Ｍの具体例としては、１，３－ブタンジオールジ（メタ）アクリレート、テトラメチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，７－ヘプタンジオールジ（メタ）アクリレート、１，８－オクタンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、１，４－シクロヘキサンジオールジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、水添ビスフェノールＡのジ（メタ）アクリレート、水添ビスフェノールＦのジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレンレングリコールジ（メタ）アクリレート、ポリ（エチレングリコール／プロピレングリコール）ジ（メタ）アクリレート、ポリブチレングリコールジ（メタ）アクリレートが挙げられる。上記エステルモノマーは混合物としても使用できる。
　上記化合物の中でも、得られる硬化膜の曲げ耐性の観点から、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、及び、ネオペンチルグリコールジ（メタ）アクリレートよりなる群から選ばれた少なくとも１種の化合物であることが好ましく、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、及び、１，１０－デカンジオールジ（メタ）アクリレートよりなる群から選ばれた少なくとも１種の化合物であることがより好ましく、１，９－ノナンジオールジ（メタ）アクリレート、及び、１，１０－デカンジオールジ（メタ）アクリレートよりなる群から選ばれた少なくとも１種の化合物であることが特に好ましい。 Specific examples of the compound M include 1,3-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. 1,7-Heptanediol di (meth) acrylate, 1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, 1, 4-Cyclohexanediol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, hydrogenated bisphenol F di (meth) acrylate, polyethylene glycol di (meth) acrylate , Polypropylene glycol di (meth) acrylate, poly (ethylene glycol / propylene glycol) di (meth) acrylate, polybutylene glycol di (meth) acrylate. The ester monomer can also be used as a mixture.
Among the above compounds, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and 1,10-decanediol di (meth) acrylate from the viewpoint of bending resistance of the obtained cured film. It is preferably at least one compound selected from the group consisting of acrylates and neopentyl glycol di (meth) acrylates, preferably 1,6-hexanediol di (meth) acrylates and 1,9-nonanediol di (). More preferably, it is at least one compound selected from the group consisting of meta) acrylate and 1,10-decanediol di (meth) acrylate, and 1,9-nonanediol di (meth) acrylate and It is particularly preferable that the compound is at least one selected from the group consisting of 1,10-decanediol di (meth) acrylate.
　化合物Ｍは、１種単独で使用してもよいし、２種以上を併用することもできる。
　化合物Ｍの含有量は、得られる硬化膜の透湿度及び曲げ耐性の観点から、ネガ型感光性樹脂層Ｎのエチレン性不飽和化合物の全質量に対し、１０質量％～９０質量％であることが好ましく、１５質量％～７０質量％であることがより好ましく、２０質量％～５０質量％であることが更に好ましく、２５質量％～３５質量％であることが特に好ましい。
　なお、本開示におけるエチレン性不飽和化合物とは、（重量平均）分子量が１０，０００以下の、エチレン性不飽和基を有する化合物をいう。
　また、化合物Ｍの含有量は、得られる硬化膜の透湿度及び曲げ耐性の観点から、ネガ型感光性樹脂層Ｎの全質量に対し、１質量％～３０質量％であることが好ましく、３質量％～２５質量％であることがより好ましく、５質量％～２０質量％であることが更に好ましく、６質量％～１４．５質量％であることが特に好ましい。 Compound M may be used alone or in combination of two or more.
The content of compound M is 10% by mass to 90% by mass with respect to the total mass of the ethylenically unsaturated compound of the negative photosensitive resin layer N from the viewpoint of moisture permeability and bending resistance of the obtained cured film. Is more preferable, 15% by mass to 70% by mass is more preferable, 20% by mass to 50% by mass is further preferable, and 25% by mass to 35% by mass is particularly preferable.
The ethylenically unsaturated compound in the present disclosure refers to a compound having an ethylenically unsaturated group having a (weight average) molecular weight of 10,000 or less.
The content of the compound M is preferably 1% by mass to 30% by mass with respect to the total mass of the negative photosensitive resin layer N from the viewpoint of moisture permeability and bending resistance of the obtained cured film. It is more preferably from mass% to 25% by mass, further preferably from 5% by mass to 20% by mass, and particularly preferably from 6% by mass to 14.5% by mass.
　また、エチレン性不飽和化合物としては、２官能以上のエチレン性不飽和化合物を含むことが好ましい。
　本開示において、「２官能以上のエチレン性不飽和化合物」とは、一分子中にエチレン性不飽和基を２つ以上有する化合物を意味する。
　エチレン性不飽和化合物におけるエチレン性不飽和基としては、（メタ）アクリロイル基が好ましい。
　エチレン性不飽和化合物としては、（メタ）アクリレート化合物が好ましい。 The ethylenically unsaturated compound preferably contains a bifunctional or higher functional ethylenically unsaturated compound.
In the present disclosure, the "bifunctional or higher functional ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule.
As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth) acryloyl group is preferable.
As the ethylenically unsaturated compound, a (meth) acrylate compound is preferable.
　エチレン性不飽和化合物としては、例えば、硬化後における硬化膜の強度の観点から、２官能のエチレン性不飽和化合物（好ましくは、２官能の（メタ）アクリレート化合物）と、３官能以上のエチレン性不飽和化合物（好ましくは、３官能以上の（メタ）アクリレート化合物）と、を含むことが特に好ましい。 Examples of the ethylenically unsaturated compound include a bifunctional ethylenically unsaturated compound (preferably a bifunctional (meth) acrylate compound) and a trifunctional or higher functional ethylenic compound from the viewpoint of the strength of the cured film after curing. It is particularly preferred to include unsaturated compounds (preferably trifunctional or higher functional (meth) acrylate compounds).
＜＜重合性化合物Ｂ＞＞
　ネガ型感光性樹脂層Ｎは、重合性化合物Ｂを含むことが好ましい。なお、重合性化合物Ｂは、上記重合体Ａとは異なる化合物である。
　重合性化合物Ｂにおける重合反応に関与する結合としては、例えば、エチレン性不飽和結合が好ましく挙げられる。 << Polymerizable Compound B >>
The negative photosensitive resin layer N preferably contains the polymerizable compound B. The polymerizable compound B is a compound different from the polymer A.
As the bond involved in the polymerization reaction in the polymerizable compound B, for example, an ethylenically unsaturated bond is preferably mentioned.
　重合性化合物Ｂにおける重合性基は、重合反応に関与する基であれば制限されない。重合性化合物Ｂにおける重合性基としては、例えば、エチレン性不飽和結合を含む基（例えば、ビニル基、アクリロイル基、メタクリロイル基、スチリル基、及びマレイミド基）、及びカチオン性重合性基（例えば、エポキシ基、及びオキセタン基）が挙げられる。重合性基は、エチレン性不飽和結合を含む基（以下、「エチレン性不飽和基」という場合がある。）であることが好ましく、アクリロイル基、又はメタアクリロイル基であることがより好ましい。 The polymerizable group in the polymerizable compound B is not limited as long as it is a group involved in the polymerization reaction. Examples of the polymerizable group in the polymerizable compound B include a group containing an ethylenically unsaturated bond (for example, a vinyl group, an acryloyl group, a methacryloyl group, a styryl group, and a maleimide group), and a cationically polymerizable group (for example, a cationically polymerizable group). Epoxide group and oxetane group). The polymerizable group is preferably a group containing an ethylenically unsaturated bond (hereinafter, may be referred to as an "ethylenically unsaturated group"), and more preferably an acryloyl group or a metaacryloyl group.
　重合性化合物Ｂは、ネガ型感光性樹脂層Ｎの感光性がより優れる点で、エチレン性不飽和結合を有する化合物であることが好ましく、一分子中に１つ以上のエチレン性不飽和基を有する化合物（すなわち、エチレン性不飽和化合物）であることがより好ましく、一分子中に２つ以上のエチレン性不飽和基を有する化合物（すなわち、多官能エチレン性不飽和化合物）であることが特に好ましい。また、解像性、及び剥離性により優れる点で、一分子のエチレン性不飽和化合物に含まれるエチレン性不飽和基の数は、６つ以下であることが好ましく、３つ以下であることがより好ましく、２つ以下であることが特に好ましい。
　また、重合性化合物Ｂは、硬化性、並びに、得られる樹脂パターン２の永久膜としての強度及び耐久性の観点から、３官能以上のエチレン性不飽和化合物を含むことが好ましく、５官能以上のエチレン性不飽和化合物を含むことがより好ましい。 The polymerizable compound B is preferably a compound having an ethylenically unsaturated bond in that the negative photosensitive resin layer N is more excellent in photosensitivity, and has one or more ethylenically unsaturated groups in one molecule. It is more preferably a compound having (ie, an ethylenically unsaturated compound), and particularly preferably a compound having two or more ethylenically unsaturated groups in one molecule (ie, a polyfunctional ethylenically unsaturated compound). preferable. In addition, the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, and preferably 3 or less, in terms of being excellent in resolution and peelability. It is more preferable, and it is particularly preferable that the number is two or less.
Further, the polymerizable compound B preferably contains a trifunctional or higher functional ethylenically unsaturated compound from the viewpoint of curability and the strength and durability of the obtained resin pattern 2 as a permanent film, and is pentafunctional or higher. More preferably, it contains an ethylenically unsaturated compound.
　エチレン性不飽和化合物は、一分子中に１つ以上の（メタ）アクリロイル基を有する（メタ）アクリレート化合物であることが好ましい。 The ethylenically unsaturated compound is preferably a (meth) acrylate compound having one or more (meth) acryloyl groups in one molecule.
　重合性化合物Ｂは、ネガ型感光性樹脂層Ｎにおける感光性、解像性、及び剥離性のバランスがより優れる観点から、一分子中に２つのエチレン性不飽和基を有する化合物（すなわち、２官能エチレン性不飽和化合物）、及び一分子中に３つのエチレン性不飽和基を有する化合物（すなわち、３官能エチレン性不飽和化合物）よりなる群から選択される少なくとも１種を含むことが好ましく、一分子中に２つのエチレン性不飽和基を有する化合物を含むことがより好ましい。 The polymerizable compound B is a compound having two ethylenically unsaturated groups in one molecule (that is, 2) from the viewpoint of having a better balance of photosensitivity, resolution, and peelability in the negative photosensitive resin layer N. It is preferable to contain at least one selected from the group consisting of a functional ethylenically unsaturated compound) and a compound having three ethylenically unsaturated groups in one molecule (that is, a trifunctional ethylenically unsaturated compound). It is more preferable to contain a compound having two ethylenically unsaturated groups in one molecule.
　また、重合性化合物Ｂは、硬化後の強度及び寸法安定性の観点から、脂肪族環式骨格を有するエチレン性不飽和化合物を含むことが好ましく、脂肪族環式骨格を有するジ（メタ）アクリレート化合物を含むことがより好ましく、ジシクロペンタニル構造又はジシクロペンテニル構造を有するジ（メタ）アクリレート化合物を含むことが特に好ましい。
　更に、重合性化合物Ｂは、硬化後の強度及び寸法安定性の観点から、ジシクロペンタニル構造又はジシクロペンテニル構造を有するエチレン性不飽和化合物を含むことが好ましい。 Further, the polymerizable compound B preferably contains an ethylenically unsaturated compound having an aliphatic cyclic skeleton from the viewpoint of strength and dimensional stability after curing, and is a di (meth) acrylate having an aliphatic cyclic skeleton. It is more preferable to contain a compound, and it is particularly preferable to contain a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure.
Further, the polymerizable compound B preferably contains an ethylenically unsaturated compound having a dicyclopentanyl structure or a dicyclopentenyl structure from the viewpoint of strength and dimensional stability after curing.
　ネガ型感光性樹脂層Ｎにおいて、重合性化合物Ｂの含有量に対する２官能エチレン性不飽和化合物の含有量の割合は、ネガ型感光性樹脂層Ｎの剥離性が優れる観点から、４０質量％以上であることが好ましく、６０質量％以上であることがより好ましく、７０質量％超であることが特に好ましい。重合性化合物Ｂの含有量に対する２官能エチレン性不飽和化合物の含有割合の上限は、制限されず、１００質量％であってもよい。すなわち、ネガ型感光性樹脂層Ｎに含まれる重合性化合物Ｂが全て２官能エチレン性不飽和化合物であってもよい。 In the negative type photosensitive resin layer N, the ratio of the content of the bifunctional ethylenically unsaturated compound to the content of the polymerizable compound B is 40% by mass or more from the viewpoint of excellent peelability of the negative type photosensitive resin layer N. It is preferably 60% by mass or more, and particularly preferably more than 70% by mass. The upper limit of the content ratio of the bifunctional ethylenically unsaturated compound to the content of the polymerizable compound B is not limited and may be 100% by mass. That is, all the polymerizable compounds B contained in the negative photosensitive resin layer N may be bifunctional ethylenically unsaturated compounds.
－重合性化合物Ｂ１－
　本開示に係るネガ型感光性樹脂層Ｎは、一分子中に、１つ以上の芳香環、及び２つのエチレン性不飽和基を有する重合性化合物Ｂ１を含むことが好ましい。重合性化合物Ｂ１は、上記した重合性化合物Ｂのうち、一分子中に１つ以上の芳香環を有する２官能エチレン性不飽和化合物である。 -Polymerizable compound B1-
The negative photosensitive resin layer N according to the present disclosure preferably contains a polymerizable compound B1 having one or more aromatic rings and two ethylenically unsaturated groups in one molecule. The polymerizable compound B1 is a bifunctional ethylenically unsaturated compound having one or more aromatic rings in one molecule among the above-mentioned polymerizable compounds B.
　ネガ型感光性樹脂層において、重合性化合物Ｂの含有量に対する重合性化合物Ｂ１の含有量の割合は、解像性がより優れる観点から、４０質量％以上であることが好ましく、５０質量％以上であることがより好ましく、５５質量％以上であることが更に好ましく、６０質量％以上であることが特に好ましい。重合性化合物Ｂの含有量に対する重合性化合物Ｂ１の含有量の割合の上限は、制限されない。重合性化合物Ｂの含有量に対する重合性化合物Ｂ１の含有量の割合は、剥離性の点から、９９質量％以下であることが好ましく、９５質量％以下であることがより好ましく、９０質量％以下であることが更に好ましく、８５質量％以下であることが特に好ましい。 In the negative photosensitive resin layer, the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is preferably 40% by mass or more, preferably 50% by mass or more, from the viewpoint of better resolution. It is more preferably 55% by mass or more, and particularly preferably 60% by mass or more. The upper limit of the ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is not limited. The ratio of the content of the polymerizable compound B1 to the content of the polymerizable compound B is preferably 99% by mass or less, more preferably 95% by mass or less, and 90% by mass or less from the viewpoint of peelability. Is more preferable, and 85% by mass or less is particularly preferable.
　重合性化合物Ｂ１における芳香環としては、例えば、芳香族炭化水素環（例えば、ベンゼン環、ナフタレン環、及びアントラセン環）、芳香族複素環（例えば、チオフェン環、フラン環、ピロール環、イミダゾール環、トリアゾール環、及びピリジン環）、及びこれらの縮合環が挙げられる。芳香環は、芳香族炭化水素環であることが好ましく、ベンゼン環であることがより好ましい。なお、芳香環は、置換基を有してもよい。 Examples of the aromatic ring in the polymerizable compound B1 include an aromatic hydrocarbon ring (for example, a benzene ring, a naphthalene ring, and an anthracene ring) and an aromatic heterocycle (for example, a thiophene ring, a furan ring, a pyrrole ring, and an imidazole ring. Triazole ring and pyridine ring), and fused rings thereof. The aromatic ring is preferably an aromatic hydrocarbon ring, more preferably a benzene ring. The aromatic ring may have a substituent.
　重合性化合物Ｂ１は、現像液によるネガ型感光性樹脂層Ｎの膨潤を抑制することにより、解像性が向上する点から、ビスフェノール構造を有することが好ましい。ビスフェノール構造としては、例えば、ビスフェノールＡ（すなわち、２，２－ビス（４－ヒドロキシフェニル）プロパン）に由来するビスフェノールＡ構造、ビスフェノールＦ（すなわち、２，２－ビス（４－ヒドロキシフェニル）メタン）に由来するビスフェノールＦ構造、及びビスフェノールＢ（すなわち、２，２－ビス（４－ヒドロキシフェニル）ブタン）に由来するビスフェノールＢ構造が挙げられる。ビスフェノール構造は、ビスフェノールＡ構造であることが好ましい。 The polymerizable compound B1 preferably has a bisphenol structure from the viewpoint of improving the resolution by suppressing the swelling of the negative photosensitive resin layer N due to the developing solution. Examples of the bisphenol structure include a bisphenol A structure derived from bisphenol A (that is, 2,2-bis (4-hydroxyphenyl) propane) and bisphenol F (that is, 2,2-bis (4-hydroxyphenyl) methane). Examples include a bisphenol F structure derived from bisphenol B and a bisphenol B structure derived from bisphenol B (that is, 2,2-bis (4-hydroxyphenyl) butane). The bisphenol structure is preferably a bisphenol A structure.
　ビスフェノール構造を有する重合性化合物Ｂ１としては、例えば、ビスフェノール構造と、上記ビスフェノール構造の両端に結合した２つの重合性基（好ましくは（メタ）アクリロイル基）と、を有する化合物が挙げられる。各重合性基は、ビスフェノール構造に直接結合してもよい。各重合性基は、１つ以上のアルキレンオキシ基を介してビスフェノール構造に結合してもよい。ビスフェノール構造の両端に付加するアルキレンオキシ基は、エチレンオキシ基、又はプロピレンオキシ基であることが好ましく、エチレンオキシ基であることがより好ましい。ビスフェノール構造に付加するアルキレンオキシ基の付加数は、制限されないが、一分子あたり４個～１６個であることが好ましく、６個～１４個であることがより好ましい。 Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two polymerizable groups (preferably (meth) acryloyl groups) bonded to both ends of the bisphenol structure. Each polymerizable group may be directly attached to the bisphenol structure. Each polymerizable group may be attached to the bisphenol structure via one or more alkyleneoxy groups. The alkyleneoxy group added to both ends of the bisphenol structure is preferably an ethyleneoxy group or a propyleneoxy group, and more preferably an ethyleneoxy group. The number of alkyleneoxy groups added to the bisphenol structure is not limited, but is preferably 4 to 16 per molecule, and more preferably 6 to 14.
　ビスフェノール構造を有する重合性化合物Ｂ１については、特開２０１６－２２４１６２号公報の段落００７２～段落００８０に記載されている。上記公報の内容は、参照により本明細書に組み込まれる。 The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A-2016-224162. The contents of the above publication are incorporated herein by reference.
　重合性化合物Ｂ１は、ビスフェノールＡ構造を有する２官能エチレン性不飽和化合物であることが好ましく、２，２－ビス（４－（（メタ）アクリロキシポリアルコキシ）フェニル）プロパンであることがより好ましい。 The polymerizable compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A structure, and more preferably 2,2-bis (4-((meth) acryloxypolyalkoxy) phenyl) propane. ..
　２，２－ビス（４－（（メタ）アクリロキシポリアルコキシ）フェニル）プロパンとしては、例えば、２，２－ビス（４－（メタクリロキシジエトキシ）フェニル）プロパン（ＦＡ－３２４Ｍ、日立化成（株））、２，２－ビス（４－（メタクリロキシエトキシプロポキシ）フェニル）プロパン、２，２－ビス（４－（メタクリロキシペンタエトキシ）フェニル）プロパン（ＢＰＥ－５００、新中村化学工業（株））、２，２－ビス（４－（メタクリロキシドデカエトキシテトラプロポキシ）フェニル）プロパン（ＦＡ－３２００ＭＹ、日立化成（株））、２，２－ビス（４－（メタクリロキシペンタデカエトキシ）フェニル）プロパン（ＢＰＥ－１３００、新中村化学工業（株））、２，２－ビス（４－（メタクリロキシジエトキシ）フェニル）プロパン（ＢＰＥ－２００、新中村化学工業（株））、及びエトキシ化（１０）ビスフェノールＡジアクリレート（ＮＫエステルＡ－ＢＰＥ－１０、新中村化学工業（株））が挙げられる。 Examples of the 2,2-bis (4-((meth) acryloxipolyalkoxy) phenyl) propane include 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (FA-324M, Hitachi Chemical Co., Ltd.). Co., Ltd.), 2,2-bis (4- (methacryloxyethoxypropoxy) phenyl) propane, 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane (BPE-500, Shin-Nakamura Chemical Industry Co., Ltd.) )), 2,2-Bis (4- (methacryloxydodecaethoxytetrapropoxy) phenyl) propane (FA-3200MY, Hitachi Chemical Co., Ltd.), 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) ) Propane (BPE-1300, Shin-Nakamura Chemical Industry Co., Ltd.), 2,2-bis (4- (methacryloxydiethoxy) phenyl) propane (BPE-200, Shin-Nakamura Chemical Industry Co., Ltd.), and ethoxylation (10) Examples thereof include bisphenol A diacrylate (NK ester A-BPE-10, Shin-Nakamura Chemical Industry Co., Ltd.).
　重合性化合物Ｂ１としては、例えば、下記一般式（Ｉ）で表される化合物も挙げられる。 Examples of the polymerizable compound B1 include a compound represented by the following general formula (I).
Figure JPOXMLDOC01-appb-C000001
 
Figure JPOXMLDOC01-appb-C000001
 
　一般式（Ｉ）中、Ｒ１、及びＲ２は、それぞれ独立して、水素原子、又はメチル基を表し、Ａは、Ｃ２Ｈ４を表し、Ｂは、Ｃ３Ｈ６を表し、ｎ１、及びｎ３は、それぞれ独立して、１～３９の整数であり、ｎ１＋ｎ３は、２～４０の整数であり、ｎ２、及びｎ４は、それぞれ独立して、０～２９の整数であり、ｎ２＋ｎ４は、０～３０の整数であり、－（Ａ－Ｏ）－、及び－（Ｂ－Ｏ）－の繰り返し単位の配列は、ランダム、又はブロックであってもよい。ブロックの場合、－（Ａ－Ｏ）－、及び－（Ｂ－Ｏ）－のいずれかがビスフェニル基側でもよい。ｎ２＋ｎ４は、０～１０の整数であることが好ましく、０～４の整数であることがより好ましく、０～２の整数であることが更に好ましく、０であることが特に好ましい。ｎ１＋ｎ２＋ｎ３＋ｎ４は、２～２０の整数であることが好ましく、２～１６の整数であることがより好ましく、４～１２の整数であることが特に好ましい。 In the general formula (I), R 1 and R 2 independently represent a hydrogen atom or a methyl group, A represents C 2 H 4 , B represents C 3 H 6 , and n. 1 and n 3 are independently integers from 1 to 39, n 1 + n 3 are integers from 2 to 40, and n 2 and n 4 are independent integers from 0 to 29, respectively. N 2 + n 4 is an integer of 0 to 30, and the sequence of repeating units of-(AO)-and-(BO)-is random or block. good. In the case of a block, either − (A—O) − or − (BO) − may be on the bisphenyl group side. n 2 + n 4 is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, further preferably an integer of 0 to 2, and particularly preferably 0. n 1 + n 2 + n 3 + n 4 is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 12.
　ネガ型感光性樹脂層Ｎは、１種単独、又は２種以上の重合性化合物Ｂ１を含んでもよい。 The negative type photosensitive resin layer N may contain one kind alone or two or more kinds of polymerizable compounds B1.
　ネガ型感光性樹脂層Ｎにおける重合性化合物Ｂ１の含有割合は、解像性がより優れる観点から、ネガ型感光性樹脂層Ｎの全質量に対して、１０質量％以上であることが好ましく、２０質量％以上であることがより好ましい。重合性化合物Ｂ１の含有割合の上限は、制限されない。ネガ型感光性樹脂層Ｎにおける重合性化合物Ｂ１の含有割合は、転写性、及び耐エッジフューズ性の観点から、ネガ型感光性樹脂層Ｎの全質量に対して、７０質量％以下であることが好ましく、６０質量％以下であることがより好ましい。 The content ratio of the polymerizable compound B1 in the negative photosensitive resin layer N is preferably 10% by mass or more with respect to the total mass of the negative photosensitive resin layer N from the viewpoint of better resolution. More preferably, it is 20% by mass or more. The upper limit of the content ratio of the polymerizable compound B1 is not limited. The content ratio of the polymerizable compound B1 in the negative photosensitive resin layer N shall be 70% by mass or less with respect to the total mass of the negative photosensitive resin layer N from the viewpoint of transferability and edge fuse resistance. Is preferable, and 60% by mass or less is more preferable.
　ネガ型感光性樹脂層Ｎは、重合性化合物Ｂ１、及び重合性化合物Ｂ１以外の重合性化合物Ｂを含んでもよい。重合性化合物Ｂ１以外の重合性化合物Ｂとしては、例えば、単官能エチレン性不飽和化合物（すなわち、一分子中に１つのエチレン性不飽和基を有する化合物）、芳香環を有しない２官能エチレン性不飽和化合物（すなわち、一分子中に芳香環を有しておらず、かつ、２つのエチレン性不飽和基を有する化合物）、及び３官能以上のエチレン性不飽和化合物（すなわち、一分子中に３つ以上のエチレン性不飽和基を有する化合物）が挙げられる。 The negative photosensitive resin layer N may contain a polymerizable compound B1 and a polymerizable compound B other than the polymerizable compound B1. Examples of the polymerizable compound B other than the polymerizable compound B1 include a monofunctional ethylenically unsaturated compound (that is, a compound having one ethylenically unsaturated group in one molecule) and a bifunctional ethylenically having no aromatic ring. Unsaturated compounds (ie, compounds that do not have an aromatic ring in one molecule and have two ethylenically unsaturated groups), and trifunctional or higher functional ethylenically unsaturated compounds (ie, in one molecule). Compounds having 3 or more ethylenically unsaturated groups).
　単官能エチレン性不飽和化合物としては、例えば、エチル（メタ）アクリレート、エチルヘキシル（メタ）アクリレート、２－（メタ）アクリロイルオキシエチルサクシネート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、及びフェノキシエチル（メタ）アクリレートが挙げられる。 Examples of the monofunctional ethylenically unsaturated compound include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinate, polyethylene glycol mono (meth) acrylate, and polypropylene glycol mono (meth) acrylate. , And phenoxyethyl (meth) acrylate.
　芳香環を有しない２官能エチレン性不飽和化合物としては、例えば、アルキレングリコールジ（メタ）アクリレート、ポリアルキレングリコールジ（メタ）アクリレート、ウレタンジ（メタ）アクリレート、及びトリメチロールプロパンジアクリレートが挙げられる。 Examples of the bifunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di (meth) acrylate, polyalkylene glycol di (meth) acrylate, urethane di (meth) acrylate, and trimethylolpropane diacrylate.
　アルキレングリコールジ（メタ）アクリレートとしては、例えば、トリシクロデカンジメタノールジアクリレート（Ａ－ＤＣＰ、新中村化学工業（株））、トリシクロデカンジメタノールジメタクリレート（ＤＣＰ、新中村化学工業（株））、１，９－ノナンジオールジアクリレート（Ａ－ＮＯＤ－Ｎ、新中村化学工業（株））、１，６－ヘキサンジオールジアクリレート（Ａ－ＨＤ－Ｎ、新中村化学工業（株））、エチレングリコールジメタクリレート、１，１０－デカンジオールジアクリレート、及びネオペンチルグリコールジ（メタ）アクリレートが挙げられる。 Examples of the alkylene glycol di (meth) acrylate include tricyclodecanedimethanol diacrylate (A-DCP, Shin-Nakamura Chemical Industry Co., Ltd.) and tricyclodecanedimethanol dimethacrylate (DCP, Shin-Nakamura Chemical Industry Co., Ltd.). ), 1,9-Nonandiol diacrylate (A-NOD-N, Shin-Nakamura Chemical Industry Co., Ltd.), 1,6-Hexanediol diacrylate (A-HD-N, Shin-Nakamura Chemical Industry Co., Ltd.), Examples thereof include ethylene glycol dimethacrylate, 1,10-decanediol diacrylate, and neopentyl glycol di (meth) acrylate.
　ポリアルキレングリコールジ（メタ）アクリレートとしては、例えば、ポリエチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジアクリレート、トリプロピレングリコールジアクリレート、及びポリプロピレングリコールジ（メタ）アクリレートが挙げられる。 Examples of the polyalkylene glycol di (meth) acrylate include polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di (meth) acrylate.
　ウレタンジ（メタ）アクリレートとしては、例えば、プロピレンオキサイド変性ウレタンジ（メタ）アクリレート、並びに、エチレンオキサイド及びプロピレンオキサイド変性ウレタンジ（メタ）アクリレートが挙げられる。市販品としては、例えば、８ＵＸ－０１５Ａ（大成ファインケミカル（株））、ＵＡ－３２Ｐ（新中村化学工業（株））、及びＵＡ－１１００Ｈ（新中村化学工業（株））が挙げられる。 Examples of the urethane di (meth) acrylate include propylene oxide-modified urethane di (meth) acrylate, and ethylene oxide and propylene oxide-modified urethane di (meth) acrylate. Examples of commercially available products include 8UX-015A (Taisei Fine Chemical Co., Ltd.), UA-32P (Shin-Nakamura Chemical Co., Ltd.), and UA-1100H (Shin-Nakamura Chemical Co., Ltd.).
　３官能以上のエチレン性不飽和化合物としては、例えば、ジペンタエリスリトール（トリ／テトラ／ペンタ／ヘキサ）（メタ）アクリレート、ペンタエリスリトール（トリ／テトラ）（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、イソシアヌル酸トリ（メタ）アクリレート、グリセリントリ（メタ）アクリレート、及びこれらのアルキレンオキサイド変性物が挙げられる。本開示において、「（トリ／テトラ／ペンタ／ヘキサ）（メタ）アクリレート」は、トリ（メタ）アクリレート、テトラ（メタ）アクリレート、ペンタ（メタ）アクリレート、及びヘキサ（メタ）アクリレートを包含する概念である。本開示において、「（トリ／テトラ）（メタ）アクリレート」は、トリ（メタ）アクリレート、及びテトラ（メタ）アクリレートを包含する概念である。 Examples of the trifunctional or higher functional ethylenically unsaturated compound include dipentaerythritol (tri / tetra / penta / hexa) (meth) acrylate, pentaerythritol (tri / tetra) (meth) acrylate, and trimethylolpropane tri (meth). Examples thereof include acrylates, trimethylolpropane tetra (meth) acrylates, trimethylolethanetri (meth) acrylates, tri (meth) acrylates of isocyanurates, glycerintri (meth) acrylates, and alkylene oxide modified products thereof. In the present disclosure, "(tri / tetra / penta / hexa) (meth) acrylate" is a concept that includes tri (meth) acrylate, tetra (meth) acrylate, penta (meth) acrylate, and hexa (meth) acrylate. be. In the present disclosure, "(tri / tetra) (meth) acrylate" is a concept including tri (meth) acrylate and tetra (meth) acrylate.
　３官能以上のエチレン性不飽和化合物のアルキレンオキサイド変性物としては、カプロラクトン変性（メタ）アクリレート化合物（例えば、日本化薬（株）製のＫＡＹＡＲＡＤ（登録商標）ＤＰＣＡ－２０、及び新中村化学工業（株）製のＡ－９３００－１ＣＬ）、アルキレンオキサイド変性（メタ）アクリレート化合物（例えば、日本化薬（株）製のＫＡＹＡＲＡＤ　ＲＰ－１０４０、新中村化学工業（株）製のＡＴＭ－３５Ｅ、新中村化学工業（株）製のＡ－９３００、及びダイセル・オルネクス社製のＥＢＥＣＲＹＬ（登録商標）　１３５）、エトキシル化グリセリントリアクリレート（例えば、新中村化学工業（株）製のＡ－ＧＬＹ－９Ｅ）、アロニックス（登録商標）ＴＯ－２３４９（東亞合成（株））、アロニックスＭ－５２０（東亞合成（株））、及びアロニックスＭ－５１０（東亞合成（株））が挙げられる。 Examples of the alkylene oxide-modified product of the trifunctional or higher functional ethylenically unsaturated compound include caprolactone-modified (meth) acrylate compound (for example, KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd.) and Shin Nakamura Chemical Industry Co., Ltd. ( A-9300-1CL manufactured by Shin Nakamura Chemical Industry Co., Ltd.), alkylene oxide-modified (meth) acrylate compound (for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E manufactured by Shin Nakamura Chemical Industry Co., Ltd., Shin Nakamura A-9300 manufactured by Chemical Industry Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Ornex, ethoxylated glycerin triacrylate (for example, A-GLY-9E manufactured by Shin Nakamura Chemical Industry Co., Ltd.), Examples thereof include Aronix (registered trademark) TO-2349 (Toa Synthetic Co., Ltd.), Aronix M-520 (Toa Synthetic Co., Ltd.), and Aronix M-510 (Toa Synthetic Co., Ltd.).
　重合性化合物Ｂ１以外の重合性化合物Ｂとしては、特開２００４－２３９９４２号公報の段落００２５～段落００３０に記載の酸基を有する重合性化合物も挙げられる。 Examples of the polymerizable compound B other than the polymerizable compound B1 include the polymerizable compounds having an acid group described in paragraphs 0025 to 0030 of JP-A-2004-239942.
　ある実施形態において、ネガ型感光性樹脂層Ｎは、重合性化合物Ｂ１、及び３官能以上のエチレン性不飽和化合物を含むことが好ましく、重合性化合物Ｂ１、及び２種以上の３官能以上のエチレン性不飽和化合物を含むことがより好ましい。上記実施形態において、重合性化合物Ｂ１と３官能以上のエチレン性不飽和化合物との質量比（［重合性化合物Ｂ１の合計質量］：［３官能以上のエチレン性不飽和化合物の合計質量］は、１：１～５：１であることが好ましく、１．２：１～４：１であることがより好ましく、１．５：１～３：１であることが特に好ましい。 In certain embodiments, the negative photosensitive resin layer N preferably contains a polymerizable compound B1 and a trifunctional or higher functional ethylenically unsaturated compound, preferably the polymerizable compound B1 and two or more trifunctional or higher ethylenes. It is more preferable to contain a sex unsaturated compound. In the above embodiment, the mass ratio of the polymerizable compound B1 to the trifunctional or higher ethylenically unsaturated compound ([total mass of the polymerizable compound B1]: [total mass of the trifunctional or higher ethylenically unsaturated compound] is It is preferably 1: 1 to 5: 1, more preferably 1.2: 1 to 4: 1, and particularly preferably 1.5: 1 to 3: 1.
　重合性化合物Ｂの重量平均分子量（Ｍｗ）は、２００～３，０００であることが好ましく、２８０～２，２００であることがより好ましく、３００～２，２００であることが特に好ましい。 The weight average molecular weight (Mw) of the polymerizable compound B is preferably 200 to 3,000, more preferably 280 to 2,200, and particularly preferably 300 to 2,200.
　ネガ型感光性樹脂層Ｎは、１種単独、又は２種以上の重合性化合物Ｂを含んでもよい。 The negative type photosensitive resin layer N may contain one kind alone or two or more kinds of polymerizable compounds B.
　ネガ型感光性樹脂層Ｎにおける重合性化合物Ｂの含有割合は、ネガ型感光性樹脂層Ｎの全質量に対して、１０質量％～７０質量％であることが好ましく、２０質量％～６０質量％であることがより好ましく、２０質量％～５０質量％であることが特に好ましい。 The content ratio of the polymerizable compound B in the negative photosensitive resin layer N is preferably 10% by mass to 70% by mass, preferably 20% by mass to 60% by mass, based on the total mass of the negative photosensitive resin layer N. It is more preferably%, and particularly preferably 20% by mass to 50% by mass.
－多官能エポキシ樹脂－
　ネガ型感光性樹脂層Ｎは、得られるパターン２の永久膜としての強度及び耐久性の観点から、多官能エポキシ樹脂を含むことが好ましく、多官能エポキシ樹脂、ヒドロキシ基含有化合物、及び、光カチオン重合開始剤を含むことがより好ましい。
　多官能エポキシ樹脂としては、例えば、１分子中に少なくとも２つのオキシラン基を有するエポキシ化合物、β位にアルキル基を有するエポキシ基を少なくとも１分子中に２つ含むエポキシ化合物などが挙げられる。 -Multifunctional epoxy resin-
The negative photosensitive resin layer N preferably contains a polyfunctional epoxy resin from the viewpoint of strength and durability of the obtained pattern 2 as a permanent film, and preferably contains a polyfunctional epoxy resin, a hydroxy group-containing compound, and a photocation. It is more preferable to include a polymerization initiator.
Examples of the polyfunctional epoxy resin include an epoxy compound having at least two oxylan groups in one molecule, an epoxy compound containing at least two epoxy groups having an alkyl group at the β-position in one molecule, and the like.
　上記１分子中に少なくとも２つのオキシラン基を有するエポキシ化合物としては、例えば、ビスフェノールＦ型エポキシ樹脂（エポトートＹＤＦ－１７０、東都化成（株）製）、ビキシレノール型もしくはビフェノール型エポキシ樹脂（「ＹＸ４０００、ジャパンエポキシレジン社製」等）又はこれらの混合物、イソシアヌレート骨格等を有する複素環式エポキシ樹脂（「ＴＥＰＩＣ、日産化学工業（株）製」、「アラルダイトＰＴ８１０、ハンツマンアドバンストマテリアルズ社製」等）、ビスフェノールＡ型エポキシ樹脂、ノボラック型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾ－ルノボラック型エポキシ樹脂、ハロゲン化エポキシ樹脂（例えば低臭素化エポキシ樹脂、高ハロゲン化エポキシ樹脂、臭素化フェノールノボラック型エポキシ樹脂など）、アリル基含有ビスフェノールＡ型エポキシ樹脂、トリスフェノールメタン型エポキシ樹脂、ジフェニルジメタノール型エポキシ樹脂、フェノールビフェニレン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂（「ＨＰ－７２００、ＨＰ－７２００Ｈ；ＤＩＣ（株）製」等）、グリシジルアミン型エポキシ樹脂（ジアミノジフェニルメタン型エポキシ樹脂、ジグリシジルアニリン、トリグリシジルアミノフェノール等）、グリジジルエステル型エポキシ樹脂（フタル酸ジグリシジルエステル、アジピン酸ジグリシジルエステル、ヘキサヒドロフタル酸ジグリシジルエステル、ダイマー酸ジグリシジルエステル等）ヒダントイン型エポキシ樹脂、脂環式エポキシ樹脂（３，４－エポキシシクロヘキシルメチル－３’，４’－エポキシシクロヘキサンカルボキシレート、ビス（３，４－エポキシシクロヘキシルメチル）アジペート、ジシクロペンタジエンジエポキシド、「ＧＴ－３００、ＧＴ－４００、ＺＥＨＰＥ３１５０；（株）ダイセル製」等、）、イミド型脂環式エポキシ樹脂、トリヒドロキシフェニルメタン型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、テトラフェニロールエタン型エポキシ樹脂、グリシジルフタレート樹脂、テトラグリシジルキシレノイルエタン樹脂、ナフタレン基含有エポキシ樹脂（ナフトールアラルキル型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、４官能ナフタレン型エポキシ樹脂、市販品としては「ＥＳＮ－１９０，ＥＳＮ－３６０；新日鉄化学（株）製」、「ＨＰ－４０３２，ＥＸＡ－４７５０，ＥＸＡ－４７００；ＤＩＣ（株）製」等）、フェノール化合物とジビニルベンゼンやジシクロペンタジエン等のジオレフィン化合物との付加反応によって得られるポリフェノール化合物と、エピクロルヒドリンとの反応物、４－ビニルシクロヘキセン－１－オキサイドの開環重合物を過酢酸等でエポキシ化したもの、ビスフェノールＡ型エポキシ樹脂、８官能ビスフェノールＡノボラック型エポキシ樹脂（例、レゾリューション・パフォーマンス・プロダクツ製　ＥＰＯＮ　ＳＵ－８）、ビスフェノールＦ型エポキシ樹脂のアルコール性ヒドロキシ基とエピクロルヒドリンとの反応により得られるエポキシ樹脂（例、日本化薬（株）製　ＮＥＲ－７６０４）、ビスフェノールＡ型エポキシ樹脂のアルコール性ヒドロキシ基とエピクロルヒドリンとの反応により得られるエポキシ樹脂（例、日本化薬（株）製　ＮＥＲ－１３０２）、ｏ－クレゾールノボラック型エポキシ樹脂（例、日本化薬（株）製　ＥＯＣＮ４４００）、ジ（メトキシメチルフェニル）とフェノールとを反応させて得られる樹脂のフェノール性ヒドロキシ基とエピクロルヒドリンとを反応させて得られるビフェニルフェノールノボラック型エポキシ樹脂（例、日本化薬（株）製　ＮＣ－３０００Ｈ）、環状含リン構造を有するエポキシ樹脂、α－メチルスチルベン型液晶エポキシ樹脂、ジベンゾイルオキシベンゼン型液晶エポキシ樹脂、アゾフェニル型液晶エポキシ樹脂、アゾメチンフェニル型液晶エポキシ樹脂、ビナフチル型液晶エポキシ樹脂、アジン型エポキシ樹脂、グリシジルメタアクリレート共重合系エポキシ樹脂（「ＣＰ－５０Ｓ，ＣＰ－５０Ｍ；日本油脂（株）製」等）、シクロヘキシルマレイミドとグリシジルメタアクリレートとの共重合エポキシ樹脂、ビス（グリシジルオキシフェニル）フルオレン型エポキシ樹脂、ビス（グリシジルオキシフェニル）アダマンタン型エポキシ樹脂などが挙げられる。これらは、１種単独で使用してもよいし、２種以上を併用してもよい。 Examples of the epoxy compound having at least two oxylan groups in one molecule include a bisphenol F type epoxy resin (Epototo YDF-170, manufactured by Toto Kasei Co., Ltd.), a bixilenol type or a biphenol type epoxy resin (“YX4000,” Japan Epoxy Resin Co., Ltd. ”, etc.) or a mixture thereof, a heterocyclic epoxy resin having an isocyanurate skeleton, etc. (“TEPIC, manufactured by Nissan Chemical Industry Co., Ltd.”, “Araldite PT810, manufactured by Huntsman Advanced Materials Co., Ltd.”, etc.) , Bisphenol A type epoxy resin, Novolak type epoxy resin, Bisphenol F type epoxy resin, Hydrogenated Bisphenol A type epoxy resin, Bisphenol S type epoxy resin, Phenol Novolak type epoxy resin, Cresole Novolak type epoxy resin, Halogenized epoxy resin ( For example, low brominated epoxy resin, high halogenated epoxy resin, brominated phenol novolac type epoxy resin, etc.), allyl group-containing bisphenol A type epoxy resin, trisphenol methane type epoxy resin, diphenyldimethanol type epoxy resin, phenol biphenylene type epoxy Resins, dicyclopentadiene type epoxy resins (“HP-7200, HP-7200H; manufactured by DIC Co., Ltd.”, etc.), glycidylamine type epoxy resins (diaminodiphenylmethane type epoxy resins, diglycidylaniline, triglycidylaminophenol, etc.), Glydil ester type epoxy resin (phthalic acid diglycidyl ester, adipic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester, etc.) Hydant-in type epoxy resin, alicyclic epoxy resin (3,4-epoxy) Cyclohexylmethyl-3', 4'-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, "GT-300, GT-400, ZEHPE3150; manufactured by Daicel Co., Ltd.", etc. ,), Imid type alicyclic epoxy resin, trihydroxyphenylmethane type epoxy resin, bisphenol A novolak type epoxy resin, tetraphenylol ethane type epoxy resin, glycidyl phthalate resin, tetraglycidyl xylenoyl ethane resin, naphthalene group-containing epoxy Resin (Naftor Aralkill type epoxy resin, naphthol novolac type epoxy resin, tetrafunctional naphthalene type d Epoxy resin, commercially available products such as "ESN-190, ESN-360; manufactured by Nippon Steel Chemical Co., Ltd.", "HP-4032, EXA-4750, EXA-4700; manufactured by DIC Co., Ltd."), phenol compounds and divinyl A reaction product of a polyphenol compound obtained by an addition reaction with a diolefin compound such as benzene or dicyclopentadiene and epichlorohydrin, or a ring-opened polymer of 4-vinylcyclohexene-1-oxide epoxidized with peracetic acid or the like. Bisphenol A type epoxy resin, octafunctional bisphenol A novolak type epoxy resin (eg, EPON SU-8 manufactured by Resolution Performance Products), epoxy obtained by reacting alcoholic hydroxy groups of bisphenol F type epoxy resin with epichlorohydrin Resin (eg, NER-7604 manufactured by Nippon Kayaku Co., Ltd.), epoxy resin obtained by reacting the alcoholic hydroxy group of bisphenol A type epoxy resin with epichlorohydrin (eg, NER-1302 manufactured by Nihon Kayaku Co., Ltd.) , O-cresol novolac type epoxy resin (eg, EOCN4400 manufactured by Nippon Kayaku Co., Ltd.), obtained by reacting the phenolic hydroxy group of the resin obtained by reacting di (methoxymethylphenyl) with phenol and epichlorohydrin. Biphenylphenol novolac type epoxy resin (eg NC-3000H manufactured by Nippon Kayaku Co., Ltd.), epoxy resin having a cyclic phosphorus-containing structure, α-methylstilben type liquid crystal epoxy resin, dibenzoyloxybenzene type liquid crystal epoxy resin, azophenyl Type liquid crystal epoxy resin, azomethinphenyl type liquid crystal epoxy resin, binaphthyl type liquid crystal epoxy resin, azine type epoxy resin, glycidyl methacrylate copolymer epoxy resin ("CP-50S, CP-50M; manufactured by Nippon Oil & Fats Co., Ltd.", etc.) , Cyclohexyl maleimide and glycidyl methacrylate copolymer epoxy resin, bis (glycidyl oxyphenyl) fluorene type epoxy resin, bis (glycidyl oxyphenyl) adamantan type epoxy resin and the like. These may be used alone or in combination of two or more.
　また、１分子中に少なくとも２つのオキシラン基を有する上記エポキシ化合物以外に、β位にアルキル基を有するエポキシ基を少なくとも１分子中に２つ含むエポキシ化合物を用いることができ、β位がアルキル基で置換されたエポキシ基（より具体的には、β－アルキル置換グリシジル基など）を含む化合物が特に好ましい。
　上記β位にアルキル基を有するエポキシ基を少なくとも含むエポキシ化合物は、１分子中に含まれる２個以上のエポキシ基のすべてがβ－アルキル置換グリシジル基であってもよく、少なくとも１個のエポキシ基がβ－アルキル置換グリシジル基であってもよい。 Further, in addition to the above-mentioned epoxy compound having at least two oxylan groups in one molecule, an epoxy compound containing at least two epoxy groups having an alkyl group at the β-position in one molecule can be used, and the β-position is an alkyl group. Compounds containing an epoxy group substituted with (more specifically, a β-alkyl substituted glycidyl group, etc.) are particularly preferable.
In the epoxy compound containing at least an epoxy group having an alkyl group at the β-position, all of the two or more epoxy groups contained in one molecule may be β-alkyl substituted glycidyl groups, and at least one epoxy group. May be a β-alkyl substituted glycidyl group.
　上記オキセタン化合物としては、例えば、１分子内に少なくとも２つのオキセタニル基を有するオキセタン化合物が挙げられる。
　具体的には、例えば、ビス［（３－メチル－３－オキセタニルメトキシ）メチル］エーテル、ビス［（３－エチル－３－オキセタニルメトキシ）メチル］エーテル、１，４－ビス［（３－メチル－３－オキセタニルメトキシ）メチル］ベンゼン、１，４－ビス［（３－エチル－３－オキセタニルメトキシ）メチル］ベンゼン、（３－メチル－３－オキセタニル）メチルアクリレート、（３－エチル－３－オキセタニル）メチルアクリレート、（３－メチル－３－オキセタニル）メチルメタクリレート、（３－エチル－３－オキセタニル）メチルメタクリレート又はこれらのオリゴマーあるいは共重合体等の多官能オキセタン類の他、オキセタン基を有する化合物と、ノボラック樹脂、ポリ（ｐ－ヒドロキシスチレン）、カルド型ビスフェノール類、カリックスアレーン類、カリックスレゾルシンアレーン類、シルセスキオキサン等の水酸基を有する樹脂など、とのエーテル化合物が挙げられ、この他、オキセタン環を有する不飽和モノマーとアルキル（メタ）アクリレートとの共重合体なども挙げられる。 Examples of the oxetane compound include an oxetane compound having at least two oxetanyl groups in one molecule.
Specifically, for example, bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl-). 3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetans such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate or oligomers or copolymers thereof, compounds having an oxetane group, and Examples include ether compounds such as novolak resin, poly (p-hydroxystyrene), cardo-type bisphenols, calix arrayes, calix resorcinarenes, resins having a hydroxyl group such as silsesquioxane, and the oxetane ring. Examples thereof include a copolymer of an unsaturated monomer having the above and an alkyl (meth) acrylate.
　エポキシ樹脂としては、一分子中にエポキシ基が二つ以上あるエポキシ樹脂であれば、いずれのエポキシ樹脂も用いることができるが、エポキシ樹脂のエポキシ当量は十分な硬化速度が得られるように１００ｇ／当量～５００ｇ／当量であることが好ましく、１００ｇ／当量～３００ｇ／当量であることがより好ましい。なお、ここで言うエポキシ当量とはＪＩＳ　Ｋ－７２３６に準拠した方法で測定した値を意味する。
　また、エポキシ樹脂の種類としてはグリシジルエーテル型、グリシジルエステル型、グリシジルアミン型、脂環型等を用いることができるが、液保存安定性が良いことからグリシジルエーテル型、グリシジルエステル型が好ましく、グリシジルエーテル型が最も好ましい。
　また、現像性の点から、エポキシ樹脂は、常温（２５℃）で液状であることが好ましく、２５℃における粘度が５，０００ｍＰａ・ｓ以下であることがより好ましく、１，０００ｍＰａ・ｓ以下であることがより好ましい。これらはエポキシ樹脂は、単独あるいは２種以上混合して用いることができる。
　上記のようなエポキシ樹脂の具体例として、グリシジルエーテル型としてのソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、トリメチロールプロパンポリグリシジルエーテル、レゾルシノールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，４－ブタンジオールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル及びポリプロピレングリコールジグリシジルエーテルが挙げられ、また、グリシジルエステル型としてのフタル酸ジグリシジルエステル、テトラヒドロフタル酸ジグリシジルエステル及びヘキサヒドロフタル酸ジグリシジルエステルが挙げられる。 As the epoxy resin, any epoxy resin can be used as long as it has two or more epoxy groups in one molecule, but the epoxy equivalent of the epoxy resin is 100 g / g so that a sufficient curing rate can be obtained. Equivalent to 500 g / equivalent is preferable, and 100 g / equivalent to 300 g / equivalent is more preferable. The epoxy equivalent referred to here means a value measured by a method based on JIS K-7236.
As the type of epoxy resin, glycidyl ether type, glycidyl ester type, glycidyl amine type, alicyclic type and the like can be used, but glycidyl ether type and glycidyl ester type are preferable because of good liquid storage stability. The ether type is most preferable.
From the viewpoint of developability, the epoxy resin is preferably liquid at room temperature (25 ° C.), more preferably has a viscosity at 25 ° C. of 5,000 mPa · s or less, and is 1,000 mPa · s or less. More preferably. These epoxy resins can be used alone or in admixture of two or more.
Specific examples of the epoxy resin as described above include sorbitol polyglycidyl ether as a glycidyl ether type, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, and trimethylolpropane polyglycidyl ether. , Resolsinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether And polypropylene glycol diglycidyl ether, and phthalic acid diglycidyl ester as a glycidyl ester type, tetrahydrophthalic acid diglycidyl ester and hexahydrophthalic acid diglycidyl ester can be mentioned.
　ネガ型感光性樹脂層Ｎは、１種単独、又は、２種以上の多官能エポキシ樹脂を含んでもよい。
　ネガ型感光性樹脂層Ｎにおける多官能エポキシ樹脂の含有割合は、ネガ型感光性樹脂層Ｎの全質量に対して、１０質量％～９０質量％であることが好ましく、２０質量％～７０質量％であることがより好ましい。 The negative photosensitive resin layer N may contain one type alone or two or more types of polyfunctional epoxy resins.
The content ratio of the polyfunctional epoxy resin in the negative photosensitive resin layer N is preferably 10% by mass to 90% by mass, preferably 20% by mass to 70% by mass, based on the total mass of the negative photosensitive resin layer N. More preferably.
－ヒドロキシ基含有化合物－
　ネガ型感光性樹脂層Ｎは、得られるパターン２の永久膜としての強度及び耐久性の観点から、ヒドロキシ基含有化合物を含むことが好ましい。
　ヒドロキシ基含有化合物は、ポリオール化合物やフェノール系化合物を適宜用いることができる。
　ポリオール化合物は、酸触媒の影響の下でエポキシ樹脂中のエポキシ基と反応するヒドロキシ基を含み、反応性希釈剤として働く。特にポリカプロラクトンポリオールを含むことが好ましい。ポリカプロラクトンポリオールを含むことにより、樹脂組成物を塗布後、必要により溶剤分を乾燥させて得られる乾燥塗膜が軟化するため、積層体の製造時での応力誘発を回避し、収縮を低減させ、永久膜である樹脂パターン２の亀裂を防止することができる。 -Hydroxy group-containing compound-
The negative photosensitive resin layer N preferably contains a hydroxy group-containing compound from the viewpoint of strength and durability of the obtained pattern 2 as a permanent film.
As the hydroxy group-containing compound, a polyol compound or a phenolic compound can be appropriately used.
The polyol compound contains a hydroxy group that reacts with the epoxy group in the epoxy resin under the influence of an acid catalyst and acts as a reactive diluent. In particular, it is preferable to contain polycaprolactone polyol. By containing the polycaprolactone polyol, the dry coating film obtained by drying the solvent component after coating the resin composition is softened, so that stress induction during the production of the laminate is avoided and shrinkage is reduced. , It is possible to prevent cracks in the resin pattern 2 which is a permanent film.
　ポリオール化合物としては、市販のポリエステルポリオールを用いることができる。具体例としては、分子量５３０でＯＨ価（「水酸基価」ともいう。）が２１０ｍｇＫＯＨ／ｇである「プラクセル２０５」、分子量が１，０００でＯＨ価が１１０ｍｇＫＯＨ／ｇである「プラクセル２１０」、分子量２，０００でＯＨ価が５６ｍｇＫＯＨ／ｇである「プラクセル２２０」（いずれも商品名、（株）ダイセル製）や、分子量５５０でＯＨ価が２０４ｍｇＫＯＨ／ｇである「Ｃａｐａ２０５４」、分子量１，０００でＯＨ価が１１２ｍｇＫＯＨ／ｇである「Ｃａｐａ２１００」、分子量２，０００でＯＨ価が５６ｍｇＫＯＨ／ｇである「Ｃａｐａ２２００」（いずれも商品名、パーストープ社製）が挙げられる。
　また、フェノール系化合物としては、例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂、多官能ビスフェノールＡノボラック樹脂、ビフェニルフェノールノボラック樹脂、トリスヒドロキシフェニルメタン骨格を有するフェノール樹脂、テルペンジフェノール骨格を有するフェノール樹脂、ビスフェノールＡやビスフェノールＦ等の各種フェノールを原料とするフェノール樹脂などが挙げられる。
　ヒドロキシ基含有化合物の好ましい水酸基含有化合物の水酸基価は、好ましくは、９０ｍｇＫＯＨ／ｇ～３００ｍｇＫＯＨ／ｇであり、より好ましくは１００ｍｇＫＯＨ／ｇ～２５０ｍｇＫＯＨ／ｇである。このヒドロキシ基含有化合物は単独若しくは２種以上を併用しても差し支えない。 As the polyol compound, a commercially available polyester polyol can be used. Specific examples include "Plaxel 205" having a molecular weight of 530 and an OH value (also referred to as "hydroxyl value") of 210 mgKOH / g, "Plaxel 210" having a molecular weight of 1,000 and an OH value of 110 mgKOH / g, and a molecular weight. "Plaxel 220" with a molecular weight of 2,000 and an OH value of 56 mgKOH / g (both trade names, manufactured by Daicel Co., Ltd.), "Capa2054" with a molecular weight of 550 and an OH value of 204 mgKOH / g, with a molecular weight of 1,000. Examples thereof include "Capa2100" having an OH value of 112 mgKOH / g and "Capa2200" having a molecular weight of 2,000 and an OH value of 56 mgKOH / g (both trade names, manufactured by Perstop).
Examples of the phenol-based compound include phenol novolac resin, cresol novolak resin, polyfunctional bisphenol A novolak resin, biphenylphenol novolac resin, phenol resin having a trishydroxyphenylmethane skeleton, phenol resin having a terpendiphenol skeleton, and bisphenol. Examples thereof include phenol resins made from various phenols such as A and bisphenol F.
The hydroxyl value of the preferred hydroxyl group-containing compound of the hydroxy group-containing compound is preferably 90 mgKOH / g to 300 mgKOH / g, and more preferably 100 mgKOH / g to 250 mgKOH / g. This hydroxy group-containing compound may be used alone or in combination of two or more.
　ネガ型感光性樹脂層Ｎは、１種単独、又は、２種以上のヒドロキシ基含有化合物を含んでもよい。
　ネガ型感光性樹脂層Ｎにおけるヒドロキシ基含有化合物の含有割合は、ネガ型感光性樹脂層Ｎの全質量に対して、１質量％～３５質量％であることが好ましく、５質量％～２５質％であることがより好ましい。 The negative photosensitive resin layer N may contain one kind alone or two or more kinds of hydroxy group-containing compounds.
The content ratio of the hydroxy group-containing compound in the negative photosensitive resin layer N is preferably 1% by mass to 35% by mass, and 5% by mass to 25% by mass, based on the total mass of the negative photosensitive resin layer N. More preferably.
－光重合開始剤－
　ネガ型感光性樹脂層Ｎは、光重合開始剤を含むことが好ましい。光重合開始剤は、活性光線（例えば、紫外線、可視光線、及びＸ線）を受けて、重合性化合物（例えば、重合性化合物Ｂ）の重合を開始する化合物である。
　また、 -Photopolymerization initiator-
The negative photosensitive resin layer N preferably contains a photopolymerization initiator. The photopolymerization initiator is a compound that receives active light (for example, ultraviolet rays, visible light, and X-rays) to initiate polymerization of a polymerizable compound (for example, polymerizable compound B).
again,
　光重合開始剤としては、制限されず、公知の光重合開始剤を用いることができる。光重合開始剤としては、例えば、光ラジカル重合開始剤、及び光カチオン重合開始剤が挙げられ、硬化性の観点からは、光ラジカル重合開始剤が好ましい。
　また、ネガ型感光性樹脂層Ｎは、得られる樹脂パターン２の永久膜としての強度及び耐久性の観点からは、光カチオン重合開始剤を含むことが好ましい。 The photopolymerization initiator is not limited, and a known photopolymerization initiator can be used. Examples of the photopolymerization initiator include a photoradical polymerization initiator and a photocationic polymerization initiator, and a photoradical polymerization initiator is preferable from the viewpoint of curability.
Further, the negative type photosensitive resin layer N preferably contains a photocationic polymerization initiator from the viewpoint of the strength and durability of the obtained resin pattern 2 as a permanent film.
　光ラジカル重合開始剤としては、例えば、オキシムエステル構造を有する光重合開始剤、α－アミノアルキルフェノン構造を有する光重合開始剤、α－ヒドロキシアルキルフェノン構造を有する光重合開始剤、アシルフォスフィンオキサイド構造を有する光重合開始剤、及びＮ－フェニルグリシン構造を有する光重合開始剤が挙げられる。 Examples of the photoradical polymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, and an acylphosphine oxide. Examples thereof include a photopolymerization initiator having a structure and a photopolymerization initiator having an N-phenylglycine structure.
　ネガ型感光性樹脂層Ｎは、感光性、露光部の視認性、非露光部の視認性、及び解像性の観点から、光ラジカル重合開始剤として、２，４，５－トリアリールイミダゾール二量体、及び２，４，５－トリアリールイミダゾール二量体の誘導体よりなる群から選択される少なくとも１種を含むことが好ましい。なお、２，４，５－トリアリールイミダゾール二量体、及びその誘導体における２つの２，４，５－トリアリールイミダゾール構造は、同一であっても異なっていてもよい。 The negative photosensitive resin layer N contains 2,4,5-triarylimidazole dimer as a photoradical polymerization initiator from the viewpoints of photosensitivity, visibility of exposed parts, visibility of unexposed parts, and resolution. It preferably contains at least one selected from the group consisting of a mer and a derivative of the 2,4,5-triarylimidazole dimer. The two 2,4,5-triarylimidazole dimers and their derivatives may have the same or different structures.
　２，４，５－トリアリールイミダゾール二量体の誘導体としては、例えば、２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－クロロフェニル）－４，５－ジ（メトキシフェニル）イミダゾール二量体、２－（ｏ－フルオロフェニル）－４，５－ジフェニルイミダゾール二量体、２－（ｏ－メトキシフェニル）－４，５－ジフェニルイミダゾール二量体、及び２－（ｐ－メトキシフェニル）－４，５－ジフェニルイミダゾール二量体が挙げられる。 Derivatives of the 2,4,5-triarylimidazole dimer include, for example, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di. (Methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, and 2- (P-methoxyphenyl) -4,5-diphenylimidazole dimer can be mentioned.
　光ラジカル重合開始剤としては、例えば、特開２０１１－９５７１６号公報の段落００３１～段落００４２、及び特開２０１５－１４７８３号公報の段落００６４～段落００８１に記載された重合開始剤も挙げられる。 Examples of the photoradical polymerization initiator include the polymerization initiators described in paragraphs 0031 to 0042 of JP2011-95716A and paragraphs 0064 to 0081 of JP2015-14783A.
　光ラジカル重合開始剤としては、例えば、ジメチルアミノ安息香酸エチル（ＤＢＥ、ＣＡＳ　Ｎｏ．１０２８７－５３－３）、ベンゾインメチルエーテル、アニシル（ｐ，ｐ’－ジメトキシベンジル）、及びベンゾフェノンが挙げられる。 Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, anisyl (p, p'-dimethoxybenzyl), and benzophenone.
　光ラジカル重合開始剤の市販品としては、例えば、ＴＡＺ－１１０（みどり化学（株））、ＴＡＺ－１１１（みどり化学（株））、１－［４－（フェニルチオ）］フェニル－１，２－オクタンジオン－２－（Ｏ－ベンゾイルオキシム）（商品名：ＩＲＧＡＣＵＲＥ（登録商標）　ＯＸＥ－０１、ＢＡＳＦ社）、１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン－１－（Ｏ－アセチルオキシム）（商品名：ＩＲＧＡＣＵＲＥ　ＯＸＥ－０２、ＢＡＳＦ社）、ＩＲＧＡＣＵＲＥ　ＯＸＥ－０３（ＢＡＳＦ社）、ＩＲＧＡＣＵＲＥ　ＯＸＥ－０４（ＢＡＳＦ社）、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルフォリニル）フェニル］－１－ブタノン（商品名：Ｏｍｎｉｒａｄ　３７９ＥＧ、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社）、２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン（商品名：Ｏｍｎｉｒａｄ　９０７、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社）、２－ヒドロキシ－１－｛４－［４－（２－ヒドロキシ－２－メチルプロピオニル）ベンジル］フェニル｝－２－メチルプロパン－１－オン（商品名：Ｏｍｎｉｒａｄ　１２７、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社）、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタノン－１（商品名：Ｏｍｎｉｒａｄ　３６９、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社）、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン（商品名：Ｏｍｎｉｒａｄ　１１７３、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社）、１－ヒドロキシシクロヘキシルフェニルケトン（商品名：Ｏｍｎｉｒａｄ　１８４、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社）、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン（商品名：Ｏｍｎｉｒａｄ　６５１、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社）、２，４，６－トリメチルベンゾイル－ジフェニルフォスフィンオキサイド（商品名：Ｏｍｎｉｒａｄ　ＴＰＯ　Ｈ、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社）、ビス（２，４，６－トリメチルベンゾイル）フェニルフォスフィンオキサイド（商品名：Ｏｍｎｉｒａｄ　８１９、ＩＧＭ　Ｒｅｓｉｎｓ　Ｂ．Ｖ．社）、オキシムエステル系の光重合開始剤（商品名：Ｌｕｎａｒ　６、ＤＫＳＨジャパン（株））、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラフェニル－１，２’－ビイミダゾール（別称：２－（２－クロロフェニル）－４，５－ジフェニルイミダゾール二量体、商品名：Ｂ－ＣＩＭ、Ｈａｍｐｆｏｒｄ社）、及び２－（ｏ－クロロフェニル）－４，５－ジフェニルイミダゾール二量体（商品名：ＢＣＴＢ、東京化成工業（株））が挙げられる。 Commercially available photoradical polymerization initiators include, for example, TAZ-110 (Midori Chemical Co., Ltd.), TAZ-111 (Midori Chemical Co., Ltd.), 1- [4- (Phenylthio)] phenyl-1,2-. Octandion-2- (O-benzoyloxime) (trade name: IRGACURE (registered trademark) OXE-01, BASF), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-3 Il] Etanon-1- (O-acetyloxime) (trade name: IRGACURE OXE-02, BASF), IRGACURE OXE-03 (BASF), IRGACURE OXE-04 (BASF), 2- (dimethylamino)- 2-[(4-Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: Omnirad 379EG, IGM Resins BV), 2-methyl-1- (4-Methylthiophenyl) -2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins BV), 2-hydroxy-1- {4- [4- (2-hydroxy-2) -Methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one (trade name: Omnirad 127, IGM Resins VV), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) Butanon-1 (trade name: Omnirad 369, IGM Resins VV), 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Omnirad 1173, IGM Resins VV) ), 1-Hydroxycyclohexylphenylketone (trade name: Omnirad 184, IGM Resins VV), 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Omnirad 651, IGM Resins B) V.), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins BV), bis (2,4,6-trimethylbenzoyl) phenylphosphine Oxide (trade name: Omnirad 819, IGM Resins BV), oxime ester-based photopolymerization initiator (trade name: Lunar 6, DKSH Japan Co., Ltd.), 2,2'-bis (2-chlorophenyl) -4, 4 ', 5,5'-Tetraphenyl-1,2'-biimidazole (also known as 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer, trade name: B-CIM, Hampford), and Examples thereof include 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer (trade name: BCTB, Tokyo Chemical Industry Co., Ltd.).
　中でも、光ラジカル重合開始剤としては、２，４，５－トリアリールイミダゾール二量体、及び２，４，５－トリアリールイミダゾール二量体の誘導体よりなる群から選択される少なくとも１種を含むことが好ましい。 Among them, the photoradical polymerization initiator includes at least one selected from the group consisting of 2,4,5-triarylimidazole dimer and derivatives of 2,4,5-triarylimidazole dimer. Is preferable.
　光カチオン重合開始剤（すなわち、光酸発生剤）は、紫外線、遠紫外線、ＫｒＦやＡｒＦなどのエキシマレーザー、Ｘ線、電子線などの放射線の照射を受けてカチオンを発生し、そのカチオンが重合開始剤となりうる化合物である。
　光カチオン重合開始剤としては、波長３００ｎｍ以上、好ましくは波長３００～４５０ｎｍの活性光線に感応し、酸を発生する化合物が好ましい。ただし、光カチオン重合開始剤の化学構造は、制限されない。また、波長３００ｎｍ以上の活性光線に直接感応しない光カチオン重合開始剤についても、増感剤と併用することによって波長３００ｎｍ以上の活性光線に感応し、酸を発生する化合物であれば、増感剤と組み合わせて好ましく用いることができる。 The photocationic polymerization initiator (that is, a photoacid generator) generates a cation by being irradiated with ultraviolet rays, far ultraviolet rays, excimer lasers such as KrF and ArF, X-rays, electron beams, etc., and the cations are polymerized. It is a compound that can be an initiator.
As the photocationic polymerization initiator, a compound that is sensitive to active light having a wavelength of 300 nm or more, preferably a wavelength of 300 to 450 nm and generates an acid is preferable. However, the chemical structure of the photocationic polymerization initiator is not limited. In addition, a photocationic polymerization initiator that is not directly sensitive to active light with a wavelength of 300 nm or more is also a sensitizer if it is a compound that is sensitive to active light with a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. Can be preferably used in combination with.
　光カチオン重合開始剤としては、芳香族ヨードニウム錯塩や芳香族スルホニウム錯塩を挙げることができる。
　芳香族ヨードニウム錯塩の具体例としては、ジフェニルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート、ジフェニルヨードニウムヘキサフルオロホスフェート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジ（４－ノニルフェニル）ヨードニウムヘキサフルオロホスフェート、トリルクミルヨードニウムテトラキス（ペンタフルオロフェニル）ボレート（ローディア社製、商品名　ロードシルＰＩ２０７４）、ジ（４－ターシャリブチル）ヨードニウムトリス（トリフルオロメタンスルホニル）メタニド（ＢＡＳＦ社製、商品名　ＣＧＩ　ＢＢＩ－Ｃ１）等が挙げられる。又、芳香族スルホニウム錯塩の具体例としては、４－チオフェニルジフェニルスルフォニウムヘキサフルオロアンチモネート（サンアプロ社製、商品名　ＣＰＩ－１０１Ａ）、チオフェニルジフェニルスルフォニウムトリス（ペンタフルオロエチル）トリフルオロホスフェート（サンアプロ社製、商品名　ＣＰＩ－２１０Ｓ）、４－｛４－（２－クロロベンゾイル）フェニルチオ｝フェニルビス（４－フルオロフェニル）スルホニウムヘキサフルオロアンチモネート（ＡＤＥＫＡ社製、商品名　ＳＰ－１７２）、４－チオフェニルジフェニルスルフォニウムヘキサフルオロアンチモネートを含有する芳香族スルフォニウムヘキサフルオロアンチモネートの混合物（ＡＣＥＴＯ　Ｃｏｒｐｏｒａｔｅ　ＵＳＡ製、商品名　ＣＰＩ－６９７６）及びトリフェニルスルホニウムトリス（トリフルオロメタンスルホニル）メタニド（ＢＡＳＦ社製、商品名　ＣＧＩ　ＴＰＳ－Ｃ１）、トリス［４－（４－アセチルフェニル）スルホニルフェニル］スルホニウムトリス（トリフルオロメチルスルホニル）メチド（ＢＡＳＦ社製、商品名　ＧＳＩＤ　２６－１）、トリス［４－（４－アセチルフェニル）スルホニルフェニル］スルホニウムテトラキス（２，３，４，５，６－ペンタフルオロフェニル）ボレート（ＢＡＳＦ社製、商品名　イルガキュアＰＡＧ２９０）等が好適に用いられる。 Examples of the photocationic polymerization initiator include aromatic iodonium complex salts and aromatic sulfonium complex salts.
Specific examples of aromatic iodonium complex salts include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and trilucmil iodonium tetrakis. Examples thereof include (pentafluorophenyl) borate (manufactured by Rhodia, trade name Rhodesyl PI2074), di (4-tershaributyl) iodonium tris (trifluoromethanesulfonyl) metanide (manufactured by BASF, trade name CGI BBI-C1) and the like. Specific examples of the aromatic sulfonium complex salt include 4-thiophenyldiphenylsulfonium hexafluoroantimonate (manufactured by San Apro, trade name CPI-101A) and thiophenyldiphenyl sulfonium tris (pentafluoroethyl) trifluoro. Phenyl phosphate (manufactured by San Apro, trade name CPI-210S), 4- {4- (2-chlorobenzoyl) phenylthio} phenylbis (4-fluorophenyl) sulfonium hexafluoroantimonate (manufactured by ADEKA, trade name SP-172) , 4-Phenyl Diphenyl Sulfonium Hexafluoro Antimonate-Containing Aromatic Sulfonium Hexafluoro Antimonate Mixture (ACETO Corporate USA, Trade Name CPI-6996) and Triphenyl Sulfonium Tris (Trifluoromethanesulfonyl) Metanide (BASF, trade name CGI TPS-C1), Tris [4- (4-acetylphenyl) sulfonylphenyl] sulfonium tris (trifluoromethylsulfonyl) methide (BASF, trade name GSID 26-1), Tris [ 4- (4-Acetylphenyl) sulfonylphenyl] Sulfonium tetrakis (2,3,4,5,6-pentafluorophenyl) borate (manufactured by BASF, trade name Irgacure PAG290) and the like are preferably used.
　以上の光カチオン重合開始剤のうち、垂直矩形加工性、及び、熱安定性の観点から、芳香族スルホニウム錯塩が好ましく、４－｛４－（２－クロロベンゾイル）フェニルチオ｝フェニルビス（４－フルオロフェニル）スルホニウムヘキサフルオロアンチモネート、４－チオフェニルジフェニルスルフォニウムヘキサフルオロアンチモネートを含有する芳香族スルフォニウムヘキサフルオロアンチモネートの混合物、又は、トリス［４－（４－アセチルフェニル）スルホニルフェニル］スルホニウムテトラキス（２，３，４，５，６－ペンタフルオロフェニル）ボレートが特に好ましい。 Among the above photocationic polymerization initiators, aromatic sulfonium complex salts are preferable from the viewpoint of vertical rectangular processability and thermal stability, and 4- {4- (2-chlorobenzoyl) phenylthio} phenylbis (4-fluoro) is preferable. Phenyl) Sulfonium hexafluoroantimonate, a mixture of aromatic sulfonium hexafluoroantimonates containing 4-thiophenyldiphenyl sulfonium hexafluoroantimonate, or tris [4- (4-acetylphenyl) sulfonylphenyl] Sulfonium tetrakis (2,3,4,5,6-pentafluorophenyl) borate is particularly preferred.
　また、光カチオン重合開始剤は、ｐＫａが４以下の酸を発生する光カチオン重合開始剤であることが好ましく、ｐＫａが３以下の酸を発生する光カチオン重合開始剤であることがより好ましく、ｐＫａが２以下の酸を発生する光カチオン重合開始剤であることが特に好ましい。ｐＫａの下限は、制限されない。光カチオン重合開始剤から生じる酸のｐＫａは、例えば、－１０．０以上であることが好ましい。 Further, the photocationic polymerization initiator is preferably a photocationic polymerization initiator that generates an acid having a pKa of 4 or less, and more preferably a photocationic polymerization initiator that generates an acid having a pKa of 3 or less. A photocationic polymerization initiator that generates an acid having a pKa of 2 or less is particularly preferable. The lower limit of pKa is not limited. The pKa of the acid generated from the photocationic polymerization initiator is preferably -10.0 or more, for example.
　光カチオン重合開始剤としては、イオン性光カチオン重合開始剤、及び非イオン性光カチオン重合開始剤が挙げられる。 Examples of the photocationic polymerization initiator include an ionic photocationic polymerization initiator and a nonionic photocationic polymerization initiator.
　イオン性光カチオン重合開始剤として、例えば、オニウム塩化合物（例えば、ジアリールヨードニウム塩化合物、及びトリアリールスルホニウム塩化合物）、及び第４級アンモニウム塩化合物が挙げられる。 Examples of the ionic photocationic polymerization initiator include onium salt compounds (for example, diaryliodonium salt compounds and triarylsulfonium salt compounds), and quaternary ammonium salt compounds.
　イオン性光カチオン重合開始剤としては、特開２０１４－８５６４３号公報の段落０１１４～段落０１３３に記載のイオン性光カチオン重合開始剤も挙げられる。 Examples of the ionic photocationic polymerization initiator include the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP-A-2014-85643.
　非イオン性光カチオン重合開始剤としては、例えば、トリクロロメチル－ｓ－トリアジン化合物、ジアゾメタン化合物、イミドスルホネート化合物、及びオキシムスルホネート化合物が挙げられる。トリクロロメチル－ｓ－トリアジン化合物、ジアゾメタン化合物、及びイミドスルホネート化合物としては、例えば、特開２０１１－２２１４９４号公報の段落００８３～段落００８８に記載の化合物があげられる。また、オキシムスルホネート化合物としては、例えば、国際公開第２０１８／１７９６４０号の段落００８４～段落００８８に記載された化合物が挙げられる。 Examples of the nonionic photocationic polymerization initiator include trichloromethyl-s-triazine compounds, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Examples of the trichloromethyl-s-triazine compound, the diazomethane compound, and the imide sulfonate compound include the compounds described in paragraphs 0083 to 0088 of Japanese Patent Application Laid-Open No. 2011-22149. Examples of the oxime sulfonate compound include the compounds described in paragraphs 0084 to 0088 of International Publication No. 2018/179640.
　ネガ型感光性樹脂層Ｎは、１種単独、又は２種以上の光重合開始剤を含んでもよい。 The negative type photosensitive resin layer N may contain one kind alone or two or more kinds of photopolymerization initiators.
　ネガ型感光性樹脂層Ｎにおける光重合開始剤の含有割合は、ネガ型感光性樹脂層Ｎの全質量に対して、０．０１質量％以上であることが好ましく、０．１質量％以上であることがより好ましく、１．０質量％以上であることが特に好ましい。光重合開始剤の含有割合の上限は、制限されない。光重合開始剤の含有割合は、ネガ型感光性樹脂層Ｎの全質量に対して、１０質量％以下であることが好ましく、５質量％以下であることがより好ましい。 The content ratio of the photopolymerization initiator in the negative photosensitive resin layer N is preferably 0.01% by mass or more, preferably 0.1% by mass or more, based on the total mass of the negative photosensitive resin layer N. It is more preferable to have it, and it is particularly preferable that it is 1.0% by mass or more. The upper limit of the content ratio of the photopolymerization initiator is not limited. The content ratio of the photopolymerization initiator is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total mass of the negative photosensitive resin layer N.
－金属酸化抑制剤－
　ネガ型感光性樹脂層Ｎは、金属酸化抑制剤を含むことが好ましい。
　金属酸化抑制剤としては、分子内に窒素原子を含む芳香環を有する化合物であることが好ましい。
　また、金属酸化抑制剤としては、上記窒素原子を含む芳香環が、イミダゾール環、トリアゾール環、テトラゾール環、チアジアゾール環、及び、それらと他の芳香環との縮合環よりなる群から選ばれた少なくとも一つの環であることが好ましく、上記窒素原子を含む芳香環が、イミダゾール環、又は、イミダゾール環と他の芳香環との縮合環であることがより好ましい。
　上記他の芳香環としては、単素環でも複素環でもよいが、単素環であることが好ましく、ベンゼン環又はナフタレン環であることがより好ましく、ベンゼン環であることが更に好ましい。
　好ましい金属酸化抑制剤としては、イミダゾール、ベンズイミダゾール、テトラゾール、メルカプトチアジアゾール、及び、ベンゾトリアゾールが好ましく例示され、イミダゾール、ベンズイミダゾール、及び、ベンゾトリアゾールがより好ましい。金属酸化抑制剤としては市販品を用いてもよく、例えば、ベンゾトリアゾールを含む城北化学工業（株）、ＢＴ１２０などを好ましく用いることができる。 -Metal oxidation inhibitor-
The negative photosensitive resin layer N preferably contains a metal oxidation inhibitor.
The metal oxidation inhibitor is preferably a compound having an aromatic ring containing a nitrogen atom in the molecule.
Further, as the metal oxidation inhibitor, at least the aromatic ring containing a nitrogen atom is selected from the group consisting of an imidazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, and a fused ring between them and another aromatic ring. It is preferably one ring, and more preferably the aromatic ring containing a nitrogen atom is an imidazole ring or a fused ring of an imidazole ring and another aromatic ring.
The other aromatic ring may be a mono-prime ring or a heterocyclic ring, but a mono-prime ring is preferable, a benzene ring or a naphthalene ring is more preferable, and a benzene ring is further preferable.
Preferred metal oxidation inhibitors are preferably imidazole, benzimidazole, tetrazole, mercaptothiazazole, and benzotriazole, with imidazole, benzimidazole, and benzotriazole being more preferred. As the metal oxidation inhibitor, a commercially available product may be used, and for example, Johoku Chemical Industry Co., Ltd., BT120, etc. containing benzotriazole can be preferably used.
　また、金属酸化抑制剤としては、ベンゾトリアゾール化合物、又は、カルボキシベンゾトリアゾール化合物が好ましく挙げられる。
　ベンゾトリアゾール化合物としては、例えば、１，２，３－ベンゾトリアゾール、１－クロロ－１，２，３－ベンゾトリアゾール、ビス（Ｎ－２－エチルヘキシル）アミノメチレン－１，２，３－ベンゾトリアゾール、ビス（Ｎ－２－エチルヘキシル）アミノメチレン－１，２，３－トリルトリアゾール、及び、ビス（Ｎ－２－ヒドロキシエチル）アミノメチレン－１，２，３－ベンゾトリアゾールが挙げられる。
　カルボキシベンゾトリアゾール化合物としては、例えば、４－カルボキシ－１，２，３－ベンゾトリアゾール、５－カルボキシ－１，２，３－ベンゾトリアゾール、Ｎ－（Ｎ，Ｎ－ジ－２－エチルヘキシル）アミノメチレンカルボキシベンゾトリアゾール、Ｎ－（Ｎ，Ｎ－ジ－２－ヒドロキシエチル）アミノメチレンカルボキシベンゾトリアゾール、及び、Ｎ－（Ｎ，Ｎ－ジ－２－エチルヘキシル）アミノエチレンカルボキシベンゾトリアゾールが挙げられる。カルボキシベンゾトリアゾール化合物の市販品としては、例えば、ＣＢＴ－１（城北化学工業（株））が挙げられる。 Moreover, as a metal oxidation inhibitor, a benzotriazole compound or a carboxybenzotriazole compound is preferably mentioned.
Examples of the benzotriazole compound include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, and the like. Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole and bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.
Examples of the carboxybenzotriazole compound include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylene carboxybenzotriazole, and N- (N, N-di-2-ethylhexyl) aminoethylene carboxybenzotriazole. Examples of commercially available products of the carboxybenzotriazole compound include CBT-1 (Johoku Chemical Industry Co., Ltd.).
　ネガ型感光性樹脂層Ｎは、１種単独、又は２種以上の金属酸化抑制剤を含んでもよい。
　また、金属酸化抑制剤の含有量は、ネガ型感光性樹脂層Ｎの全質量に対し、０．１質量％～２０質量％であることが好ましく、０．５質量％～１０質量％であることがより好ましく、１質量％～５質量％であることが更に好ましい。 The negative photosensitive resin layer N may contain one kind alone or two or more kinds of metal oxidation inhibitors.
The content of the metal oxidation inhibitor is preferably 0.1% by mass to 20% by mass, preferably 0.5% by mass to 10% by mass, based on the total mass of the negative photosensitive resin layer N. More preferably, it is more preferably 1% by mass to 5% by mass.
－任意成分－
　ネガ型感光性樹脂層Ｎは、上記した成分以外の成分（以下、「任意成分」という場合がある。）を含んでもよい。任意成分としては、例えば、色素、界面活性剤、及び上記成分以外の添加剤が挙げられる。 -Arbitrary component-
The negative photosensitive resin layer N may contain components other than the above-mentioned components (hereinafter, may be referred to as “arbitrary components”). Optional components include, for example, dyes, surfactants, and additives other than the above components.
＜＜色素＞＞
　ネガ型感光性樹脂層Ｎは、露光部の視認性、非露光部の視認性、現像後のパターン視認性、及び解像性の観点から、発色時の波長範囲である４００ｎｍ～７８０ｎｍにおける最大吸収波長が４５０ｎｍ以上であり、かつ、酸、塩基、又はラジカルにより最大吸収波長が変化する色素（以下、「色素ＮＣ」という場合がある。）を含むことが好ましい。詳細なメカニズムは不明であるが、ネガ型感光性樹脂層Ｎが色素ＮＣを含むことで、ネガ型感光性樹脂層Ｎに隣接する層との密着性が向上し、解像性により優れる。 << Dye >>
The negative photosensitive resin layer N has a maximum absorption in the wavelength range of 400 nm to 780 nm at the time of color development from the viewpoints of the visibility of the exposed portion, the visibility of the non-exposed portion, the pattern visibility after development, and the resolution. It is preferable to contain a dye having a wavelength of 450 nm or more and whose maximum absorption wavelength is changed by an acid, a base, or a radical (hereinafter, may be referred to as “dye NC”). Although the detailed mechanism is unknown, the inclusion of the dye NC in the negative photosensitive resin layer N improves the adhesion with the layer adjacent to the negative photosensitive resin layer N, and is more excellent in resolution.
　本開示において、色素に関して使用される用語「酸、塩基、又はラジカルにより極大吸収波長が変化する」とは、発色状態にある色素が、酸、塩基、又はラジカルにより消色する態様、消色状態にある色素が、酸、塩基又はラジカルにより発色する態様、及び発色状態にある色素が、他の色相の発色状態に変化する態様のいずれの態様を意味してもよい。 In the present disclosure, the term "maximum absorption wavelength changes by acid, base, or radical" used with respect to a dye is a mode in which a dye in a color-developing state is decolorized by an acid, base, or radical. It may mean any aspect of a mode in which the dye in the above color is developed by an acid, a base or a radical, and a mode in which the dye in a color-developing state changes to a color-developing state of another hue.
　具体的に、色素ＮＣは、露光により消色状態から変化して発色する化合物であってもよく、又は露光により発色状態から変化して消色する化合物であってもよい。上記態様において、色素ＮＣは、露光により発生する、酸、塩基、又はラジカルの作用によって、発色、又は消色の状態が変化する色素であってもよい。また、色素ＮＣは、露光により発生する、酸、塩基、又はラジカルによりネガ型感光性樹脂層Ｎ内の状態（例えばｐＨ）が変化することで、発色、又は消色の状態が変化する色素であってもよい。一方、色素ＮＣは、露光を介さずに、酸、塩基、又はラジカルを刺激として直接受けて、発色、又は消色の状態が変化する色素であってもよい。 Specifically, the dye NC may be a compound that changes from the decolorized state by exposure to develop a color, or may be a compound that changes from the decolorized state by exposure to decolorize. In the above aspect, the dye NC may be a dye whose color development or decolorization state is changed by the action of an acid, a base, or a radical generated by exposure. Further, the dye NC is a dye whose color development or decolorization state changes by changing the state (for example, pH) in the negative photosensitive resin layer N by an acid, a base, or a radical generated by exposure. There may be. On the other hand, the dye NC may be a dye whose color development or decolorization state changes by directly receiving an acid, a base, or a radical as a stimulus without exposure.
　色素ＮＣは、露光部の視認性、非露光部の視認性、及び解像性の観点から、酸、又はラジカルにより最大吸収波長が変化する色素であることが好ましく、ラジカルにより最大吸収波長が変化する色素であることがより好ましい。 The dye NC is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical from the viewpoint of visibility of an exposed portion, visibility of a non-exposed portion, and resolution, and the maximum absorption wavelength is changed by a radical. It is more preferable that the dye is a dye.
　ネガ型感光性樹脂層Ｎは、露光部の視認性、非露光部の視認性、及び解像性の観点から、色素ＮＣとして、ラジカルにより最大吸収波長が変化する色素、及び光ラジカル重合開始剤の両方を含むことが好ましい。 The negative photosensitive resin layer N is a dye NC whose maximum absorption wavelength is changed by radicals and a photoradical polymerization initiator from the viewpoints of visibility of exposed parts, visibility of non-exposed parts, and resolution. It is preferable to include both of the above.
　色素ＮＣは、露光部の視認性、非露光部の視認性の観点から、酸、塩基、又はラジカルにより発色する色素であることが好ましい。 The dye NC is preferably a dye that develops color with an acid, a base, or a radical from the viewpoint of visibility of the exposed part and visibility of the non-exposed part.
　色素ＮＣの発色機構の例としては、光ラジカル重合開始剤、光カチオン重合開始剤（すなわち、光酸発生剤）、又は光塩基発生剤を含むネガ型感光性樹脂層Ｎを露光することで、光ラジカル重合開始剤、光カチオン重合開始剤、又は光塩基発生剤から発生する、ラジカル、酸、又は塩基によって、ラジカル反応性色素、酸反応性色素、又は塩基反応性色素（例えばロイコ色素）が発色する態様が挙げられる。 An example of the color-developing mechanism of dye NC is by exposing a negative photosensitive resin layer N containing a photoradical polymerization initiator, a photocationic polymerization initiator (that is, a photoacid generator), or a photobase generator. Radical-reactive dyes, acid-reactive dyes, or base-reactive dyes (eg, leuco dyes) are produced by radicals, acids, or bases generated from photoradical polymerization initiators, photocationic polymerization initiators, or photobase generators. An aspect of developing color can be mentioned.
　色素ＮＣにおいて、発色時の波長範囲である４００ｎｍ～７８０ｎｍにおける極大吸収波長は、露光部の視認性、及び非露光部の視認性の観点から、５５０ｎｍ以上であることが好ましく、５５０ｎｍ～７００ｎｍであることがより好ましく、５５０～６５０ｎｍであることが特に好ましい。 In the dye NC, the maximum absorption wavelength in the wavelength range of 400 nm to 780 nm at the time of color development is preferably 550 nm or more, preferably 550 nm to 700 nm, from the viewpoint of the visibility of the exposed portion and the visibility of the non-exposed portion. More preferably, it is particularly preferably 550 to 650 nm.
　また、色素ＮＣは、発色時の波長範囲である４００ｎｍ～７８０ｎｍにおける極大吸収波長を１つ、又は２つ以上有してもよい。色素ＮＣが発色時の波長範囲である４００ｎｍ～７８０ｎｍにおける極大吸収波長を２つ以上有する場合は、２つ以上の極大吸収波長のうち吸光度が最も高い極大吸収波長が４５０ｎｍ以上であればよい。 Further, the dye NC may have one or two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm at the time of color development. When the dye NC has two or more maximum absorption wavelengths in the wavelength range of 400 nm to 780 nm at the time of color development, the maximum absorption wavelength having the highest absorbance among the two or more maximum absorption wavelengths may be 450 nm or more.
　色素ＮＣの極大吸収波長は、大気雰囲気下で、分光光度計（ＵＶ３１００、（株）島津製作所）を用いて、４００ｎｍ～７８０ｎｍの範囲で色素ＮＣを含む溶液（液温２５℃）の透過スペクトルを測定し、そして、光の強度が極小となる波長（極大吸収波長）を検出することによって測定する。 The maximum absorption wavelength of the dye NC is the transmission spectrum of the solution containing the dye NC (liquid temperature 25 ° C.) in the range of 400 nm to 780 nm using a spectrophotometer (UV3100, Shimadzu Corporation) in an atmospheric atmosphere. It is measured and then measured by detecting the wavelength at which the intensity of light is minimized (maximum absorption wavelength).
　露光により、発色、又は消色する色素としては、例えば、ロイコ化合物が挙げられる。露光により消色する色素としては、例えば、ロイコ化合物、ジアリールメタン系色素、オキザジン系色素、キサンテン系色素、イミノナフトキノン系色素、アゾメチン系色素、及びアントラキノン系色素が挙げられる。色素ＮＣは、露光部の視認性、及び非露光部の視認性の観点から、ロイコ化合物であることが好ましい。 Examples of the dye that develops or decolorizes by exposure include leuco compounds. Examples of dyes that are decolorized by exposure include leuco compounds, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes. The dye NC is preferably a leuco compound from the viewpoint of the visibility of the exposed portion and the visibility of the non-exposed portion.
　ロイコ化合物としては、例えば、トリアリールメタン骨格を有するロイコ化合物（トリアリールメタン系色素）、スピロピラン骨格を有するロイコ化合物（スピロピラン系色素）、フルオラン骨格を有するロイコ化合物（フルオラン系色素）、ジアリールメタン骨格を有するロイコ化合物（ジアリールメタン系色素）、ローダミンラクタム骨格を有するロイコ化合物（ローダミンラクタム系色素）、インドリルフタリド骨格を有するロイコ化合物（インドリルフタリド系色素）、及びロイコオーラミン骨格を有するロイコ化合物（ロイコオーラミン系色素）が挙げられる。ロイコ化合物は、トリアリールメタン系色素、又はフルオラン系色素であることが好ましく、トリフェニルメタン骨格を有するロイコ化合物（トリフェニルメタン系色素）、又はフルオラン系色素であることがより好ましい。 Examples of the leuco compound include a leuco compound having a triarylmethane skeleton (triarylmethane dye), a leuco compound having a spiropylan skeleton (spiropylan dye), a leuco compound having a fluorane skeleton (fluorane dye), and a diarylmethane skeleton. It has a leuco compound (diarylmethane dye) having a rhodamine lactam skeleton, a rhodamine lactam skeleton (rhodamine lactam dye), a leuco compound having an indrill phthalide skeleton (indolyl phthalide dye), and a leuco auramine skeleton. Leuco compounds (leuco auramine dyes) can be mentioned. The leuco compound is preferably a triarylmethane dye or a fluorane dye, and more preferably a leuco compound having a triphenylmethane skeleton (triphenylmethane dye) or a fluorane dye.
　ロイコ化合物は、露光部の視認性、及び非露光部の視認性の観点から、ラクトン環、スルチン環、又はスルトン環を有することが好ましい。ロイコ化合物に含まれるラクトン環、スルチン環、又はスルトン環を、光ラジカル重合開始剤から発生するラジカル、又は光カチオン重合開始剤から発生する酸と反応させることで、ロイコ化合物を閉環状態に変化させて消色させること、又はロイコ化合物を開環状態に変化させて発色させることができる。ロイコ化合物は、ラクトン環、スルチン環、又はスルトン環を有し、かつ、ラジカル、又は酸によりラクトン環、スルチン環、又はスルトン環が開環して発色する化合物であることが好ましく、ラクトン環を有し、かつ、ラジカル、又は酸によりラクトン環が開環して発色する化合物であることがより好ましい。 The leuco compound preferably has a lactone ring, a surujin ring, or a sultone ring from the viewpoint of visibility of the exposed portion and visibility of the non-exposed portion. By reacting the lactone ring, sultin ring, or sulton ring contained in the leuco compound with a radical generated from the photoradical polymerization initiator or an acid generated from the photocationic polymerization initiator, the leuco compound is changed to a closed ring state. The color can be decolorized, or the radical compound can be changed to a ring-opened state to develop a color. The leuco compound is preferably a compound having a lactone ring, a sultone ring, or a sultone ring, and the lactone ring, the sultone ring, or the sultone ring is opened by a radical or an acid to develop a color. It is more preferable that the compound has, and the lactone ring is opened by a radical or an acid to develop a color.
　ロイコ化合物の具体例としては、ｐ，ｐ’，ｐ”－ヘキサメチルトリアミノトリフェニルメタン（ロイコクリスタルバイオレット）、Ｐｅｒｇａｓｃｒｉｐｔ　Ｂｌｕｅ　ＳＲＢ（チバガイギー社）、クリスタルバイオレットラクトン、マラカイトグリーンラクトン、ベンゾイルロイコメチレンブルー、２－（Ｎ－フェニル－Ｎ－メチルアミノ）－６－（Ｎ－ｐ－トリル－Ｎ－エチル）アミノフルオラン、２－アニリノ－３－メチル－６－（Ｎ－エチル－ｐ－トルイジノ）フルオラン、３，６－ジメトキシフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－５－メチル－７－（Ｎ，Ｎ－ジベンジルアミノ）フルオラン、３－（Ｎ－シクロヘキシル－Ｎ－メチルアミノ）－６－メチル－７－アニリノフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－６－メチル－７－アニリノフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－６－メチル－７－キシリジノフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－６－メチル－７－クロロフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－６－メトキシ－７－アミノフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－７－（４－クロロアニリノ）フルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－７－クロロフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－７－ベンジルアミノフルオラン、３－（Ｎ，Ｎ－ジエチルアミノ）－７，８－ベンゾフロオラン、３－（Ｎ，Ｎ－ジブチルアミノ）－６－メチル－７－アニリノフルオラン、３－（Ｎ，Ｎ－ジブチルアミノ）－６－メチル－７－キシリジノフルオラン、３－ピペリジノ－６－メチル－７－アニリノフルオラン、３－ピロリジノ－６－メチル－７－アニリノフルオラン、３，３－ビス（１－エチル－２－メチルインドール－３－イル）フタリド、３，３－ビス（１－ｎ－ブチル－２－メチルインドール－３－イル）フタリド、３，３－ビス（ｐ－ジメチルアミノフェニル）－６－ジメチルアミノフタリド、３－（４－ジエチルアミノ－２－エトキシフェニル）－３－（１－エチル－２－メチルインドール－３－イル）－４－アザフタリド、３－（４－ジエチルアミノフェニル）－３－（１－エチル－２－メチルインドール－３－イル）フタリド、及び３’，６’－ビス（ジフェニルアミノ）スピロイソベンゾフラン－１（３Ｈ），９’－［９Ｈ］キサンテン－３－オンが挙げられる。 Specific examples of leuco compounds include p, p', p "-hexamethyltriaminotriphenylmethane (leucocrystal violet), Pergascript Blue SRB (Ciba Geigy), crystal violet lactone, malakite green lactone, benzoyl leucomethylene blue, 2 -(N-phenyl-N-methylamino) -6- (N-p-tolyl-N-ethyl) aminofluorane, 2-anilino-3-methyl-6- (N-ethyl-p-toluizino) fluorane, 3,6-dimethoxyfluorane, 3- (N, N-diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluorane, 3- (N-cyclohexyl-N-methylamino) -6- Methyl-7-anilinofluorane, 3- (N, N-diethylamino) -6-methyl-7-anilinofluorane, 3- (N, N-diethylamino) -6-methyl-7-xylidinofluorane , 3- (N, N-diethylamino) -6-methyl-7-chlorofluorine, 3- (N, N-diethylamino) -6-methoxy-7-aminofluorane, 3- (N, N-diethylamino) -7- (4-Chloroanilino) fluorane, 3- (N, N-diethylamino) -7-chlorofluorane, 3- (N, N-diethylamino) -7-benzylaminofluorane, 3- (N, N-) Diethylamino) -7,8-benzofluorolane, 3- (N, N-dibutylamino) -6-methyl-7-anilinofluorane, 3- (N, N-dibutylamino) -6-methyl-7- Xylidinofluolane, 3-piperidino-6-methyl-7-anilinofluoran, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis (1-ethyl-2-methylindol-) 3-yl) phthalide, 3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide, 3 -(4-Diethylamino-2-ethoxyphenyl) -3- (1-ethyl-2-methylindole-3-yl) -4-azaphthalide, 3- (4-diethylaminophenyl) -3- (1-ethyl-2) -Methylindole-3-yl) phthalide and 3', 6'-bis (diphenylamino) spiroisobenzofuran-1 (3H), 9'-[9H] xanthen-3-one can be mentioned.
　色素ＮＣとしては、例えば、染料も挙げられる。染料の具体例としては、ブリリアントグリーン、エチルバイオレット、メチルグリーン、クリスタルバイオレット、ベイシックフクシン、メチルバイオレット２Ｂ、キナルジンレッド、ローズベンガル、メタニルイエロー、チモールスルホフタレイン、キシレノールブルー、メチルオレンジ、パラメチルレッド、コンゴーフレッド、ベンゾプルプリン４Ｂ、α－ナフチルレッド、ナイルブルー２Ｂ、ナイルブルーＡ、メチルバイオレット、マラカイトグリーン、パラフクシン、ビクトリアピュアブルー－ナフタレンスルホン酸塩、ビクトリアピュアブルーＢＯＨ（保土谷化学工業（株））、オイルブルー＃６０３（オリヱント化学工業（株））、オイルピンク＃３１２（オリヱント化学工業（株））、オイルレッド５Ｂ（オリヱント化学工業（株））、オイルスカーレット＃３０８（オリヱント化学工業（株））、オイルレッドＯＧ（オリヱント化学工業（株））、オイルレッドＲＲ（オリヱント化学工業（株））、オイルグリーン＃５０２（オリヱント化学工業（株））、スピロンレッドＢＥＨスペシャル（保土谷化学工業（株））、ｍ－クレゾールパープル、クレゾールレッド、ローダミンＢ、ローダミン６Ｇ、スルホローダミンＢ、オーラミン、４－ｐ－ジエチルアミノフェニルイミノナフトキノン、２－カルボキシアニリノ－４－ｐ－ジエチルアミノフェニルイミノナフトキノン、２－カルボキシステアリルアミノ－４－ｐ－Ｎ，Ｎ－ビス（ヒドロキシエチル）アミノ－フェニルイミノナフトキノン、１－フェニル－３－メチル－４－ｐ－ジエチルアミノフェニルイミノ－５－ピラゾロン、及び１－β－ナフチル－４－ｐ－ジエチルアミノフェニルイミノ－５－ピラゾロンが挙げられる。 Examples of the dye NC include a dye. Specific examples of dyes include Brilliant Green, Ethyl Violet, Methyl Green, Crystal Violet, Basic Fuxin, Methyl Violet 2B, Kinaldine Red, Rose Bengal, Metanyl Yellow, Timor Sulfophthalene, Xylenol Blue, Methyl Orange, Paramethyl. Red, Congofred, Benzopurpurin 4B, α-Naftil Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malakite Green, Parafuxin, Victoria Pure Blue-Naphthalene Sulfonate, Victoria Pure Blue BOH (Hodoya Chemical Industry (Hodoya Chemical Industry) ), Oil Blue # 603 (Orient Chemical Industry Co., Ltd.), Oil Pink # 312 (Orient Chemical Industry Co., Ltd.), Oil Red 5B (Orient Chemical Industry Co., Ltd.), Oil Scarlet # 308 (Orient Chemical Industry Co., Ltd.) ), Oil Red OG (Orient Chemical Industry Co., Ltd.), Oil Red RR (Orient Chemical Industry Co., Ltd.), Oil Green # 502 (Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Industry Co., Ltd.) Co., Ltd.), m-cresol purple, cresol red, rhodamine B, rhodamine 6G, sulfordamine B, auramine, 4-p-diethylaminophenyliminonaphthoquinone, 2-carboxyanilino-4-p-diethylaminophenyliminonaphthoquinone, 2 -Carboxystearylamino-4-p-N, N-bis (hydroxyethyl) amino-phenyliminonaphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone, and 1-β-naphthyl -4-p-diethylaminophenylimino-5-pyrazolone can be mentioned.
　色素ＮＣは、露光部の視認性、非露光部の視認性、現像後のパターン視認性、及び解像性の観点から、ラジカルにより最大吸収波長が変化する色素であることが好ましく、ラジカルにより発色する色素であることがより好ましい。 The dye NC is preferably a dye whose maximum absorption wavelength is changed by radicals from the viewpoints of visibility of exposed parts, visibility of non-exposed parts, pattern visibility after development, and resolution, and color is developed by radicals. It is more preferable that the dye is a radical.
　色素ＮＣは、ロイコクリスタルバイオレット、クリスタルバイオレットラクトン、ブリリアントグリーン、又はビクトリアピュアブルー－ナフタレンスルホン酸塩であることが好ましい。 The dye NC is preferably leuco crystal violet, crystal violet lactone, brilliant green, or Victoria pure blue-naphthalene sulfonate.
　ネガ型感光性樹脂層Ｎは、１種単独、又は２種以上の色素を含んでもよい。 The negative type photosensitive resin layer N may contain one kind alone or two or more kinds of dyes.
　色素の含有割合は、露光部の視認性、非露光部の視認性、現像後のパターン視認性及び解像性の観点から、ネガ型感光性樹脂層Ｎの全質量に対して、０．１質量％以上であることが好ましく、０．１質量％～１０質量％であることがより好ましく、０．１質量％～５質量％であることが更に好ましく、０．１質量％～１質量％であることが特に好ましい。 The content ratio of the dye is 0.1 with respect to the total mass of the negative photosensitive resin layer N from the viewpoints of the visibility of the exposed portion, the visibility of the non-exposed portion, the pattern visibility after development, and the resolution. It is preferably 0% by mass or more, more preferably 0.1% by mass to 10% by mass, further preferably 0.1% by mass to 5% by mass, and 0.1% by mass to 1% by mass. Is particularly preferable.
　色素ＮＣの含有割合は、ネガ型感光性樹脂層Ｎに含まれる色素ＮＣの全てを発色状態にした場合の色素の含有割合を意味する。以下、ラジカルにより発色する色素を例として、色素ＮＣの含有割合の定量方法を説明する。メチルエチルケトン（１００ｍＬ）に、色素（０．００１ｇ）、及び色素（０．０１ｇ）をそれぞれ溶かした２つの溶液を調製する。得られた各溶液に、光ラジカル重合開始剤としてＩＲＧＡＣＵＲＥ　ＯＸＥ－０１（ＢＡＳＦ社）を加えた後、３６５ｎｍの光を照射することによりラジカルを発生させ、全ての色素を発色状態にする。次に、大気雰囲気下で、分光光度計（ＵＶ３１００、（株）島津製作所）を用いて、液温が２５℃である各溶液の吸光度を測定し、検量線を作成する。次に、色素に代えてネガ型感光性樹脂層Ｎ（３ｇ）をメチルエチルケトンに溶かすこと以外は上記と同様の方法で、色素を全て発色させた溶液の吸光度を測定する。得られたネガ型感光性樹脂層Ｎを含む溶液の吸光度から、検量線に基づいてネガ型感光性樹脂層Ｎに含まれる色素の含有量を算出する。 The content ratio of the dye NC means the content ratio of the dye when all of the dye NC contained in the negative type photosensitive resin layer N is in a colored state. Hereinafter, a method for quantifying the content ratio of dye NC will be described by taking a dye that develops color by radicals as an example. Two solutions are prepared by dissolving the dye (0.001 g) and the dye (0.01 g) in methyl ethyl ketone (100 mL). IRGACURE OXE-01 (BASF) is added to each of the obtained solutions as a photoradical polymerization initiator, and then radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state. Next, in an air atmosphere, the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve is prepared. Next, the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that the negative photosensitive resin layer N (3 g) is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the negative photosensitive resin layer N, the content of the dye contained in the negative photosensitive resin layer N is calculated based on the calibration curve.
＜＜界面活性剤＞＞
　ネガ型感光性樹脂層Ｎは、厚さの均一性の観点から、界面活性剤を含むことが好ましい。界面活性剤としては、例えば、アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性（非イオン性）界面活性剤、及び両性界面活性剤が挙げられ、ノニオン性界面活性剤が好ましい。 << Surfactant >>
The negative photosensitive resin layer N preferably contains a surfactant from the viewpoint of thickness uniformity. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants, and nonionic surfactants are preferable.
　ノニオン性界面活性剤としては、例えば、ポリオキシエチレン高級アルキルエーテル化合物、ポリオキシエチレン高級アルキルフェニルエーテル化合物、ポリオキシエチレングリコールの高級脂肪酸ジエステル化合物、シリコーン系ノニオン性界面活性剤、及びフッ素系ノニオン性界面活性剤が挙げられる。 Examples of the nonionic surfactant include a polyoxyethylene higher alkyl ether compound, a polyoxyethylene higher alkylphenyl ether compound, a higher fatty acid diester compound of polyoxyethylene glycol, a silicone-based nonionic surfactant, and a fluorine-based nonionic property. Surfactants can be mentioned.
　ネガ型感光性樹脂層Ｎは、解像性がより優れる点から、フッ素系ノニオン性界面活性剤を含むことが好ましい。ネガ型感光性樹脂層Ｎがフッ素系ノニオン性界面活性剤を含むことで、エッチング液のネガ型感光性樹脂層Ｎへの浸透を抑制してサイドエッチングを低減するためと考えられる。フッ素系ノニオン性界面活性剤の市販品としては、例えば、メガファック（登録商標）Ｆ－５５１、Ｆ－５５２（ＤＩＣ（株））、及びメガファックＦ－５５４（ＤＩＣ（株））が挙げられる。 The negative photosensitive resin layer N preferably contains a fluorine-based nonionic surfactant from the viewpoint of being more excellent in resolution. It is considered that the negative type photosensitive resin layer N contains a fluorine-based nonionic surfactant to suppress the penetration of the etching solution into the negative type photosensitive resin layer N and reduce the side etching. Commercially available products of the fluorine-based nonionic surfactant include, for example, Megafvck (registered trademark) F-551, F-552 (DIC Corporation), and Megafvck F-554 (DIC Corporation). ..
　界面活性剤としては、例えば、国際公開第２０１８／１７９６４０号の段落０１２０～段落０１２５に記載の界面活性剤、特許第４５０２７８４号公報の段落００１７に記載の界面活性剤、及び特開２００９－２３７３６２号公報の段落００６０～段落００７１に記載の界面活性剤も挙げられる。 Examples of the surfactant include the surfactant described in paragraphs 0120 to 0125 of International Publication No. 2018/179640, the surfactant described in paragraph 0017 of Japanese Patent No. 45027884, and JP-A-2009-237362. The surfactants described in paragraphs 0060 to 0071 of the publication are also mentioned.
　ネガ型感光性樹脂層Ｎは、１種単独、又は２種以上の界面活性剤を含んでもよい。 The negative type photosensitive resin layer N may contain one type alone or two or more types of surfactants.
　界面活性剤の含有割合は、ネガ型感光性樹脂層Ｎの全質量に対して、０．００１質量％～１０質量％であることが好ましく、０．０１質量％～３質量％であることがより好ましい。 The content ratio of the surfactant is preferably 0.001% by mass to 10% by mass, and preferably 0.01% by mass to 3% by mass, based on the total mass of the negative photosensitive resin layer N. More preferred.
＜＜添加剤＞＞
　添加剤としては、例えば、ラジカル重合禁止剤、増感剤、可塑剤、ヘテロ環状化合物、上述した以外の樹脂、及び溶剤が挙げられる。
　ネガ型感光性樹脂層Ｎは、１種単独、又は２種以上の添加剤を含んでもよい。 << Additives >>
Examples of the additive include a radical polymerization inhibitor, a sensitizer, a plasticizer, a heterocyclic compound, a resin other than those described above, and a solvent.
The negative type photosensitive resin layer N may contain one kind alone or two or more kinds of additives.
　ネガ型感光性樹脂層Ｎは、ラジカル重合禁止剤を含んでもよい。ラジカル重合禁止剤としては、例えば、特許第４５０２７８４号公報の段落００１８に記載された熱重合防止剤が挙げられる。ラジカル重合禁止剤は、フェノチアジン、フェノキサジン、又は４－メトキシフェノールであることが好ましい。上記以外のラジカル重合禁止剤としては、例えば、ナフチルアミン、塩化第一銅、ニトロソフェニルヒドロキシアミンアルミニウム塩、及びジフェニルニトロソアミンが挙げられる。ネガ型感光性樹脂層Ｎの感度を損なわないために、ニトロソフェニルヒドロキシアミンアルミニウム塩をラジカル重合禁止剤として使用することが好ましい。 The negative type photosensitive resin layer N may contain a radical polymerization inhibitor. Examples of the radical polymerization inhibitor include the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784. The radical polymerization inhibitor is preferably phenothiazine, phenoxazine, or 4-methoxyphenol. Examples of the radical polymerization inhibitor other than the above include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. It is preferable to use a nitrosophenylhydroxyamine aluminum salt as a radical polymerization inhibitor so as not to impair the sensitivity of the negative photosensitive resin layer N.
　ラジカル重合禁止剤、ベンゾトリアゾ－ル化合物、及びカルボキシベンゾトリアゾ－ル化合物の合計含有量の割合は、ネガ型感光性樹脂層Ｎの全質量に対して、０．０１質量％～３質量％であることが好ましく、０．０５質量％～１質量％であることがより好ましい。上記した各成分の合計含有量の割合を０．０１質量％以上にすることは、ネガ型感光性樹脂層Ｎに保存安定性を付与する観点から好ましい。一方で、上記した各成分の合計含有量の割合を３質量％以下にすることは、感度を維持し、染料の脱色を抑える観点から好ましい。 The ratio of the total content of the radical polymerization inhibitor, the benzotriazol compound, and the carboxybenzotriazol compound is 0.01% by mass to 3% by mass with respect to the total mass of the negative photosensitive resin layer N. It is preferably 0.05% by mass to 1% by mass, and more preferably 0.05% by mass to 1% by mass. It is preferable that the ratio of the total content of each of the above components is 0.01% by mass or more from the viewpoint of imparting storage stability to the negative photosensitive resin layer N. On the other hand, it is preferable that the ratio of the total content of each of the above-mentioned components is 3% by mass or less from the viewpoint of maintaining the sensitivity and suppressing the decolorization of the dye.
　ネガ型感光性樹脂層Ｎは、増感剤を含んでもよい。増感剤としては、制限されず、公知の増感剤を用いることができる。また、増感剤として、染料、及び顔料を用いることもできる。増感剤としては、例えば、ジアルキルアミノベンゾフェノン化合物、ピラゾリン化合物、アントラセン化合物、クマリン化合物、キサントン化合物、チオキサントン化合物、アクリドン化合物、オキサゾール化合物、ベンゾオキサゾール化合物、チアゾール化合物、ベンゾチアゾール化合物、トリアゾール化合物（例えば、１，２，４－トリアゾール）、スチルベン化合物、トリアジン化合物、チオフェン化合物、ナフタルイミド化合物、トリアリールアミン化合物、及びアミノアクリジン化合物が挙げられる。 The negative type photosensitive resin layer N may contain a sensitizer. The sensitizer is not limited, and a known sensitizer can be used. In addition, dyes and pigments can also be used as the sensitizer. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, and triazole compounds (for example, 1,2,4-triazole), stillben compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds, and aminoaclysin compounds.
　ネガ型感光性樹脂層Ｎは、１種単独、又は２種以上の増感剤を含んでもよい。 The negative type photosensitive resin layer N may contain one type alone or two or more types of sensitizers.
　ネガ型感光性樹脂層Ｎが増感剤を含む場合、増感剤の含有割合は、目的により適宜選択できるが、光源に対する感度の向上、及び重合速度と連鎖移動のバランスによる硬化速度の向上の観点から、ネガ型感光性樹脂層Ｎの全質量に対して、０．０１質量％～５質量％であることが好ましく、０．０５質量％～１質量％であることがより好ましい。 When the negative photosensitive resin layer N contains a sensitizer, the content ratio of the sensitizer can be appropriately selected depending on the purpose, but the sensitivity to the light source is improved and the curing rate is improved by the balance between the polymerization rate and the chain transfer. From the viewpoint, it is preferably 0.01% by mass to 5% by mass, and more preferably 0.05% by mass to 1% by mass with respect to the total mass of the negative type photosensitive resin layer N.
　ネガ型感光性樹脂層Ｎは、可塑剤、及びヘテロ環状化合物よりなる群から選択される少なくとも１種を含んでもよい。可塑剤、及びヘテロ環状化合物としては、例えば、国際公開第２０１８／１７９６４０号の段落００９７～段落０１０３、及び段落０１１１～段落０１１８に記載された化合物が挙げられる。 The negative photosensitive resin layer N may contain at least one selected from the group consisting of a plasticizer and a heterocyclic compound. Examples of the plasticizer and the heterocyclic compound include the compounds described in paragraphs 097 to 0103 and 0111 to 0118 of International Publication No. 2018/179640.
　ネガ型感光性樹脂層Ｎは、上述した以外の樹脂を含んでもよい。
　上述した以外の樹脂としては、アクリル樹脂、スチレン－アクリル共重合体（ただし、スチレン含有率が４０質量％以下の共重合体に限る。）、ポリウレタン樹脂、ポリビニルアルコール、ポリビニルホルマール、ポリアミド樹脂、ポリエステル樹脂、ポリアミド樹脂、エポキシ樹脂、ポリアセタール樹脂、ポリヒドロキシスチレン樹脂、ポリイミド樹脂、ポリベンゾオキサゾール樹脂、ポリシロキサン樹脂、ポリエチレンイミン、ポリアリルアミン、及びポリアルキレングリコールが挙げられる。 The negative photosensitive resin layer N may contain a resin other than those described above.
Resins other than those described above include acrylic resins, styrene-acrylic copolymers (however, limited to copolymers having a styrene content of 40% by mass or less), polyurethane resins, polyvinyl alcohols, polyvinyl formals, polyamide resins, and polyesters. Examples thereof include resins, polyamide resins, epoxy resins, polyacetal resins, polyhydroxystyrene resins, polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines, and polyalkylene glycols.
　ネガ型感光性樹脂層Ｎは、溶剤を含んでもよい。溶剤を含む感光性樹脂組成物によりネガ型感光性樹脂層Ｎを形成した場合、ネガ型感光性樹脂層Ｎに溶剤が残留することがある。溶剤については後述する。 The negative type photosensitive resin layer N may contain a solvent. When the negative type photosensitive resin layer N is formed by the photosensitive resin composition containing a solvent, the solvent may remain in the negative type photosensitive resin layer N. The solvent will be described later.
　ネガ型感光性樹脂層Ｎは、添加剤として、例えば、金属酸化物粒子、酸化防止剤、分散剤、酸増殖剤、現像促進剤、導電性繊維、熱ラジカル重合開始剤、熱酸発生剤、紫外線吸収剤、増粘剤、架橋剤、有機沈殿防止剤、及び無機沈殿防止剤よりなる群から選択される少なくとも１種を含んでもよい。添加剤については、例えば、特開２０１４－８５６４３号公報の段落０１６５～段落０１８４に記載されている。上記公報の内容は、参照により本明細書に組み込まれる。 The negative photosensitive resin layer N has, as an additive, for example, a metal oxide particle, an antioxidant, a dispersant, an acid growth agent, a development accelerator, a conductive fiber, a thermal radical polymerization initiator, a thermal acid generator, and the like. It may contain at least one selected from the group consisting of UV absorbers, thickeners, cross-linking agents, organic precipitation inhibitors, and inorganic precipitation inhibitors. Additives are described, for example, in paragraphs 0165 to 0184 of JP2014-85643A. The contents of the above publication are incorporated herein by reference.
－不純物等－
　ネガ型感光性樹脂層Ｎは、所定量の不純物を含んでいてもよい。不純物の具体例としては、ナトリウム、カリウム、マグネシウム、カルシウム、鉄、マンガン、銅、アルミニウム、チタン、クロム、コバルト、ニッケル、亜鉛、スズ、ハロゲン、及びこれらのイオンが挙げられる。上記の中でも、ハロゲン化物イオン、ナトリウムイオン、及びカリウムイオンは不純物として混入し易いため、下記の含有量にすることが好ましい。 -Impurities, etc.-
The negative photosensitive resin layer N may contain a predetermined amount of impurities. Specific examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Among the above, halide ions, sodium ions, and potassium ions are likely to be mixed as impurities, so the content is preferably as follows.
　ネガ型感光性樹脂層Ｎにおける不純物の含有量は、質量基準で、８０ｐｐｍ以下であることが好ましく、１０ｐｐｍ以下であることがより好ましく、２ｐｐｍ以下であることが更に好ましい。ネガ型感光性樹脂層Ｎにおける不純物の含有量は、質量基準で、１ｐｐｂ以上、又は０．１ｐｐｍ以上とすることができる。 The content of impurities in the negative photosensitive resin layer N is preferably 80 ppm or less, more preferably 10 ppm or less, and further preferably 2 ppm or less on a mass basis. The content of impurities in the negative photosensitive resin layer N can be 1 ppb or more or 0.1 ppm or more on a mass basis.
　不純物を上記範囲にする方法としては、ネガ型感光性樹脂層Ｎの原料として不純物の含有量が少ない原料を選択すること、ネガ型感光性樹脂層Ｎの形成時に不純物の混入を防ぐこと、及び製造設備を洗浄して不純物を除去することが挙げられる。このような方法により、不純物量を上記範囲内とすることができる。 As a method of setting impurities in the above range, a raw material having a low impurity content is selected as the raw material of the negative photosensitive resin layer N, prevention of contamination of impurities during the formation of the negative photosensitive resin layer N, and Cleaning the manufacturing equipment to remove impurities. By such a method, the amount of impurities can be kept within the above range.
　不純物は、公知の方法、例えば、ＩＣＰ（Ｉｎｄｕｃｔｉｖｅｌｙ　Ｃｏｕｐｌｅｄ　Ｐｌａｓｍａ）発光分光分析法、原子吸光分光法、又はイオンクロマトグラフィー法で定量できる。 Impurities can be quantified by a known method, for example, ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, or ion chromatography.
　ネガ型感光性樹脂層Ｎにおける、ベンゼン、ホルムアルデヒド、トリクロロエチレン、１，３－ブタジエン、四塩化炭素、クロロホルム、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、及びヘキサンの含有量は、少ないことが好ましい。上記した化合物のネガ型感光性樹脂層Ｎ中における含有量としては、質量基準で、１００ｐｐｍ以下が好ましく、２０ｐｐｍ以下がより好ましく、４ｐｐｍ以下が更に好ましい。上記した化合物のネガ型感光性樹脂層Ｎ中における含有量は、質量基準で、１０ｐｐｂ以上、又は１００ｐｐｂ以上とすることができる。上記した化合物は、上記の金属の不純物と同様の方法で含有量を抑制できる。また、公知の測定法により定量できる。 The content of benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and hexane in the negative photosensitive resin layer N is low. Is preferable. The content of the above compound in the negative photosensitive resin layer N is preferably 100 ppm or less, more preferably 20 ppm or less, still more preferably 4 ppm or less on a mass basis. The content of the above compound in the negative photosensitive resin layer N can be 10 ppb or more or 100 ppb or more on a mass basis. The content of the above-mentioned compound can be suppressed in the same manner as the above-mentioned metal impurities. Moreover, it can be quantified by a known measurement method.
　ネガ型感光性樹脂層Ｎにおける水の含有量は、信頼性及びラミネート性を向上させる点から、０．０１質量％～１．０質量％であることが好ましく、０．０５質量％～０．５質量％であることがより好ましい。 The water content in the negative photosensitive resin layer N is preferably 0.01% by mass to 1.0% by mass, preferably 0.05% by mass to 0% by mass, from the viewpoint of improving reliability and laminateability. More preferably, it is 5% by mass.
－厚さ－
　ネガ型感光性樹脂層Ｎの厚さは、例えば、後述する現像工程において形成する樹脂パターン２の厚さに応じて決定すればよい。ネガ型感光性樹脂層Ｎの厚さは、例えば、１μｍ～１００μｍの範囲で決定すればよい。 -thickness-
The thickness of the negative photosensitive resin layer N may be determined, for example, according to the thickness of the resin pattern 2 formed in the developing step described later. The thickness of the negative photosensitive resin layer N may be determined, for example, in the range of 1 μm to 100 μm.
－透過率－
　ネガ型感光性樹脂層Ｎにおいて、波長３６５ｎｍの光の透過率は、密着性により優れる点から、１０％以上であることが好ましく、３０％以上であることがより好ましく、５０％以上であることが特に好ましい。透過率の上限は、制限されない。ネガ型感光性樹脂層Ｎにおいて、波長３６５ｎｍの光の透過率は、９９．９％以下であることが好ましい。 -Transmittance-
In the negative photosensitive resin layer N, the transmittance of light having a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and more preferably 50% or more from the viewpoint of being more excellent in adhesion. Is particularly preferable. The upper limit of transmittance is not limited. In the negative photosensitive resin layer N, the transmittance of light having a wavelength of 365 nm is preferably 99.9% or less.
　準備工程は、透明基材と、上記透明基材の上に遮光性パターン１と、を有する積層前駆体を準備する工程と、上記透明基材及び上記遮光性パターン１の上に上記ネガ型感光性樹脂層Ｎを形成する工程と、を含むことが好ましい。上記ネガ型感光性樹脂層Ｎを形成する工程において、感光性転写材料（「ドライフィルム」ともいう。）を用いて上記ネガ型感光性樹脂層Ｎを形成することが好ましい。
　すなわち、上記ネガ型感光性樹脂層Ｎは、感光性転写材料により形成されてなる層であることが好ましい。 The preparation step includes a step of preparing a laminated precursor having a transparent base material and a light-shielding pattern 1 on the transparent base material, and a negative type photosensitive on the transparent base material and the light-shielding pattern 1. It is preferable to include a step of forming the sex resin layer N. In the step of forming the negative type photosensitive resin layer N, it is preferable to form the negative type photosensitive resin layer N by using a photosensitive transfer material (also referred to as “dry film”).
That is, the negative type photosensitive resin layer N is preferably a layer formed of a photosensitive transfer material.
　準備工程は、透明基材を準備する工程と、上記透明基材の上に遮光性パターン１を形成する工程と、上記透明基材及び上記遮光性パターン１の上にネガ型感光性樹脂層Ｎを形成する工程と、を含むことが好ましい。上記遮光性パターン１を形成する工程は、上記透明基材の上に遮光性層を形成する工程と、上記遮光性層の上に感光性樹脂層を形成する工程と、上記感光性樹脂層の露光及び現像によってレジストパターンを形成する工程と、上記レジストパターンによって覆われていない上記遮光性層を除去する工程と、を含むことが好ましい。上記ネガ型感光性樹脂層Ｎを形成する工程において、感光性転写材料を用いて上記ネガ型感光性樹脂層Ｎを形成することが好ましい。 The preparation steps include a step of preparing a transparent base material, a step of forming a light-shielding pattern 1 on the transparent base material, and a negative type photosensitive resin layer N on the transparent base material and the light-shielding pattern 1. It is preferable to include a step of forming the above. The steps of forming the light-shielding pattern 1 include a step of forming a light-shielding layer on the transparent base material, a step of forming a photosensitive resin layer on the light-shielding layer, and a step of forming the photosensitive resin layer. It is preferable to include a step of forming a resist pattern by exposure and development, and a step of removing the light-shielding layer not covered by the resist pattern. In the step of forming the negative type photosensitive resin layer N, it is preferable to form the negative type photosensitive resin layer N by using a photosensitive transfer material.
　準備工程は、例えば、透明基材を準備する工程と、上記透明基材の上に遮光性パターン１を形成する工程と、上記透明基材及び上記遮光性パターン１の上にネガ型感光性樹脂層Ｎを形成する工程と、を含む態様が挙げられる。 The preparation steps include, for example, a step of preparing a transparent base material, a step of forming a light-shielding pattern 1 on the transparent base material, and a negative photosensitive resin on the transparent base material and the light-shielding pattern 1. Examples thereof include a step of forming the layer N and the like.
　また、準備工程は、例えば、透明基材と、上記透明基材の上に遮光性層と、を有する積層前駆体を準備する工程と、上記遮光性層から遮光性パターン１を形成する工程と、上記透明基材及び上記遮光性パターン１の上にネガ型感光性樹脂層Ｎを形成する工程と、を含む態様が挙げられる。遮光性層は、遮光性パターン１の材料となる層である。透明基材と遮光性層とを有する積層前駆体の製造方法としては、例えば、透明基材の上に遮光性層を形成する方法が挙げられる。 Further, the preparation steps include, for example, a step of preparing a laminated precursor having a transparent base material and a light-shielding layer on the transparent base material, and a step of forming a light-shielding pattern 1 from the light-shielding layer. An embodiment including a step of forming a negative type photosensitive resin layer N on the transparent base material and the light-shielding pattern 1 can be mentioned. The light-shielding layer is a layer that is a material for the light-shielding pattern 1. Examples of the method for producing a laminated precursor having a transparent base material and a light-shielding layer include a method of forming a light-shielding layer on the transparent base material.
　更に、準備工程は、例えば、透明基材の一方の面に遮光性層を形成する工程、遮光性層上にフォトレジスト層を形成する工程、上記フォトレジスト層を露光及び現像してレジストパターンを形成する工程、並びに、上記遮光性層をエッチングし上記遮光性パターン１を形成する工程を含む態様が挙げられる。フォトレジスト層の形成方法としては、特に制限はなく、公知のフォトレジスト組成物及び感光性転写材料を用いることができる。 Further, the preparatory steps include, for example, a step of forming a light-shielding layer on one surface of the transparent substrate, a step of forming a photoresist layer on the light-shielding layer, and exposing and developing the photoresist layer to form a resist pattern. Examples thereof include a step of forming and a step of etching the light-shielding layer to form the light-shielding pattern 1. The method for forming the photoresist layer is not particularly limited, and known photoresist compositions and photosensitive transfer materials can be used.
－遮光性パターン１の形成方法－
　以下、遮光性パターン１の形成方法について説明する。
　遮光性パターン１の形成方法としては、例えば、透明基材の上に遮光性層を形成し、次いで、上記遮光性層をパターン状に加工する方法が挙げられる。 -Method of forming light-shielding pattern 1-
Hereinafter, a method for forming the light-shielding pattern 1 will be described.
Examples of the method of forming the light-shielding pattern 1 include a method of forming a light-shielding layer on a transparent base material and then processing the light-shielding layer into a pattern.
　遮光性層を形成する方法としては、例えば、スパッタリング、及びめっきが挙げられる。スパッタリングにおいては、例えば、透明基材の上にＣｕ、Ｔｉ、又はＮｉを含む層（遮光性層）を形成することができる。上記金属の中でも、電気抵抗が小さく、安価なＣｕが好ましい。スパッタリングによって形成される層（遮光性層）の成分は、Ｎｉ、Ａｌ、Ｎｂ、Ｗ、Ｎｉ－Ｐ、又はＮｉ－Ｂであってもよい。めっきとしては、例えば、無電解めっきが挙げられる。無電解めっきの方法としては、公知の方法を利用することができる。例えば、無電解銅めっきにおいては、銅イオンと還元剤との反応によって透明基材の上に銅を析出させることができる。無電解めっきにおいて使用される触媒は、パラジウム－スズの混合触媒であることが好ましい。触媒の１次粒子径は、１０ｎｍ以下であることが好ましい。無電解めっきに使用されるめっき液は、還元剤として次亜リン酸を含むことが好ましい。めっきとしては、例えば、下記「パターン３形成工程」の項で説明するめっきも挙げられる。遮光性層の構造は、単層構造、又は多層構造であってもよい。多層構造を有する遮光性層を形成することで、多層構造を有する導電性パターンを形成することができる。多層構造を有する遮光性層に含まれる各層の形成方法としては、例えば、無電解めっき、スパッタリング、蒸着、及びカップリング剤塗布が挙げられる。 Examples of the method for forming the light-shielding layer include sputtering and plating. In sputtering, for example, a layer containing Cu, Ti, or Ni (light-shielding layer) can be formed on a transparent substrate. Among the above metals, Cu, which has low electrical resistance and is inexpensive, is preferable. The component of the layer (light-shielding layer) formed by sputtering may be Ni, Al, Nb, W, Ni-P, or Ni-B. Examples of plating include electroless plating. As a method of electroless plating, a known method can be used. For example, in electroless copper plating, copper can be deposited on a transparent substrate by the reaction of copper ions and a reducing agent. The catalyst used in electroless plating is preferably a palladium-tin mixed catalyst. The primary particle size of the catalyst is preferably 10 nm or less. The plating solution used for electroless plating preferably contains hypophosphorous acid as a reducing agent. Examples of the plating include the plating described in the section "Pattern 3 forming step" below. The structure of the light-shielding layer may be a single-layer structure or a multi-layer structure. By forming the light-shielding layer having a multi-layer structure, a conductive pattern having a multi-layer structure can be formed. Examples of the method for forming each layer included in the light-shielding layer having a multi-layer structure include electroless plating, sputtering, vapor deposition, and coating of a coupling agent.
　遮光性層をパターン状に加工する方法としては、例えば、フォトリソグラフィが挙げられる。フォトリソグラフィとしては、公知のフォトリソグラフィを利用することができる。例えば、遮光性層の上に感光性樹脂層を形成し、次いで、上記感光性樹脂層の露光及び現像によってレジストパターンを形成した後、上記レジストパターンによって覆われていない上記遮光性層を除去することで、遮光性パターンを形成することができる。 As a method of processing the light-shielding layer into a pattern, for example, photolithography can be mentioned. As the photolithography, a known photolithography can be used. For example, a photosensitive resin layer is formed on the light-shielding layer, then a resist pattern is formed by exposure and development of the photosensitive resin layer, and then the light-shielding layer not covered by the resist pattern is removed. As a result, a light-shielding pattern can be formed.
　遮光性層の上に形成される感光性樹脂層の種類は、制限されない。感光性樹脂層は、ポジ型感光性樹脂層、又はネガ型感光性樹脂層であってもよい。ネガ型感光性樹脂層としては、例えば、上記「ネガ型感光性樹脂層Ｎ」の項において説明したネガ型感光性樹脂層が挙げられる。感光性樹脂層を形成する方法としては、例えば、感光性樹脂組成物を用いる方法、及び感光性転写材料を用いる方法が挙げられる。感光性樹脂組成物を用いる方法としては、例えば、遮光性層の上に、感光性樹脂組成物を塗布し、次いで、感光性樹脂組成物を乾燥する方法が挙げられる。感光性樹脂組成物は、感光性樹脂層の材料を含む組成物である。感光性転写材料を用いる方法としては、例えば、感光性樹脂層を有する感光性転写材料と遮光性層とを貼り合わせることで、遮光性層の上に感光性樹脂層を配置する方法が挙げられる。ネガ型感光性樹脂層を形成する方法については、下記「ネガ型感光性樹脂層Ｎの形成方法」の項を参照することができる。 The type of the photosensitive resin layer formed on the light-shielding layer is not limited. The photosensitive resin layer may be a positive type photosensitive resin layer or a negative type photosensitive resin layer. Examples of the negative photosensitive resin layer include the negative photosensitive resin layer described in the above section “Negative photosensitive resin layer N”. Examples of the method for forming the photosensitive resin layer include a method using a photosensitive resin composition and a method using a photosensitive transfer material. Examples of the method using the photosensitive resin composition include a method of applying the photosensitive resin composition on the light-shielding layer and then drying the photosensitive resin composition. The photosensitive resin composition is a composition containing a material for a photosensitive resin layer. Examples of the method using the photosensitive transfer material include a method of arranging the photosensitive resin layer on the light-shielding layer by laminating the photosensitive transfer material having the photosensitive resin layer and the light-shielding layer. .. For the method of forming the negative type photosensitive resin layer, the following section "Method of forming the negative type photosensitive resin layer N" can be referred to.
　感光性樹脂層の露光方法は、感光性樹脂層において露光部及び非露光部を形成可能な方法であれば制限されない。露光方法としては、公知の方法を利用することができる。露光される感光性樹脂層の領域は、目的とする遮光性パターンの形状に応じて決定すればよい。露光条件については、下記「露光工程」の項を参照することができる。 The exposure method of the photosensitive resin layer is not limited as long as it is a method capable of forming an exposed portion and a non-exposed portion in the photosensitive resin layer. As the exposure method, a known method can be used. The region of the photosensitive resin layer to be exposed may be determined according to the shape of the target light-shielding pattern. For the exposure conditions, the section "Exposure step" below can be referred to.
　感光性樹脂層の現像方法は、感光性樹脂層の露光部又は非露光部を除去することで、感光性樹脂層をパターン状に加工可能な方法であれば制限されない。ネガ型感光性樹脂層の現像においては、ネガ型感光性樹脂層の非露光部が除去される。ポジ型感光性樹脂層の現像においては、ポジ型感光性樹脂層の露光部が除去される。現像方法としては、公知の方法を利用することができる。現像条件については、下記「現像工程」の項を参照することができる。 The method for developing the photosensitive resin layer is not limited as long as the photosensitive resin layer can be processed into a pattern by removing the exposed portion or the non-exposed portion of the photosensitive resin layer. In the development of the negative photosensitive resin layer, the unexposed portion of the negative photosensitive resin layer is removed. In the development of the positive photosensitive resin layer, the exposed portion of the positive photosensitive resin layer is removed. As a developing method, a known method can be used. For the development conditions, the section "Development process" below can be referred to.
　レジストパターンによって覆われていない遮光性層（すなわち、露出した遮光性層）を除去する方法としては、公知の方法を利用することができる。例えば、遮光性層が金属を含む場合、エッチングによって、レジストパターンによって覆われていない遮光性層を除去することができる。エッチングとしては、例えば、ウェットエッチング、及びドライエッチングが挙げられる。エッチングは、ウェットエッチングであることが好ましい。ウェットエッチングは、エッチング液と称される薬品を用いるエッチングである。エッチング液としては、例えば、硫酸－過酸化水素水溶液が挙げられる。硫酸－過酸化水素水溶液の組成は、制限されない。硫酸－過酸化水素水溶液としては、例えば、硫酸の濃度が１体積％～１０体積％であり、かつ、過酸化水素の濃度が１体積％～１０体積％である硫酸－過酸化水素水溶液が挙げられる。硫酸－過酸化水素水溶液の温度は、例えば、２０℃～３５℃の範囲で設定することができる。硫酸－過酸化水素水溶液への浸漬時間は、例えば、１分間～１０分間の範囲で設定することができる。遮光性層が銅を含む場合、硫酸－過酸化水素水溶液に溶解した銅の濃度が例えば５０ｇ／Ｌとなるまで、硫酸－過酸化水素水溶液を使用することができる。エッチング液としては、例えば、塩化第二銅溶液も挙げられる。塩化第二銅溶液の組成は、制限されない。塩化第二銅溶液として、例えば、２０質量％～３５質量％の塩化第二銅、及び１質量％～７質量％の塩素を含む溶液を好ましく用いることができる。ただし、エッチングの条件は、上記した条件に制限されるものではない。例えば、エッチング液の温度、及びエッチング液への浸漬時間は、遮光性層の組成、遮光性層の厚さ、及びエッチング液の種類に応じて決定すればよい。 A known method can be used as a method for removing the light-shielding layer (that is, the exposed light-shielding layer) that is not covered by the resist pattern. For example, when the light-shielding layer contains metal, the light-shielding layer that is not covered by the resist pattern can be removed by etching. Examples of the etching include wet etching and dry etching. The etching is preferably wet etching. Wet etching is etching using a chemical called an etching solution. Examples of the etching solution include a sulfuric acid-hydrogen peroxide aqueous solution. The composition of the sulfuric acid-hydrogen peroxide aqueous solution is not limited. Examples of the sulfuric acid-hydrogen acid aqueous solution include a sulfuric acid-hydrogen acid aqueous solution in which the concentration of sulfuric acid is 1% by volume to 10% by volume and the concentration of hydrogen peroxide is 1% by volume to 10% by volume. Be done. The temperature of the sulfuric acid-hydrogen peroxide aqueous solution can be set, for example, in the range of 20 ° C. to 35 ° C. The immersion time in the sulfuric acid-hydrogen peroxide aqueous solution can be set, for example, in the range of 1 minute to 10 minutes. When the light-shielding layer contains copper, the sulfuric acid-hydrogen peroxide aqueous solution can be used until the concentration of copper dissolved in the sulfuric acid-hydrogen peroxide aqueous solution becomes, for example, 50 g / L. Examples of the etching solution include a cupric chloride solution. The composition of the cupric chloride solution is not limited. As the cupric chloride solution, for example, a solution containing 20% by mass to 35% by mass of cupric chloride and 1% by mass to 7% by mass of chlorine can be preferably used. However, the etching conditions are not limited to the above conditions. For example, the temperature of the etching solution and the immersion time in the etching solution may be determined according to the composition of the light-shielding layer, the thickness of the light-shielding layer, and the type of the etching solution.
　積層体は、透明基材と遮光性パターン１との間に密着層を有していてもよい。密着層の形成は、例えば、遮光性パターン１を形成する前に、透明基材の上に密着層を形成すればよい。密着層の形成方法としては、例えば、無電解めっき、スパッタリング、及び蒸着が挙げられる。密着層の形成方法としては、金属粒子を分散した金属粒子分散液の塗布、乾燥、及び焼結を含む方法も挙げられる。 The laminated body may have an adhesion layer between the transparent base material and the light-shielding pattern 1. The adhesion layer may be formed, for example, by forming the adhesion layer on the transparent base material before forming the light-shielding pattern 1. Examples of the method for forming the adhesion layer include electroless plating, sputtering, and thin film deposition. Examples of the method for forming the adhesion layer include a method including application, drying, and sintering of a metal particle dispersion liquid in which metal particles are dispersed.
　積層体の製造方法においては、密着層、及び遮光性パターンを形成する前に、必要に応じてデスミア処理により透明基材の表面を粗化してもよい。デスミア処理液（酸化性粗化液）としては、例えば、クロム／硫酸粗化液、アルカリ過マンガン酸粗化液（例えば、過マンガン酸ナトリウム粗化液）、及びフッ化ナトリウム／クロム／硫酸粗化液が挙げられる。 In the method for producing a laminated body, the surface of the transparent base material may be roughened by desmear treatment, if necessary, before forming the adhesion layer and the light-shielding pattern. Examples of the desmear treatment liquid (oxidizing roughening liquid) include chromium / sulfuric acid roughening liquid, alkaline permanganate roughening liquid (for example, sodium permanganate roughening liquid), and sodium fluoride / chromium / sulfuric acid crude liquid. Examples include chemicals.
－ネガ型感光性樹脂層Ｎの形成方法－
　以下、ネガ型感光性樹脂層Ｎの形成方法について説明する。ネガ型感光性樹脂層Ｎの形成方法としては、例えば、感光性樹脂組成物を用いる方法、及び感光性転写材料を用いる方法が挙げられる。 -Method of forming negative photosensitive resin layer N-
Hereinafter, a method for forming the negative photosensitive resin layer N will be described. Examples of the method for forming the negative type photosensitive resin layer N include a method using a photosensitive resin composition and a method using a photosensitive transfer material.
－感光性樹脂組成物－
　感光性樹脂組成物を用いる方法としては、例えば、透明基材及び遮光性パターンの上に、感光性樹脂組成物を塗布し、次いで、感光性樹脂組成物を乾燥する方法が挙げられる。 -Photosensitive resin composition-
Examples of the method using the photosensitive resin composition include a method of applying the photosensitive resin composition on a transparent base material and a light-shielding pattern, and then drying the photosensitive resin composition.
　感光性樹脂組成物の成分は、目的とするネガ型感光性樹脂層Ｎの成分に応じて決定すればよい。感光性樹脂組成物の好ましい成分としては、例えば、上記「ネガ型感光性樹脂層Ｎ」の項において説明した成分が挙げられる。感光性樹脂組成物としては、例えば、重合体Ａ、重合性化合物Ｂ、及び光重合開始剤を含む組成物が挙げられる。感光性樹脂組成物は、感光性樹脂組成物の粘度を調節し、感光性樹脂層の形成を容易にするため、溶剤を含むことが好ましい。 The components of the photosensitive resin composition may be determined according to the components of the target negative photosensitive resin layer N. Preferred components of the photosensitive resin composition include, for example, the components described in the above section "Negative type photosensitive resin layer N". Examples of the photosensitive resin composition include a composition containing a polymer A, a polymerizable compound B, and a photopolymerization initiator. The photosensitive resin composition preferably contains a solvent in order to adjust the viscosity of the photosensitive resin composition and facilitate the formation of the photosensitive resin layer.
　溶剤としては、感光性樹脂組成物の成分（例えば、重合体Ａ、重合性化合物Ｂ、及び重合開始剤）を溶解又は分散可能な溶剤であれば制限されず、公知の溶剤を利用することができる。溶剤としては、例えば、アルキレングリコールエーテル溶剤、アルキレングリコールエーテルアセテート溶剤、アルコール溶剤（例えば、メタノール、及びエタノール）、ケトン溶剤（例えば、アセトン、及びメチルエチルケトン）、芳香族炭化水素溶剤（例えば、トルエン）、非プロトン性極性溶剤（例えば、Ｎ，Ｎ－ジメチルホルムアミド）、環状エーテル溶剤（例えば、テトラヒドロフラン）、エステル溶剤、アミド溶剤、及びラクトン溶剤が挙げられる。 The solvent is not limited as long as it can dissolve or disperse the components of the photosensitive resin composition (for example, the polymer A, the polymerizable compound B, and the polymerization initiator), and a known solvent can be used. can. Examples of the solvent include an alkylene glycol ether solvent, an alkylene glycol ether acetate solvent, an alcohol solvent (for example, methanol and ethanol), a ketone solvent (for example, acetone and methyl ethyl ketone), and an aromatic hydrocarbon solvent (for example, toluene). Examples include aprotonic polar solvents (eg, N, N-dimethylformamide), cyclic ether solvents (eg, tetrahydrofuran), ester solvents, amide solvents, and lactone solvents.
　感光性樹脂組成物は、アルキレングリコールエーテル溶剤、及びアルキレングリコールエーテルアセテート溶剤よりなる群から選択される少なくとも１種を含むことが好ましい。感光性樹脂組成物は、アルキレングリコールエーテル溶剤、及びアルキレングリコールエーテルアセテート溶剤よりなる群から選択される少なくとも１種と、ケトン溶剤、及び環状エーテル溶剤よりなる群から選択される少なくとも１種と、を含むことがより好ましい。感光性樹脂組成物は、アルキレングリコールエーテル溶剤、及びアルキレングリコールエーテルアセテート溶剤よりなる群から選択される少なくとも１種と、ケトン溶剤と、環状エーテル溶剤と、を含むことが特に好ましい。 The photosensitive resin composition preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. The photosensitive resin composition comprises at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent. It is more preferable to include it. It is particularly preferable that the photosensitive resin composition contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, a ketone solvent, and a cyclic ether solvent.
　アルキレングリコールエーテル溶剤としては、例えば、エチレングリコールモノアルキルエーテル、エチレングリコールジアルキルエーテル、プロピレングリコールモノアルキルエーテル、プロピレングリコールジアルキルエーテル、ジエチレングリコールジアルキルエーテル、ジプロピレングリコールモノアルキルエーテル、及びジプロピレングリコールジアルキルエーテルが挙げられる。 Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether. Be done.
　アルキレングリコールエーテルアセテート溶剤としては、例えば、エチレングリコールモノアルキルエーテルアセテート、プロピレングリコールモノアルキルエーテルアセテート、ジエチレングリコールモノアルキルエーテルアセテート、及びジプロピレングリコールモノアルキルエーテルアセテートが挙げられる。 Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.
　溶剤としては、国際公開第２０１８／１７９６４０号の段落００９２～段落００９４に記載された溶剤、及び特開２０１８－１７７８８９号公報の段落００１４に記載された溶剤を用いてもよい。これらの内容は、参照により本明細書に組み込まれる。 As the solvent, the solvent described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvent described in paragraph 0014 of JP-A-2018-177789 may be used. These contents are incorporated herein by reference.
　感光性樹脂組成物は、１種単独、又は２種以上の溶剤を含んでもよい。 The photosensitive resin composition may contain one kind of solvent alone or two or more kinds of solvents.
　感光性樹脂組成物における溶剤の含有割合は、感光性樹脂組成物中の全固形分１００質量部に対して、５０質量部～１，９００質量部であることが好ましく、１００質量部～９００質量部であることがより好ましい。 The content ratio of the solvent in the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. It is more preferable that it is a part.
　感光性樹脂組成物の調製方法は、制限されない。感光性樹脂組成物の調製方法としては、例えば、各成分を溶剤に溶解した溶液を予め調製し、得られた各溶液を所定の割合で混合することにより、感光性樹脂組成物を調製する方法が挙げられる。感光性樹脂組成物は、ネガ型感光性樹脂層を形成する前に、孔径が０．２μｍ～３０μｍのフィルターを用いてろ過することが好ましい。 The method for preparing the photosensitive resin composition is not limited. As a method for preparing the photosensitive resin composition, for example, a method of preparing a photosensitive resin composition by preparing a solution in which each component is dissolved in a solvent in advance and mixing the obtained solutions in a predetermined ratio. Can be mentioned. The photosensitive resin composition is preferably filtered using a filter having a pore size of 0.2 μm to 30 μm before forming the negative photosensitive resin layer.
　感光性樹脂組成物の塗布方法としては、制限されず、公知の方法を用いることができる。塗布方法としては、例えば、スリット塗布、スピン塗布、カーテン塗布、及びインクジェット塗布が挙げられる。 The method for applying the photosensitive resin composition is not limited, and a known method can be used. Examples of the coating method include slit coating, spin coating, curtain coating, and inkjet coating.
－感光性転写材料－
　感光性転写材料を用いる方法としては、例えば、ネガ型感光性樹脂層Ｎを有する感光性転写材料と、遮光性パターンを有する透明基材とを貼り合わせることで、透明基材及び遮光性パターンの上にネガ型感光性樹脂層Ｎを配置する方法が挙げられる。ネガ型感光性樹脂層Ｎを有する感光性転写材料と、遮光性パターンを有する透明基材とを貼り合わせる方法においては、上記感光性転写材料と上記透明基材とを重ね合わせて、ロール等の手段を用いて加圧及び加熱を行うことが好ましい。貼り合わせには、ラミネーター、真空ラミネーター、及び、より生産性を高めることができるオートカットラミネーターを用いることができる。以下、感光性転写材料の構成要素について説明する。 -Photosensitive transfer material-
As a method of using the photosensitive transfer material, for example, a photosensitive transfer material having a negative photosensitive resin layer N and a transparent base material having a light-shielding pattern are bonded to each other to form a transparent base material and a light-shielding pattern. A method of arranging the negative type photosensitive resin layer N on the surface can be mentioned. In the method of laminating a photosensitive transfer material having a negative photosensitive resin layer N and a transparent base material having a light-shielding pattern, the photosensitive transfer material and the transparent base material are superposed on each other, and a roll or the like is used. It is preferable to pressurize and heat by means. For bonding, a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used. Hereinafter, the components of the photosensitive transfer material will be described.
－－感光性樹脂層－－
　感光性転写材料は、ネガ型感光性樹脂層Ｎを有する。ネガ型感光性樹脂層Ｎについては、上記「ネガ型感光性樹脂層Ｎ」の項において説明したとおりである。 －－Photosensitive resin layer －－
The photosensitive transfer material has a negative photosensitive resin layer N. The negative type photosensitive resin layer N is as described in the above section “Negative type photosensitive resin layer N”.
－－仮支持体－－
　感光性転写材料は、仮支持体を有することが好ましい。仮支持体は、感光性転写材料から剥離可能な支持体である。仮支持体は、少なくともネガ型感光性樹脂層Ｎを支持することができる。仮支持体は、露光工程の前に剥離してもよい。露光工程において仮支持体を剥離せずに光を照射した後、仮支持体を剥離してもよい。露光工程において仮支持体を剥離せずに光を照射することで、露光環境中のごみ及び埃の影響を避けることができる。 －－Temporary support －－
The photosensitive transfer material preferably has a temporary support. The temporary support is a support that can be peeled off from the photosensitive transfer material. The temporary support can support at least the negative photosensitive resin layer N. The temporary support may be peeled off before the exposure step. After irradiating light without peeling the temporary support in the exposure step, the temporary support may be peeled off. By irradiating light without peeling off the temporary support in the exposure process, the influence of dust and dirt in the exposure environment can be avoided.
　仮支持体としては、光透過性を有する仮支持体を用いることができる。本開示において、「光透過性を有する」とは、パターン露光に使用する波長の光の透過率が５０％以上であることを意味する。仮支持体において、パターン露光に使用する波長（好ましくは波長３６５ｎｍ）の光の透過率は、ネガ型感光性樹脂層Ｎの露光感度の向上の観点から、６０％以上であることが好ましく、７０％以上であることがより好ましい。 As the temporary support, a temporary support having light transmission can be used. In the present disclosure, "having light transmittance" means that the transmittance of light having a wavelength used for pattern exposure is 50% or more. In the temporary support, the transmittance of light having a wavelength (preferably a wavelength of 365 nm) used for pattern exposure is preferably 60% or more from the viewpoint of improving the exposure sensitivity of the negative photosensitive resin layer N, which is 70. % Or more is more preferable.
　仮支持体としては、例えば、ガラス基板、樹脂フィルム、及び紙が挙げられる。仮支持体は、強度、可撓性、及び光透過性の観点から、樹脂フィルムであることが好ましい。 Examples of the temporary support include a glass substrate, a resin film, and paper. The temporary support is preferably a resin film from the viewpoint of strength, flexibility, and light transmission.
　樹脂フィルムとしては、例えば、ポリエチレンテレフタレートフィルム（すなわち、ＰＥＴフィルム）、トリ酢酸セルロースフィルム、ポリスチレンフィルム、及びポリカーボネートフィルムが挙げられる。樹脂フィルムは、ＰＥＴフィルムであることが好ましく、２軸延伸ＰＥＴフィルムであることがより好ましい。 Examples of the resin film include polyethylene terephthalate film (that is, PET film), cellulose triacetate film, polystyrene film, and polycarbonate film. The resin film is preferably a PET film, more preferably a biaxially stretched PET film.
　仮支持体の厚さは、制限されない。仮支持体の平均厚さは、例えば、仮支持体としての強度、光透過性、材質、及び感光性転写材料と透明基材との貼り合わせに求められる可撓性に応じて決定すればよい。仮支持体の平均厚さは、５μｍ～１００μｍであることが好ましい。更に、仮支持体の平均厚さは、取り扱い易さ、及び汎用性の観点から、５μｍ～５０μｍであることが好ましく、５μｍ～２０μｍであることがより好ましく、１０μｍ～２０μｍであることが更に好ましく、１０μｍ～１６μｍであることが特に好ましい。 The thickness of the temporary support is not limited. The average thickness of the temporary support may be determined, for example, according to the strength of the temporary support, the light transmittance, the material, and the flexibility required for bonding the photosensitive transfer material and the transparent base material. .. The average thickness of the temporary support is preferably 5 μm to 100 μm. Further, the average thickness of the temporary support is preferably 5 μm to 50 μm, more preferably 5 μm to 20 μm, and further preferably 10 μm to 20 μm from the viewpoint of ease of handling and versatility. It is particularly preferably 10 μm to 16 μm.
　仮支持体のネガ型感光性樹脂層Ｎが配置された側の面の算術平均粗さＲａは、０．１μｍ以下であることが好ましく、０．０５μｍ以下であることがより好ましく、０．０２μｍ以下であることが特に好ましい。算術平均粗さＲａの下限は、制限されない。仮支持体のネガ型感光性樹脂層Ｎが配置された側の面の算術平均粗さＲａは、例えば、０μｍ以上の範囲で決定すればよい。 The arithmetic mean roughness Ra of the surface of the temporary support on the side on which the negative photosensitive resin layer N is arranged is preferably 0.1 μm or less, more preferably 0.05 μm or less, and 0.02 μm. The following is particularly preferable. The lower limit of the arithmetic mean roughness Ra is not limited. The arithmetic mean roughness Ra of the surface of the temporary support on the side on which the negative photosensitive resin layer N is arranged may be determined, for example, in the range of 0 μm or more.
　算術平均粗さＲａは、以下の方法によって測定する。３次元光学プロファイラー（Ｎｅｗ　Ｖｉｅｗ７３００、Ｚｙｇｏ社製）を用いて、以下の条件にて測定対象物の表面プロファイルを得る。測定及び解析ソフトウェアとしては、ＭｅｔｒｏＰｒｏ　ｖｅｒ８．３．２のＭｉｃｒｏｓｃｏｐｅ　Ａｐｐｌｉｃａｔｉｏｎを用いる。次に、上記ソフトウェアを用いてＳｕｒｆａｃｅ　Ｍａｐ画面を表示し、Ｓｕｒｆａｃｅ　Ｍａｐ画面中でヒストグラムデータを得る。得られたヒストグラムデータから、測定対象物の表面の算術平均粗さＲａを得る。なお、測定対象物の表面が他の層の表面と接触している場合、測定対象物を他の層から剥離することで露出した測定対象物の表面の算術平均粗さＲａを測定すればよい。 Arithmetic mean roughness Ra is measured by the following method. Using a three-dimensional optical profiler (New View7300, manufactured by Zygo), a surface profile of the object to be measured is obtained under the following conditions. As the measurement and analysis software, Microscope Application of MetroPro ver 8.3.2 is used. Next, the Surface Map screen is displayed using the above software, and histogram data is obtained in the Surface Map screen. From the obtained histogram data, the arithmetic mean roughness Ra of the surface of the object to be measured is obtained. When the surface of the object to be measured is in contact with the surface of another layer, the arithmetic mean roughness Ra of the surface of the exposed object to be measured may be measured by peeling the object to be measured from the other layer. ..
　仮支持体（特に樹脂フィルム）には、例えば、変形（例えば、シワ）、傷、及び欠陥がないことが好ましい。仮支持体の透明性の観点から、仮支持体に含まれる微粒子、異物、欠陥、及び析出物の数は少ないことが好ましい。仮支持体において、直径が１μｍ以上である、微粒子、異物、及び欠陥の数は、５０個／１０ｍｍ２以下であることが好ましく、１０個／１０ｍｍ２以下であることがより好ましく、３個／１０ｍｍ２以下であることが更に好ましく、０個／１０ｍｍ２であることが特に好ましい。 It is preferable that the temporary support (particularly the resin film) is free from, for example, deformation (for example, wrinkles), scratches, and defects. From the viewpoint of transparency of the temporary support, it is preferable that the number of fine particles, foreign substances, defects, and precipitates contained in the temporary support is small. In the temporary support, the number of fine particles, foreign substances, and defects having a diameter of 1 μm or more is preferably 50 pieces / 10 mm 2 or less, more preferably 10 pieces / 10 mm 2 or less, and 3 pieces / It is more preferably 10 mm 2 or less, and particularly preferably 0/10 mm 2.
　仮支持体の好ましい態様については、例えば、特開２０１４－８５６４３号公報の段落００１７～段落００１８、特開２０１６－２７３６３号公報の段落００１９～段落００２６、国際公開第２０１２／０８１６８０号の段落００４１～段落００５７、国際公開第２０１８／１７９３７０号の段落００２９～段落００４０、及び特開２０１９－１０１４０５号公報の段落００１２～段落００３２に記載がある。これらの公報の内容は、参照により本明細書に組み込まれる。 Regarding preferred embodiments of the provisional support, for example, paragraphs 0017 to 0018 of JP-A-2014-85643, paragraphs 0019 to paragraph 0026 of JP-A-2016-27363, and paragraphs 0041 to International Publication No. 2012/081680. It is described in paragraph 0057, paragraphs 0029 to 0040 of International Publication No. 2018/179370, and paragraphs 0012 to 0032 of JP-A-2019-101405. The contents of these publications are incorporated herein by reference.
－－カバーフィルム－－
　感光性転写材料は、カバーフィルム（保護フィルムともいう。）を有してもよい。カバーフィルムによれば、カバーフィルムに接触する層（例えば、ネガ型感光性樹脂層Ｎ）の表面を保護することができる。感光性転写材料は、仮支持体と、ネガ型感光性樹脂層Ｎと、カバーフィルムと、をこの順で含むことが好ましい。感光性転写材料は、ネガ型感光性樹脂層Ｎの仮支持体が配置された側とは反対側の面に接するカバーフィルムを有することが好ましい。 －－Cover film －－
The photosensitive transfer material may have a cover film (also referred to as a protective film). According to the cover film, the surface of the layer in contact with the cover film (for example, the negative photosensitive resin layer N) can be protected. The photosensitive transfer material preferably includes a temporary support, a negative photosensitive resin layer N, and a cover film in this order. The photosensitive transfer material preferably has a cover film in contact with the surface of the negative photosensitive resin layer N opposite to the side on which the temporary support is arranged.
　カバーフィルムとしては、例えば、樹脂フィルム、及び紙が挙げられる。カバーフィルムは、強度、及び可撓性の観点から、樹脂フィルムであることが好ましい。 Examples of the cover film include a resin film and paper. The cover film is preferably a resin film from the viewpoint of strength and flexibility.
　樹脂フィルムとしては、例えば、ポリエチレンフィルム、ポリプロピレンフィルム、ポリエチレンテレフタレートフィルム、トリ酢酸セルロースフィルム、ポリスチレンフィルム、及びポリカーボネートフィルムが挙げられる。樹脂フィルムは、ポリエチレンフィルム、ポリプロピレンフィルム、又はポリエチレンテレフタレートフィルムであることが好ましい。 Examples of the resin film include polyethylene film, polypropylene film, polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film. The resin film is preferably a polyethylene film, a polypropylene film, or a polyethylene terephthalate film.
　カバーフィルムの厚さは、制限されない。カバーフィルムの平均厚さは、５μｍ～１００μｍであることが好ましく、１０μｍ～５０μｍであることがより好ましく、１０μｍ～２０μｍであることが特に好ましい。 The thickness of the cover film is not limited. The average thickness of the cover film is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm, and particularly preferably 10 μm to 20 μm.
　カバーフィルムのネガ型感光性樹脂層Ｎが配置された側の面の算術平均粗さＲａは、解像性により優れる点から、０．３μｍ以下であることが好ましく、０．１μｍ以下であることがより好ましく、０．０５μｍ以下であることが特に好ましい。カバーフィルムのネガ型感光性樹脂層Ｎが配置された側の面の算術平均粗さが上記範囲であることで、ネガ型感光性樹脂層、及び形成される樹脂パターンの厚さの均一性が向上する。算術平均粗さＲａの下限は、制限されない。カバーフィルムのネガ型感光性樹脂層Ｎが配置された側の面の算術平均粗さＲａは、０．００１μｍ以上であることが好ましい。カバーフィルムのネガ型感光性樹脂層Ｎが配置された側の面の算術平均粗さＲａは、上記「仮支持体」の項において説明した算術平均粗さＲａの測定方法に準ずる方法によって測定する。 The arithmetic mean roughness Ra of the surface of the cover film on the side on which the negative photosensitive resin layer N is arranged is preferably 0.3 μm or less, preferably 0.1 μm or less, from the viewpoint of excellent resolution. Is more preferable, and 0.05 μm or less is particularly preferable. When the arithmetic mean roughness of the surface on the side where the negative photosensitive resin layer N of the cover film is arranged is within the above range, the thickness of the negative photosensitive resin layer and the formed resin pattern can be made uniform. improves. The lower limit of the arithmetic mean roughness Ra is not limited. The arithmetic average roughness Ra of the surface of the cover film on the side on which the negative photosensitive resin layer N is arranged is preferably 0.001 μm or more. The arithmetic mean roughness Ra of the surface of the cover film on the side on which the negative photosensitive resin layer N is arranged is measured by a method according to the method for measuring the arithmetic mean roughness Ra described in the above section "Temporary Support". ..
－－熱可塑性樹脂層－－
　本開示に係る感光性転写材料は、熱可塑性樹脂層Ｎを有してもよい。感光性転写材料は、仮支持体とネガ型感光性樹脂層Ｎとの間に熱可塑性樹脂層を有することが好ましい。感光性転写材料が仮支持体とネガ型感光性樹脂層Ｎとの間に熱可塑性樹脂層を有することで、被着物への追従性が向上して、被着物と感光性転写材料との間の気泡の混入が抑制される結果、層間の密着性が向上するためである。 －－Thermoplastic resin layer －－
The photosensitive transfer material according to the present disclosure may have a thermoplastic resin layer N. The photosensitive transfer material preferably has a thermoplastic resin layer between the temporary support and the negative type photosensitive resin layer N. When the photosensitive transfer material has a thermoplastic resin layer between the temporary support and the negative type photosensitive resin layer N, the followability to the adherend is improved, and the space between the adherend and the photosensitive transfer material is improved. This is because, as a result of suppressing the mixing of air bubbles, the adhesion between layers is improved.
　熱可塑性樹脂層は、熱可塑性樹脂として、アルカリ可溶性樹脂を含むことが好ましい。 The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin.
　アルカリ可溶性樹脂としては、例えば、アクリル樹脂、ポリスチレン樹脂、スチレン－アクリル共重合体、ポリウレタン樹脂、ポリビニルアルコール、ポリビニルホルマール、ポリアミド樹脂、ポリエステル樹脂、エポキシ樹脂、ポリアセタール樹脂、ポリヒドロキシスチレン樹脂、ポリイミド樹脂、ポリベンゾオキサゾール樹脂、ポリシロキサン樹脂、ポリエチレンイミン、ポリアリルアミン、及びポリアルキレングリコールが挙げられる。 Examples of the alkali-soluble resin include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, and polyimide resin. Examples thereof include polybenzoxazole resin, polysiloxane resin, polyethyleneimine, polyallylamine, and polyalkylene glycol.
　アルカリ可溶性樹脂は、現像性、及び熱可塑性樹脂層に隣接する層との密着性の観点から、アクリル樹脂であることが好ましい。ここで、「アクリル樹脂」とは、（メタ）アクリル酸に由来する構成単位、（メタ）アクリル酸エステルに由来する構成単位、及び（メタ）アクリル酸アミドに由来する構成単位よりなる群から選択される少なくとも１種を有する樹脂を意味する。 The alkali-soluble resin is preferably an acrylic resin from the viewpoint of developability and adhesion to a layer adjacent to the thermoplastic resin layer. Here, the "acrylic resin" is selected from the group consisting of a structural unit derived from (meth) acrylic acid, a structural unit derived from (meth) acrylic acid ester, and a structural unit derived from (meth) acrylic acid amide. It means a resin having at least one kind.
　アクリル樹脂において、（メタ）アクリル酸に由来する構成単位、（メタ）アクリル酸エステルに由来する構成単位、及び（メタ）アクリル酸アミドに由来する構成単位の合計含有量の割合は、アクリル樹脂の全質量に対して、５０質量％以上であることが好ましい。アクリル樹脂において、（メタ）アクリル酸に由来する構成単位、及び（メタ）アクリル酸エステルに由来する構成単位の合計含有量の割合は、アクリル樹脂の全質量に対して、３０質量％～１００質量％であることが好ましく、５０質量％～１００質量％であることがより好ましい。 In the acrylic resin, the ratio of the total content of the structural unit derived from (meth) acrylic acid, the structural unit derived from (meth) acrylic acid ester, and the structural unit derived from (meth) acrylic acid amide is the ratio of the total content of the acrylic resin. It is preferably 50% by mass or more with respect to the total mass. In the acrylic resin, the ratio of the total content of the structural unit derived from (meth) acrylic acid and the structural unit derived from (meth) acrylic acid ester is 30% by mass to 100% by mass with respect to the total mass of the acrylic resin. %, More preferably 50% by mass to 100% by mass.
　また、アルカリ可溶性樹脂は、酸基を有する重合体であることが好ましい。酸基としては、例えば、カルボキシ基、スルホ基、リン酸基、及びホスホン酸基が挙げられ、カルボキシ基が好ましい。 Further, the alkali-soluble resin is preferably a polymer having an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group, and a carboxy group is preferable.
　アルカリ可溶性樹脂は、現像性の観点から、酸価が６０ｍｇＫＯＨ／ｇ以上であるアルカリ可溶性樹脂であることが好ましく、酸価が６０ｍｇＫＯＨ／ｇ以上であるカルボキシ基含有アクリル樹脂であることがより好ましい。酸価の上限は、制限されない。アルカリ可溶性樹脂の酸価は、２００ｍｇＫＯＨ／ｇ以下であることが好ましく、１５０ｍｇＫＯＨ／ｇ以下であることがより好ましい。 From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH / g or more, and more preferably a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more. The upper limit of acid value is not limited. The acid value of the alkali-soluble resin is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.
　酸価が６０ｍｇＫＯＨ／ｇ以上であるカルボキシ基含有アクリル樹脂としては、制限されず、公知の樹脂から適宜選択して用いることができる。酸価が６０ｍｇＫＯＨ／ｇ以上であるカルボキシ基含有アクリル樹脂としては、例えば、特開２０１１－９５７１６号公報の段落００２５に記載のポリマーのうち酸価が６０ｍｇＫＯＨ／ｇ以上であるカルボキシ基含有アクリル樹脂、特開２０１０－２３７５８９号公報の段落００３３～段落００５２に記載のポリマーのうち酸価が６０ｍｇＫＯＨ／ｇ以上であるカルボキシ基含有アクリル樹脂、及び特開２０１６－２２４１６２号公報の段落００５３～段落００６８に記載のバインダーポリマーのうち酸価が６０ｍｇＫＯＨ／ｇ以上であるカルボキシ基含有アクリル樹脂が挙げられる。 The carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more is not limited and can be appropriately selected from known resins and used. Examples of the carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more include carboxy group-containing acrylic resins having an acid value of 60 mgKOH / g or more among the polymers described in paragraph 0025 of JP-A-2011-95716. Described in paragraphs 0033 to 0052 of Japanese Patent Application Laid-Open No. 2010-237589, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more, and paragraphs 0053 to 0068 of JP-A-2016-224162. Among the binder polymers of the above, a carboxy group-containing acrylic resin having an acid value of 60 mgKOH / g or more can be mentioned.
　カルボキシ基含有アクリル樹脂におけるカルボキシ基を有する構成単位の含有割合は、カルボキシ基含有アクリル樹脂の全質量に対して、５質量％～５０質量％であることが好ましく、１０質量％～４０質量％であることがより好ましく、１２質量％～３０質量％であることが特に好ましい。 The content ratio of the structural unit having a carboxy group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, preferably 10% by mass to 40% by mass, based on the total mass of the carboxy group-containing acrylic resin. It is more preferable, and it is particularly preferable that it is 12% by mass to 30% by mass.
　アルカリ可溶性樹脂は、現像性、及び熱可塑性樹脂層に隣接する層との密着性の観点から、（メタ）アクリル酸に由来する構成単位を有するアクリル樹脂であることが特に好ましい。 The alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth) acrylic acid from the viewpoint of developability and adhesion to a layer adjacent to the thermoplastic resin layer.
　アルカリ可溶性樹脂は、反応性基を有してもよい。反応性基は、例えば、付加重合可能な基であればよい。反応性基としては、例えば、エチレン性不飽和基、重縮合性基（例えば、ヒドロキシ基、及びカルボキシ基）、及び重付加反応性基（例えば、エポキシ基、及び（ブロック）イソシアネート基）が挙げられる。 The alkali-soluble resin may have a reactive group. The reactive group may be, for example, a group capable of addition polymerization. Reactive groups include, for example, ethylenically unsaturated groups, polycondensable groups (eg, hydroxy and carboxy groups), and polyaddition reactive groups (eg, epoxy groups and (blocking) isocyanate groups). Be done.
　アルカリ可溶性樹脂の重量平均分子量（Ｍｗ）は、１，０００以上であることが好ましく、１万～１０万であることがより好ましく、２万～５万であることが特に好ましい。 The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and particularly preferably 20,000 to 50,000.
　熱可塑性樹脂層は、１種単独、又は２種以上のアルカリ可溶性樹脂を含んでもよい。 The thermoplastic resin layer may contain one type alone or two or more types of alkali-soluble resins.
　アルカリ可溶性樹脂の含有割合は、現像性、及び熱可塑性樹脂層に隣接する層との密着性の観点から、熱可塑性樹脂層の全質量に対して、１０質量％～９９質量％であることが好ましく、２０質量％～９０質量％であることがより好ましく、４０質量％～８０質量％であることが更に好ましく、５０質量％～７０質量％であることが特に好ましい。 The content ratio of the alkali-soluble resin is 10% by mass to 99% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of developability and adhesion to the layer adjacent to the thermoplastic resin layer. It is more preferably 20% by mass to 90% by mass, further preferably 40% by mass to 80% by mass, and particularly preferably 50% by mass to 70% by mass.
　熱可塑性樹脂層は、発色時の波長範囲である４００ｎｍ～７８０ｎｍにおける最大吸収波長が４５０ｎｍ以上であり、かつ、酸、塩基、又はラジカルにより最大吸収波長が変化する色素（以下、「色素Ｂ」という場合がある。）を含むことが好ましい。色素Ｂの好ましい態様は、後述する点以外は、上記した色素ＮＣの好ましい態様と同様である。 The thermoplastic resin layer has a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm at the time of color development, and the maximum absorption wavelength is changed by an acid, a base, or a radical (hereinafter referred to as “dye B”). In some cases), it is preferable to include. The preferred embodiment of the dye B is the same as the preferred embodiment of the dye NC described above, except for the points described later.
　色素Ｂは、露光部の視認性、非露光部の視認性、及び解像性の観点から、酸、又はラジカルにより最大吸収波長が変化する色素であることが好ましく、酸により最大吸収波長が変化する色素であることがより好ましい。 The dye B is preferably a dye whose maximum absorption wavelength is changed by an acid or a radical from the viewpoint of visibility of the exposed part, visibility of the non-exposed part, and resolution, and the maximum absorption wavelength is changed by the acid. It is more preferable that the dye is a radical.
　熱可塑性樹脂層は、露光部の視認性、非露光部の視認性、及び解像性の観点から、色素Ｂとして酸により最大吸収波長が変化する色素と、後述する光により酸を発生する化合物と、を含むことが好ましい。 The thermoplastic resin layer is composed of a dye whose maximum absorption wavelength is changed by an acid as dye B and a compound which generates an acid by light, which will be described later, from the viewpoints of visibility of an exposed part, visibility of a non-exposed part, and resolution. And, preferably.
　熱可塑性樹脂層は、１種単独、又は２種以上の色素Ｂを含んでもよい。 The thermoplastic resin layer may contain one type alone or two or more types of dye B.
　色素Ｂの含有割合は、露光部の視認性、非露光部の視認性の観点から、熱可塑性樹脂層の全質量に対して、０．２質量％以上であることが好ましく、０．２質量％～６質量％であることがより好ましく、０．２質量％～５質量％であることが更に好ましく、０．２５質量％～３．０質量％であることが特に好ましい。 The content ratio of the dye B is preferably 0.2% by mass or more, preferably 0.2% by mass, based on the total mass of the thermoplastic resin layer from the viewpoint of the visibility of the exposed portion and the visibility of the non-exposed portion. It is more preferably% to 6% by mass, further preferably 0.2% by mass to 5% by mass, and particularly preferably 0.25% by mass to 3.0% by mass.
　ここで、色素Ｂの含有割合は、熱可塑性樹脂層に含まれる色素Ｂの全てを発色状態にした場合の色素の含有割合を意味する。以下、ラジカルにより発色する色素を例として、色素Ｂの含有割合の定量方法を説明する。メチルエチルケトン（１００ｍＬ）に、色素（０．００１ｇ）、及び色素（０．０１ｇ）をそれぞれ溶かした２つの溶液を調製する。得られた各溶液に、光ラジカル重合開始剤としてＩＲＧＡＣＵＲＥ　ＯＸＥ－０１（ＢＡＳＦ社）を加えた後、３６５ｎｍの光を照射することによりラジカルを発生させ、全ての色素を発色状態にする。次に、大気雰囲気下で、分光光度計（ＵＶ３１００、（株）島津製作所）を用いて、液温が２５℃である各溶液の吸光度を測定し、検量線を作成する。次に、色素に代えて熱可塑性樹脂層（０．１ｇ）をメチルエチルケトンに溶かすこと以外は上記と同様の方法で、色素を全て発色させた溶液の吸光度を測定する。得られた熱可塑性樹脂層を含有する溶液の吸光度から、検量線に基づいて熱可塑性樹脂層に含まれる色素の量を算出する。 Here, the content ratio of the dye B means the content ratio of the dye when all of the dye B contained in the thermoplastic resin layer is in a colored state. Hereinafter, a method for quantifying the content ratio of dye B will be described by taking a dye that develops color by radicals as an example. Two solutions are prepared by dissolving the dye (0.001 g) and the dye (0.01 g) in methyl ethyl ketone (100 mL). IRGACURE OXE-01 (BASF) is added to each of the obtained solutions as a photoradical polymerization initiator, and then radicals are generated by irradiating with light of 365 nm to bring all the dyes into a colored state. Next, in an air atmosphere, the absorbance of each solution having a liquid temperature of 25 ° C. is measured using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve is prepared. Next, the absorbance of the solution in which all the dyes are colored is measured by the same method as above except that the thermoplastic resin layer (0.1 g) is dissolved in methyl ethyl ketone instead of the dye. From the absorbance of the obtained solution containing the thermoplastic resin layer, the amount of the dye contained in the thermoplastic resin layer is calculated based on the calibration curve.
　熱可塑性樹脂層は、光により酸、塩基、又はラジカルを発生する化合物（以下、「化合物Ｃ」という場合がある。）を含んでもよい。化合物Ｃは、活性光線（例えば、紫外線、及び可視光線）を受けて、酸、塩基、又はラジカルを発生する化合物であることが好ましい。化合物Ｃとしては、公知の、光酸発生剤、光塩基発生剤、及び光ラジカル重合開始剤（光ラジカル発生剤）が挙げられる。化合物Ｃは、光酸発生剤であることが好ましい。 The thermoplastic resin layer may contain a compound that generates an acid, a base, or a radical by light (hereinafter, may be referred to as "compound C"). Compound C is preferably a compound that receives active rays (for example, ultraviolet rays and visible rays) to generate acids, bases, or radicals. Examples of compound C include known photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators). Compound C is preferably a photoacid generator.
　熱可塑性樹脂層は、解像性の観点から、光酸発生剤を含むことが好ましい。光酸発生剤としては、上述したネガ型感光性樹脂層に含まれてもよい光カチオン重合開始剤が挙げられ、後述する点以外は好ましい態様も同じである。 The thermoplastic resin layer preferably contains a photoacid generator from the viewpoint of resolution. Examples of the photoacid generator include a photocationic polymerization initiator that may be contained in the negative-type photosensitive resin layer described above, and the same preferred embodiments are used except for the points described below.
　光酸発生剤は、感度、及び解像性の観点から、オニウム塩化合物、及びオキシムスルホネート化合物よりなる群から選択された少なくとも１種を含むことが好ましく、感度、解像性、及び密着性の観点から、オキシムスルホネート化合物を含むことがより好ましい。 From the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least one selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and has sensitivity, resolution and adhesion. From the viewpoint, it is more preferable to contain an oxime sulfonate compound.
　また、光酸発生剤は、以下の構造を有する光酸発生剤であることも好ましい。 It is also preferable that the photoacid generator is a photoacid generator having the following structure.
Figure JPOXMLDOC01-appb-C000002
 
Figure JPOXMLDOC01-appb-C000002
 
　熱可塑性樹脂層は、光塩基発生剤を含んでもよい。光塩基発生剤としては、例えば、２－ニトロベンジルシクロヘキシルカルバメート、トリフェニルメタノール、Ｏ－カルバモイルヒドロキシルアミド、Ｏ－カルバモイルオキシム、［［（２，６－ジニトロベンジル）オキシ］カルボニル］シクロヘキシルアミン、ビス［［（２－ニトロベンジル）オキシ］カルボニル］ヘキサン１，６－ジアミン、４－（メチルチオベンゾイル）－１－メチル－１－モルホリノエタン、（４－モルホリノベンゾイル）－１－ベンジル－１－ジメチルアミノプロパン、Ｎ－（２－ニトロベンジルオキシカルボニル）ピロリジン、ヘキサアンミンコバルト（ＩＩＩ）トリス（トリフェニルメチルボレート）、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタノン、２，６－ジメチル－３，５－ジアセチル－４－（２－ニトロフェニル）－１，４－ジヒドロピリジン、及び２，６－ジメチル－３，５－ジアセチル－４－（２，４－ジニトロフェニル）－１，４－ジヒドロピリジンが挙げられる。 The thermoplastic resin layer may contain a photobase generator. Examples of the photobase generator include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, and bis [ [(2-Nitrobenzyl) oxy] carbonyl] hexane 1,6-diamine, 4- (methylthiobenzoyl) -1-methyl-1-morpholinoetan, (4-morpholinobenzoyl) -1-benzyl-1-dimethylaminopropane , N- (2-nitrobenzyloxycarbonyl) pyrrolidine, hexaammine cobalt (III) tris (triphenylmethylborate), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2,6 -Dimethyl-3,5-diacetyl-4- (2-nitrophenyl) -1,4-dihydropyridine, and 2,6-dimethyl-3,5-diacetyl-4- (2,4-dinitrophenyl) -1, 4-Dihydropyridine can be mentioned.
　熱可塑性樹脂層は、光ラジカル重合開始剤を含んでもよい。光ラジカル重合開始剤としては、例えば、上述したネガ型感光性樹脂層に含まれてもよい光ラジカル重合開始剤が挙げられ、好ましい態様も同じである。 The thermoplastic resin layer may contain a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include a photoradical polymerization initiator that may be contained in the negative photosensitive resin layer described above, and the preferred embodiment is also the same.
　熱可塑性樹脂層は、１種単独、又は２種以上の化合物Ｃを含んでもよい。 The thermoplastic resin layer may contain one kind alone or two or more kinds of compound C.
　化合物Ｃの含有割合は、露光部の視認性、非露光部の視認性、及び解像性の観点から、熱可塑性樹脂層の全質量に対して、０．１質量％～１０質量％であることが好ましく、０．５質量％～５質量％であることがより好ましい。 The content ratio of the compound C is 0.1% by mass to 10% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of the visibility of the exposed portion, the visibility of the non-exposed portion, and the resolution. It is preferable, and it is more preferable that it is 0.5% by mass to 5% by mass.
　熱可塑性樹脂層は、解像性、熱可塑性樹脂層に隣接する層との密着性、及び現像性の観点から、可塑剤を含むことが好ましい。 The thermoplastic resin layer preferably contains a plasticizer from the viewpoints of resolution, adhesion to a layer adjacent to the thermoplastic resin layer, and developability.
　可塑剤の分子量（オリゴマー又はポリマーの分子量については重量平均分子量（Ｍｗ）をいう。以下、本段落において同じ。）は、アルカリ可溶性樹脂の分子量よりも小さいことが好ましい。可塑剤の分子量は、２００～２，０００であることが好ましい。 The molecular weight of the plasticizer (the molecular weight of the oligomer or polymer is the weight average molecular weight (Mw); the same applies hereinafter in this paragraph) is preferably smaller than the molecular weight of the alkali-soluble resin. The molecular weight of the plasticizer is preferably 200 to 2,000.
　可塑剤は、アルカリ可溶性樹脂と相溶して可塑性を発現する化合物であれば制限されない。可塑剤は、可塑性付与の観点から、分子中にアルキレンオキシ基を有する化合物であることが好ましく、ポリアルキレングリコール化合物であることがより好ましい。可塑剤に含まれるアルキレンオキシ基は、ポリエチレンオキシ構造、又はポリプロピレンオキシ構造を有することが好ましい。 The plasticizer is not limited as long as it is a compound that develops plasticity by being compatible with an alkali-soluble resin. From the viewpoint of imparting plasticity, the plasticizer is preferably a compound having an alkyleneoxy group in the molecule, and more preferably a polyalkylene glycol compound. The alkyleneoxy group contained in the plasticizer preferably has a polyethyleneoxy structure or a polypropyleneoxy structure.
　可塑剤は、解像性、及び保存安定性の観点から、（メタ）アクリレート化合物を含むことが好ましい。相溶性、解像性、及び熱可塑性樹脂層に隣接する層との密着性の観点から、アルカリ可溶性樹脂がアクリル樹脂であり、かつ、可塑剤が（メタ）アクリレート化合物を含むことがより好ましい。 The plasticizer preferably contains a (meth) acrylate compound from the viewpoint of resolution and storage stability. From the viewpoint of compatibility, resolution, and adhesion to the layer adjacent to the thermoplastic resin layer, it is more preferable that the alkali-soluble resin is an acrylic resin and the plasticizer contains a (meth) acrylate compound.
　可塑剤として用いられる（メタ）アクリレート化合物としては、例えば、上記「重合性化合物Ｂ」の項に記載した（メタ）アクリレート化合物が挙げられる。感光性転写材料において、熱可塑性樹脂層とネガ型感光性樹脂層とが直接接触して配置される場合、熱可塑性樹脂層、及びネガ型感光性樹脂層は、それぞれ、同じ（メタ）アクリレート化合物を含むことが好ましい。熱可塑性樹脂層、及びネガ型感光性樹脂層Ｎが、それぞれ、同じ（メタ）アクリレート化合物を含むことで、層間の成分拡散が抑制され、保存安定性が向上するためである。 Examples of the (meth) acrylate compound used as a plasticizer include the (meth) acrylate compound described in the above-mentioned "Polymerizable Compound B" section. In the photosensitive transfer material, when the thermoplastic resin layer and the negative type photosensitive resin layer are arranged in direct contact with each other, the thermoplastic resin layer and the negative type photosensitive resin layer are each the same (meth) acrylate compound. Is preferably included. This is because the thermoplastic resin layer and the negative photosensitive resin layer N each contain the same (meth) acrylate compound, so that the diffusion of components between the layers is suppressed and the storage stability is improved.
　熱可塑性樹脂層が可塑剤として（メタ）アクリレート化合物を含む場合、熱可塑性樹脂層に隣接する層との密着性の観点から、露光後の露光部においても（メタ）アクリレート化合物は重合しないことが好ましい。 When the thermoplastic resin layer contains a (meth) acrylate compound as a plasticizer, the (meth) acrylate compound may not polymerize even in the exposed portion after exposure from the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer. preferable.
　ある実施形態において、可塑剤として用いられる（メタ）アクリレート化合物は、解像性、熱可塑性樹脂層に隣接する層との密着性、及び現像性の観点から、一分子中に２つ以上の（メタ）アクリロイル基を有する（メタ）アクリレート化合物であることが好ましい。 In certain embodiments, the (meth) acrylate compound used as a plasticizer is composed of two or more (meth) acrylate compounds in one molecule from the viewpoints of resolution, adhesion to a layer adjacent to a thermoplastic resin layer, and developability. It is preferably a (meth) acrylate compound having a meta) acryloyl group.
　ある実施形態において、可塑剤として用いられる（メタ）アクリレート化合物は、酸基を有する（メタ）アクリレート化合物、又はウレタン（メタ）アクリレート化合物であることが好ましい。 In certain embodiments, the (meth) acrylate compound used as a plasticizer is preferably a (meth) acrylate compound having an acid group or a urethane (meth) acrylate compound.
　熱可塑性樹脂層は、１種単独、又は２種以上の可塑剤を含んでもよい。 The thermoplastic resin layer may contain one type alone or two or more types of plasticizers.
　可塑剤の含有割合は、解像性、熱可塑性樹脂層に隣接する層との密着性、及び現像性の観点から、熱可塑性樹脂層の全質量に対して、１質量％～７０質量％であることが好ましく、１０質量％～６０質量％であることがより好ましく、２０質量％～５０質量％であることが特に好ましい。 The content ratio of the plasticizer is 1% by mass to 70% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoints of resolution, adhesion to the layer adjacent to the thermoplastic resin layer, and developability. It is preferably 10% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass.
　熱可塑性樹脂層は、厚さの均一性の観点から、界面活性剤を含むことが好ましい。界面活性剤としては、例えば、上述したネガ型感光性樹脂層Ｎに含まれてもよい界面活性剤が挙げられ、好ましい態様も同じである。 The thermoplastic resin layer preferably contains a surfactant from the viewpoint of thickness uniformity. Examples of the surfactant include a surfactant that may be contained in the negative photosensitive resin layer N described above, and the preferred embodiment is also the same.
　熱可塑性樹脂層は、１種単独、又は２種以上の界面活性剤を含んでもよい。 The thermoplastic resin layer may contain one type alone or two or more types of surfactants.
　界面活性剤の含有割合は、熱可塑性樹脂層の全質量に対して、０．００１質量％～１０質量％であることが好ましく、０．０１質量％～３質量％であることがより好ましい。 The content ratio of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the thermoplastic resin layer.
　熱可塑性樹脂層は、増感剤を含んでもよい。増感剤としては、例えば、上述したネガ型感光性樹脂層に含まれてもよい増感剤が挙げられる。 The thermoplastic resin layer may contain a sensitizer. Examples of the sensitizer include the sensitizer that may be contained in the negative photosensitive resin layer described above.
　熱可塑性樹脂層は、１種単独、又は２種以上の増感剤を含んでもよい。 The thermoplastic resin layer may contain one type alone or two or more types of sensitizers.
　増感剤の含有割合は、光源に対する感度の向上、露光部の視認性、及び非露光部の視認性の観点から、熱可塑性樹脂層の全質量に対して、０．０１質量％～５質量％であることが好ましく、０．０５質量％～１質量％であることがより好ましい。 The content ratio of the sensitizer is 0.01% by mass to 5% by mass with respect to the total mass of the thermoplastic resin layer from the viewpoint of improving the sensitivity to the light source, the visibility of the exposed part, and the visibility of the non-exposed part. %, More preferably 0.05% by mass to 1% by mass.
　熱可塑性樹脂層は、上記成分以外に、必要に応じて公知の添加剤を含んでもよい。 The thermoplastic resin layer may contain known additives in addition to the above components, if necessary.
　また、熱可塑性樹脂層については、特開２０１４－８５６４３号公報の段落０１８９～段落０１９３に記載されている。上記公報の内容は、参照により本明細書に組み込まれる。 Further, the thermoplastic resin layer is described in paragraphs 0189 to 0193 of Japanese Patent Application Laid-Open No. 2014-85643. The contents of the above publication are incorporated herein by reference.
　熱可塑性樹脂層の厚さは、制限されない。熱可塑性樹脂層の平均厚さは、熱可塑性樹脂層に隣接する層との密着性の観点から、１μｍ以上であることが好ましく、２μｍ以上であることがより好ましい。熱可塑性樹脂層の平均厚さの上限は、制限されない。熱可塑性樹脂層の平均厚さは、現像性、及び解像性の観点から、２０μｍ以下であることが好ましく、１０μｍ以下であることがより好ましく、５μｍ以下であることが特に好ましい。 The thickness of the thermoplastic resin layer is not limited. The average thickness of the thermoplastic resin layer is preferably 1 μm or more, and more preferably 2 μm or more, from the viewpoint of adhesion to the layer adjacent to the thermoplastic resin layer. The upper limit of the average thickness of the thermoplastic resin layer is not limited. From the viewpoint of developability and resolvability, the average thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less.
　熱可塑性樹脂層の形成方法は、上記の成分を含む層を形成可能な方法であれば制限されない。熱可塑性樹脂層の形成方法としては、例えば、仮支持体の表面に、熱可塑性樹脂組成物を塗布し、熱可塑性樹脂組成物の塗膜を乾燥する方法が挙げられる。 The method for forming the thermoplastic resin layer is not limited as long as it is a method capable of forming a layer containing the above components. Examples of the method for forming the thermoplastic resin layer include a method in which the thermoplastic resin composition is applied to the surface of the temporary support and the coating film of the thermoplastic resin composition is dried.
　熱可塑性樹脂組成物としては、例えば、上記の成分を含む組成物が挙げられる。熱可塑性樹脂組成物は、熱可塑性樹脂組成物の粘度を調節し、熱可塑性樹脂層の形成を容易にするため、溶剤を含むことが好ましい。 Examples of the thermoplastic resin composition include a composition containing the above components. The thermoplastic resin composition preferably contains a solvent in order to adjust the viscosity of the thermoplastic resin composition and facilitate the formation of the thermoplastic resin layer.
　熱可塑性樹脂組成物に含まれる溶剤としては、熱可塑性樹脂層に含まれる成分を溶解、又は分散可能な溶剤であれば制限されない。溶剤としては、上述した感光性樹脂組成物が含んでもよい溶剤が挙げられ、好ましい態様も同じである。 The solvent contained in the thermoplastic resin composition is not limited as long as it is a solvent capable of dissolving or dispersing the components contained in the thermoplastic resin layer. Examples of the solvent include a solvent that may be contained in the above-mentioned photosensitive resin composition, and the preferred embodiment is also the same.
　熱可塑性樹脂組成物は、１種単独、又は２種以上の溶剤を含んでもよい。 The thermoplastic resin composition may contain one kind alone or two or more kinds of solvents.
　熱可塑性樹脂組成物における溶剤の含有割合は、熱可塑性樹脂組成物中の全固形分１００質量部に対して、５０質量部～１，９００質量部であることが好ましく、１００質量部～９００質量部であることがより好ましい。 The content ratio of the solvent in the thermoplastic resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass with respect to 100 parts by mass of the total solid content in the thermoplastic resin composition. It is more preferable that it is a part.
　熱可塑性樹脂組成物の調製、及び熱可塑性樹脂層の形成は、上述した感光性樹脂組成物の調製方法、及びネガ型感光性樹脂層Ｎの形成方法に準じて行えばよい。例えば、熱可塑性樹脂層に含まれる各成分を溶剤に溶解した溶液を予め調製し、得られた各溶液を所定の割合で混合することにより、熱可塑性樹脂組成物を調製した後、得られた熱可塑性樹脂組成物を仮支持体の表面に塗布し、熱可塑性樹脂組成物の塗膜を乾燥させることにより、熱可塑性樹脂層を形成することができる。また、カバーフィルム上に、ネガ型感光性樹脂層Ｎを形成した後、ネガ型感光性樹脂層Ｎの表面に熱可塑性樹脂層を形成してもよい。 The preparation of the thermoplastic resin composition and the formation of the thermoplastic resin layer may be carried out according to the above-mentioned method for preparing the photosensitive resin composition and the method for forming the negative type photosensitive resin layer N. For example, a thermoplastic resin composition was prepared by preparing a solution in which each component contained in the thermoplastic resin layer was dissolved in a solvent in advance and mixing the obtained solutions in a predetermined ratio, and then obtained. The thermoplastic resin layer can be formed by applying the thermoplastic resin composition to the surface of the temporary support and drying the coating film of the thermoplastic resin composition. Further, after forming the negative type photosensitive resin layer N on the cover film, the thermoplastic resin layer may be formed on the surface of the negative type photosensitive resin layer N.
－－中間層－－
　感光性転写材料は、熱可塑性樹脂層とネガ型感光性樹脂層Ｎとの間に、中間層を有することが好ましい。中間層によれば、複数の層を形成する際、及び保存の際における成分の混合を抑制できる。 －－Intermediate layer －－
The photosensitive transfer material preferably has an intermediate layer between the thermoplastic resin layer and the negative photosensitive resin layer N. According to the intermediate layer, it is possible to suppress the mixing of components when forming a plurality of layers and during storage.
　中間層は、現像性、並びに、複数層を塗布する際及び塗布後の保存の際における成分の混合を抑制する観点から、水溶性の層であることが好ましい。本開示において、「水溶性」とは、液温が２２℃であるｐＨ７．０の水１００ｇへの溶解度が０．１ｇ以上であることを意味する。 The intermediate layer is preferably a water-soluble layer from the viewpoint of developability and suppressing mixing of components during application of the plurality of layers and storage after application. In the present disclosure, "water-soluble" means that the solubility in 100 g of water having a liquid temperature of 22 ° C. and a pH of 7.0 is 0.1 g or more.
　中間層としては、例えば、特開平５－７２７２４号公報に「分離層」として記載されている、酸素遮断機能のある酸素遮断層が挙げられる。中間層が酸素遮断層であることで、露光時の感度が向上し、露光機の時間負荷が低減する結果、生産性が向上する。中間層として用いられる酸素遮断層は、公知の層から適宜選択すればよい。中間層として用いられる酸素遮断層は、低い酸素透過性を示し、水、若しくはアルカリ水溶液（２２℃の炭酸ナトリウムの１質量％水溶液）に分散、又は溶解する酸素遮断層であることが好ましい。 Examples of the intermediate layer include an oxygen blocking layer having an oxygen blocking function, which is described as a “separation layer” in JP-A-5-72724. Since the intermediate layer is an oxygen blocking layer, the sensitivity at the time of exposure is improved, the time load of the exposure machine is reduced, and as a result, the productivity is improved. The oxygen blocking layer used as the intermediate layer may be appropriately selected from known layers. The oxygen blocking layer used as the intermediate layer is preferably an oxygen blocking layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous solution of sodium carbonate at 22 ° C.).
　中間層は、樹脂を含むことが好ましい。中間層に含まれる樹脂としては、例えば、ポリビニルアルコール系樹脂、ポリビニルピロリドン系樹脂、セルロース系樹脂、アクリルアミド系樹脂、ポリエチレンオキサイド系樹脂、ゼラチン、ビニルエーテル系樹脂、ポリアミド樹脂、及びこれらの共重合体が挙げられる。中間層に含まれる樹脂は、水溶性樹脂であることが好ましい。 The intermediate layer preferably contains a resin. Examples of the resin contained in the intermediate layer include polyvinyl alcohol-based resin, polyvinylpyrrolidone-based resin, cellulose-based resin, acrylamide-based resin, polyethylene oxide-based resin, gelatin, vinyl ether-based resin, polyamide resin, and copolymers thereof. Can be mentioned. The resin contained in the intermediate layer is preferably a water-soluble resin.
　中間層に含まれる樹脂は、複数の層間の成分の混合を抑制する観点から、ネガ型感光性樹脂層Ｎに含まれる重合体Ａ、及び熱可塑性樹脂層に含まれる熱可塑性樹脂（アルカリ可溶性樹脂）のいずれとも異なる樹脂であることが好ましい。 The resin contained in the intermediate layer is a polymer A contained in the negative photosensitive resin layer N and a thermoplastic resin (alkali-soluble resin) contained in the thermoplastic resin layer from the viewpoint of suppressing mixing of components between a plurality of layers. ), It is preferable that the resin is different from any of the above.
　中間層は、酸素遮断性、並びに、複数層を塗布する際及び塗布後の保存の際における成分の混合を抑制する観点から、ポリビニルアルコールを含むことが好ましく、ポリビニルアルコール、及びポリビニルピロリドンを含むことがより好ましい。 The intermediate layer preferably contains polyvinyl alcohol, and preferably contains polyvinyl alcohol and polyvinylpyrrolidone, from the viewpoint of oxygen blocking property and suppressing mixing of components during application of the plurality of layers and storage after application. Is more preferable.
　中間層は、１種単独、又は２種以上の樹脂を含んでもよい。 The intermediate layer may contain one kind of resin alone or two or more kinds of resins.
　中間層における樹脂の含有割合は、酸素遮断性、並びに、複数層を塗布する際及び塗布後の保存の際における成分の混合を抑制する観点から、中間層の全質量に対して、５０質量％～１００質量％であることが好ましく、７０質量％～１００質量％であることがより好ましく、８０質量％～１００質量％であることが更に好ましく、９０質量％～１００質量％であることが特に好ましい。 The content ratio of the resin in the intermediate layer is 50% by mass with respect to the total mass of the intermediate layer from the viewpoint of oxygen blocking property and suppressing mixing of components during application of the plurality of layers and storage after application. It is preferably ~ 100% by mass, more preferably 70% by mass to 100% by mass, further preferably 80% by mass to 100% by mass, and particularly preferably 90% by mass to 100% by mass. preferable.
　また、中間層は、必要に応じて添加剤を含んでもよい。添加剤としては、例えば、界面活性剤が挙げられる。 Further, the intermediate layer may contain an additive if necessary. Examples of the additive include a surfactant.
　中間層の厚さは、制限されない。中間層の平均厚さは、０．１μｍ～５μｍであることが好ましく、０．５μｍ～３μｍであることがより好ましい。中間層の厚さが上記範囲であることで、酸素遮断性を低下させることがなく、複数の層を形成する際、及び保存の際における成分の混合を抑制でき、また、現像時の中間層の除去時間の増大を抑制できる。 The thickness of the intermediate layer is not limited. The average thickness of the intermediate layer is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm. When the thickness of the intermediate layer is within the above range, the oxygen blocking property is not deteriorated, the mixing of the components at the time of forming a plurality of layers and at the time of storage can be suppressed, and the intermediate layer at the time of development can be suppressed. The increase in removal time can be suppressed.
　中間層の形成方法は、上記の成分を含む層を形成可能な方法であれば制限されない。中間層の形成方法としては、例えば、熱可塑性樹脂層、又はネガ型感光性樹脂層Ｎの表面に、中間層用組成物を塗布した後、中間層用組成物の塗膜を乾燥する方法が挙げられる。 The method of forming the intermediate layer is not limited as long as it is a method capable of forming a layer containing the above components. As a method for forming the intermediate layer, for example, a method of applying the composition for the intermediate layer to the surface of the thermoplastic resin layer or the negative photosensitive resin layer N and then drying the coating film of the composition for the intermediate layer is used. Can be mentioned.
　中間層用組成物としては、例えば、樹脂、及び任意の添加剤を含む組成物が挙げられる。中間層用組成物は、中間層用組成物の粘度を調節し、中間層の形成を容易にするため、溶剤を含むことが好ましい。溶剤としては、樹脂を溶解、又は分散可能な溶剤であれば制限されない。溶剤は、水、及び水混和性の有機溶剤よりなる群から選択される少なくとも１種であることが好ましく、水、又は水と水混和性の有機溶剤との混合溶剤であることがより好ましい。
　水混和性の有機溶剤としては、例えば、炭素数が１～３であるアルコール、アセトン、エチレングリコール、及びグリセリンが挙げられる。水混和性の有機溶剤は、炭素数が１～３であるアルコールであることが好ましく、メタノール、又はエタノールであることがより好ましい。 Examples of the composition for the intermediate layer include a composition containing a resin and an optional additive. The composition for the intermediate layer preferably contains a solvent in order to adjust the viscosity of the composition for the intermediate layer and facilitate the formation of the intermediate layer. The solvent is not limited as long as it is a solvent that can dissolve or disperse the resin. The solvent is preferably at least one selected from the group consisting of water and a water-miscible organic solvent, and more preferably water or a mixed solvent of water and a water-miscible organic solvent.
Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, and more preferably methanol or ethanol.
　また、感光性転写材料は、屈折率調整層等のその他の層を更に有していてもよい。
　屈折率調整層としては、特に制限はなく、公知の屈折率調整層を用いることができる。
　屈折率調整層の屈折率は、配線視認抑制性の観点から、感光性層の屈折率よりも高いことが好ましい。
　屈折率調整層の屈折率は、１．５０以上であることが好ましく、１．５５以上であることがより好ましく、１．６０以上であることが更に好ましく、１．７０以上であることが特に好ましい。
　屈折率調整層の屈折率の上限は、特に制限されないが、２．１０以下であることが好ましく、１．８５以下であることがより好ましく、１．７８以下であることが更に好ましく、１．７４以下であることが特に好ましい。
　屈折率調整層の厚さとしては、特に制限はない。
　屈折率調整層の厚さは、５０ｎｍ以上５００ｎｍ以下であることが好ましく、５５ｎｍ以上１１０ｎｍ以下であることがより好ましく、６０ｎｍ以上１００ｎｍ以下であることが更に好ましい。
　屈折率調整層の屈折率を制御する方法は、特に制限されず、例えば、所定の屈折率の樹脂を単独で用いる方法、樹脂と金属酸化物粒子又は金属粒子とを用いる方法、金属塩と樹脂との複合体を用いる方法等が挙げられる。
　金属酸化物粒子の種類としては、特に制限はなく、公知の金属酸化物粒子を用いることができる。
　金属酸化物粒子としては、具体的には、酸化ジルコニウム粒子（ＺｒＯ２粒子）、Ｎｂ２Ｏ５粒子、酸化チタン粒子（ＴｉＯ２粒子）、及び二酸化珪素粒子（ＳｉＯ２粒子）よりなる群から選ばれる少なくとも１種が好ましい。
　これらの中でも、金属酸化物粒子としては、例えば、第二の樹脂層の屈折率を１．６以上に調整しやすいという観点から、酸化ジルコニウム粒子及び酸化チタン粒子よりなる群から選ばれる少なくとも１種がより好ましい。 Further, the photosensitive transfer material may further have another layer such as a refractive index adjusting layer.
The refractive index adjusting layer is not particularly limited, and a known refractive index adjusting layer can be used.
The refractive index of the refractive index adjusting layer is preferably higher than that of the photosensitive layer from the viewpoint of suppressing the visibility of wiring.
The refractive index of the refractive index adjusting layer is preferably 1.50 or more, more preferably 1.55 or more, further preferably 1.60 or more, and particularly preferably 1.70 or more. preferable.
The upper limit of the refractive index of the refractive index adjusting layer is not particularly limited, but is preferably 2.10 or less, more preferably 1.85 or less, still more preferably 1.78 or less. It is particularly preferably 74 or less.
The thickness of the refractive index adjusting layer is not particularly limited.
The thickness of the refractive index adjusting layer is preferably 50 nm or more and 500 nm or less, more preferably 55 nm or more and 110 nm or less, and further preferably 60 nm or more and 100 nm or less.
The method of controlling the refractive index of the refractive index adjusting layer is not particularly limited, and for example, a method of using a resin having a predetermined refractive index alone, a method of using a resin and metal oxide particles or metal particles, a metal salt and a resin. A method using a complex with and the like can be mentioned.
The type of the metal oxide particles is not particularly limited, and known metal oxide particles can be used.
Specifically, the metal oxide particles are selected from the group consisting of zirconium oxide particles (ZrO 2 particles), Nb 2 O 5 particles, titanium oxide particles (TiO 2 particles), and silicon dioxide particles (SiO 2 particles). At least one kind is preferable.
Among these, as the metal oxide particles, for example, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles from the viewpoint that the refractive index of the second resin layer can be easily adjusted to 1.6 or more. Is more preferable.
－－平均厚さ－－
　感光性転写材料の平均厚さは、５μｍ～５５μｍであることが好ましく、１０μｍ～５０μｍであることがより好ましく、２０μｍ～４０μｍであることが特に好ましい。感光性転写材料の平均厚さは、上記透明基材の平均厚さの測定方法に準ずる方法によって測定する。 --Average thickness ---
The average thickness of the photosensitive transfer material is preferably 5 μm to 55 μm, more preferably 10 μm to 50 μm, and particularly preferably 20 μm to 40 μm. The average thickness of the photosensitive transfer material is measured by a method according to the method for measuring the average thickness of the transparent substrate.
－－形状－－
　感光性転写材料の形状は、制限されない。感光性転写材料の形状は、汎用性、及び運搬性の観点から、ロール状であることが好ましい。感光性転写材料を巻き取ることで、感光性転写材料の形状をロール状にすることができる。 --shape--
The shape of the photosensitive transfer material is not limited. The shape of the photosensitive transfer material is preferably roll-shaped from the viewpoint of versatility and transportability. By winding the photosensitive transfer material, the shape of the photosensitive transfer material can be made into a roll.
－感光性転写材料の製造方法－－
　感光性転写材料の製造方法は、制限されない。感光性転写材料の製造方法としては、例えば、仮支持体の上に、感光性樹脂組成物を塗布することによってネガ型感光性樹脂層Ｎを形成する工程と、上記ネガ型感光性樹脂層Ｎの上にカバーフィルムを配置する工程と、を含む方法が挙げられる。上記方法においては、必要に応じて、仮支持体の上に塗布された感光性樹脂組成物を乾燥してもよい。乾燥方法としては、制限されず、公知の乾燥方法を利用することができる。ネガ型感光性樹脂層Ｎの上に、カバーフィルムを配置する方法としては、例えば、ネガ型感光性樹脂層Ｎにカバーフィルムを圧着させる方法が挙げられる。 -Manufacturing method of photosensitive transfer material-
The method for producing the photosensitive transfer material is not limited. Examples of the method for producing the photosensitive transfer material include a step of forming a negative photosensitive resin layer N by applying a photosensitive resin composition on a temporary support, and the above-mentioned negative photosensitive resin layer N. A method including a step of arranging a cover film on the surface and a method including the step of placing the cover film on the surface can be mentioned. In the above method, the photosensitive resin composition applied on the temporary support may be dried, if necessary. The drying method is not limited, and a known drying method can be used. Examples of the method of arranging the cover film on the negative type photosensitive resin layer N include a method of crimping the cover film to the negative type photosensitive resin layer N.
＜露光工程＞
　本開示に係る構造体の製造方法は、上記透明基材の上記遮光性パターン１が設けられている面とは反対側の面から上記ネガ型感光性樹脂層Ｎの一部に光を照射する工程（露光工程）を含む。
　露光工程では、透明基材の遮光性パターン１が設けられている面とは反対側の面から光を照射する。本開示において、「透明基材の遮光性パターン１が設けられている面」とは、透明基材の表面のうち遮光性パターン１を有する側の面を意味する。例えば、図１（ｂ）において、「透明基材の遮光性パターン１が設けられている面」とは、遮光性パターン２０に接している透明基材１０の表面、すなわち、被露光面１０ａとは反対側を向く面をいう。例えば、図１（ｂ）に示されるように、透明基材の遮光性パターンに対向する面とは反対側の面に対して光を照射すると、遮光性パターンによってネガ型感光性樹脂層Ｎに到達する光の一部が遮られることで、ネガ型感光性樹脂層Ｎの一部を選択的に露光することができる。ネガ型感光性樹脂層Ｎの露光部は、現像液に対する溶解性が低下する。また、ネガ型感光性樹脂層Ｎから透明基材へ向かう方向に光を照射する場合に比べて、透明基材の遮光性パターンに対向する面とは反対側の面に対して光を照射することで、透明基材の近傍にあるネガ型感光性樹脂層Ｎの硬化を促進することができる。この結果、後述する現像工程において、樹脂パターンの解像性を向上させることができる。また、直線性の高い側壁を有する樹脂パターンを形成することができる。 <Exposure process>
In the method for producing a structure according to the present disclosure, a part of the negative photosensitive resin layer N is irradiated with light from a surface of the transparent base material opposite to the surface on which the light-shielding pattern 1 is provided. Includes process (exposure process).
In the exposure step, light is irradiated from the surface of the transparent substrate opposite to the surface on which the light-shielding pattern 1 is provided. In the present disclosure, the "surface provided with the light-shielding pattern 1 of the transparent base material" means the surface of the transparent base material on the side having the light-shielding pattern 1. For example, in FIG. 1B, the “surface provided with the light-shielding pattern 1 of the transparent base material” refers to the surface of the transparent base material 10 in contact with the light-shielding pattern 20, that is, the surface to be exposed 10a. Refers to the side facing the other side. For example, as shown in FIG. 1B, when light is applied to the surface of the transparent substrate opposite to the surface facing the light-shielding pattern, the negative-type photosensitive resin layer N is formed by the light-shielding pattern. By blocking a part of the reaching light, a part of the negative photosensitive resin layer N can be selectively exposed. The exposed portion of the negative photosensitive resin layer N has reduced solubility in a developing solution. Further, as compared with the case of irradiating light in the direction from the negative type photosensitive resin layer N toward the transparent substrate, the surface of the transparent substrate is irradiated with light on the surface opposite to the surface facing the light-shielding pattern. This makes it possible to accelerate the curing of the negative photosensitive resin layer N in the vicinity of the transparent substrate. As a result, the resolution of the resin pattern can be improved in the developing process described later. Further, it is possible to form a resin pattern having a side wall having high linearity.
　露光工程において使用される光源は、ネガ型感光性樹脂層Ｎを露光可能な波長の光（例えば、３６５ｎｍ、又は４０５ｎｍ）を照射する光源であればよい。具体的な光源としては、例えば、超高圧水銀灯、高圧水銀灯、メタルハライドランプ、及びＬＥＤ（Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）が挙げられる。 The light source used in the exposure step may be a light source that irradiates the negative photosensitive resin layer N with light having a wavelength that allows exposure (for example, 365 nm or 405 nm). Specific examples of the light source include an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).
　露光工程において照射される光は、２００ｎｍ～１，５００ｎｍの波長域に含まれる波長を含むことが好ましく、２５０ｎｍ～４５０ｎｍの波長域に含まれる波長を含むことがより好ましく、３００ｎｍ～４１０ｎｍの波長域に含まれる波長を含むことが好ましく、３６５ｎｍの波長を含むことがより好ましい。 The light irradiated in the exposure step preferably contains a wavelength included in the wavelength range of 200 nm to 1,500 nm, more preferably contains a wavelength included in the wavelength range of 250 nm to 450 nm, and has a wavelength range of 300 nm to 410 nm. It is preferable to include the wavelength contained in, and it is more preferable to include the wavelength of 365 nm.
　露光量は、５ｍＪ／ｃｍ２～２００ｍＪ／ｃｍ２であることが好ましく、１０ｍＪ／ｃｍ２～１００ｍＪ／ｃｍ２であることがより好ましい。 The exposure amount is preferably 5 mJ / cm 2 to 200 mJ / cm 2 , and more preferably 10 mJ / cm 2 to 100 mJ / cm 2 .
　露光工程においては、遮光性パターンによってネガ型感光性樹脂層Ｎの一部を選択的に露光することができるため、透明基材の遮光性パターン１が設けられている面とは反対側の面の全域に対して光を照射してもよい。 In the exposure step, a part of the negative photosensitive resin layer N can be selectively exposed by the light-shielding pattern, so that the surface of the transparent base material is opposite to the surface on which the light-shielding pattern 1 is provided. You may irradiate the whole area of.
＜現像工程＞
　本開示に係る構造体の製造方法は、光を照射された上記ネガ型感光性樹脂層Ｎを現像することで、上記透明基材上に樹脂パターン２を形成する工程（現像工程）を含む。
　現像工程では、ネガ型感光性樹脂層Ｎを現像することで、透明基材と遮光性パターンとによって画定される領域に樹脂パターン２を形成する。例えば、図１（ｃ）に示されるように、現像工程では、ネガ型感光性樹脂層Ｎの非露光部が除去されることで、ネガ型感光性樹脂層Ｎの露光部の形状に対応する形状を有する樹脂パターンが形成される。 <Development process>
The method for producing a structure according to the present disclosure includes a step (development step) of forming a resin pattern 2 on the transparent substrate by developing the negative photosensitive resin layer N irradiated with light.
In the developing step, the negative type photosensitive resin layer N is developed to form the resin pattern 2 in the region defined by the transparent base material and the light-shielding pattern. For example, as shown in FIG. 1C, in the developing step, the non-exposed portion of the negative photosensitive resin layer N is removed to correspond to the shape of the exposed portion of the negative photosensitive resin layer N. A resin pattern having a shape is formed.
　現像方法としては、公知の方法を利用することができる。ネガ型感光性樹脂層Ｎの現像は、例えば、現像液を用いて行うことができる。現像液の種類は、ネガ型感光性樹脂層Ｎの非露光部を除去することができれば制限されない。現像液としては、公知の現像液（例えば、特開平５－７２７２４号公報に記載の現像液）を利用することができる。 As a developing method, a known method can be used. The negative photosensitive resin layer N can be developed using, for example, a developing solution. The type of developer is not limited as long as the non-exposed portion of the negative photosensitive resin layer N can be removed. As the developing solution, a known developing solution (for example, the developing solution described in JP-A-5-72724) can be used.
　現像液は、ｐＫａが７～１３である化合物を０．０５ｍｏｌ／Ｌ～５ｍｏｌ／Ｌの濃度で含むアルカリ水溶液系の現像液であることが好ましい。現像液は、水溶性の有機溶剤及び／又は界面活性剤を含んでもよい。現像液としては、国際公開第２０１５／０９３２７１号の段落０１９４に記載の現像液も好ましい。 The developer is preferably an alkaline aqueous solution-based developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L to 5 mol / L. The developer may contain a water-soluble organic solvent and / or a surfactant. As the developing solution, the developing solution described in paragraph 0194 of International Publication No. 2015/093271 is also preferable.
　現像方式としては、特に制限されず、パドル現像、シャワー現像、シャワー及びスピン現像、並びに、ディップ現像のいずれであってもよい。シャワー現像とは、露光後の感光性樹脂層に現像液をシャワーにより吹き付けることにより、露光部、又は非露光部を除去する現像処理である。 The development method is not particularly limited, and may be any of paddle development, shower development, shower and spin development, and dip development. Shower development is a development process in which an exposed portion or a non-exposed portion is removed by spraying a developing solution onto the photosensitive resin layer after exposure by a shower.
　現像工程の後に、洗浄剤をシャワーにより吹き付け、ブラシで擦りながら、現像残渣を除去することが好ましい。 After the developing step, it is preferable to spray the cleaning agent with a shower and rub with a brush to remove the developing residue.
　現像液の液温は、制限されない。現像液の液温は、２０℃～４０℃であることが好ましい。 The temperature of the developer is not limited. The liquid temperature of the developing solution is preferably 20 ° C. to 40 ° C.
　樹脂パターン２の平均厚さは、遮光性パターン１の平均厚さより大きいことが好ましい。樹脂パターン２の平均厚さが遮光性パターンの平均厚さより大きいことで、厚みのある遮光性パターン１を形成することができる。遮光性パターン１の平均厚さに対する樹脂パターン２の平均厚さの比（［樹脂パターン２の平均厚さ］／［遮光性パターン１の平均厚さ］）は、１．１以上であることが好ましく、１．５以上であることがより好ましく、３以上であることが特に好ましい。遮光性パターン１の平均厚さに対する樹脂パターン２の平均厚さの比は、４、５、又は１０であってもよい。樹脂パターン２の平均厚さは、上記透明基材の平均厚さの測定方法に準ずる方法によって想定する。 The average thickness of the resin pattern 2 is preferably larger than the average thickness of the light-shielding pattern 1. When the average thickness of the resin pattern 2 is larger than the average thickness of the light-shielding pattern, a thick light-shielding pattern 1 can be formed. The ratio of the average thickness of the resin pattern 2 to the average thickness of the light-shielding pattern 1 ([average thickness of the resin pattern 2] / [average thickness of the light-shielding pattern 1]) must be 1.1 or more. It is preferably 1.5 or more, and particularly preferably 3 or more. The ratio of the average thickness of the resin pattern 2 to the average thickness of the light-shielding pattern 1 may be 4, 5, or 10. The average thickness of the resin pattern 2 is assumed by a method according to the method for measuring the average thickness of the transparent base material.
　樹脂パターン２の平均厚さは、１μｍ以上であることが好ましく、２μｍ以上であることがより好ましく、２μｍを超えることが特に好ましい。更に、樹脂パターンの平均厚さは、３μｍ以上であることが好ましく、５μｍ以上であることがより好ましく、１０μｍ以上であることが特に好ましい。樹脂パターン２の厚さの上限は、制限されない。樹脂パターンの平均厚さは、例えば、１００μｍ以下の範囲で決定すればよい。 The average thickness of the resin pattern 2 is preferably 1 μm or more, more preferably 2 μm or more, and particularly preferably more than 2 μm. Further, the average thickness of the resin pattern is preferably 3 μm or more, more preferably 5 μm or more, and particularly preferably 10 μm or more. The upper limit of the thickness of the resin pattern 2 is not limited. The average thickness of the resin pattern may be determined, for example, in the range of 100 μm or less.
　樹脂パターン２の平均幅は、５０μｍ以下であることが好ましく、５μｍ以下であることがより好ましい。樹脂パターン２の平均幅は、０．３μｍ以上であることが好ましく、０．５μｍ以上であることがより好ましい。樹脂パターン２の平均幅は、遮光性パターン１の平均幅の測定方法に準ずる方法によって測定する。 The average width of the resin pattern 2 is preferably 50 μm or less, and more preferably 5 μm or less. The average width of the resin pattern 2 is preferably 0.3 μm or more, and more preferably 0.5 μm or more. The average width of the resin pattern 2 is measured by a method according to the method for measuring the average width of the light-shielding pattern 1.
＜パターン３形成工程＞
　本開示に係る構造体の製造方法は、上記遮光性パターン１と上記樹脂パターン２とによって画定される領域にパターン３を形成する工程（パターン３形成工程）を含む。
　パターン３形成工程では、遮光性パターン１の上にパターン３を形成する。例えば、図１（ｄ）に示されるように、パターン３形成工程では、遮光性パターン１と樹脂パターン２とによって画定される領域にパターン３が形成される。
　パターン３は、本開示における効果をより発揮する観点から、導電性を有することが好ましい。
　また、パターン形成性及び得られるパターン３の寸法安定性の観点から、上記遮光性パターン１の平均厚さよりも上記パターン３の平均厚さのほうが厚いことが好ましい。 <Pattern 3 forming process>
The method for producing a structure according to the present disclosure includes a step of forming a pattern 3 in a region defined by the light-shielding pattern 1 and the resin pattern 2 (pattern 3 forming step).
In the pattern 3 forming step, the pattern 3 is formed on the light-shielding pattern 1. For example, as shown in FIG. 1D, in the pattern 3 forming step, the pattern 3 is formed in the region defined by the light-shielding pattern 1 and the resin pattern 2.
Pattern 3 is preferably conductive from the viewpoint of more exerting the effects in the present disclosure.
Further, from the viewpoint of pattern formability and dimensional stability of the obtained pattern 3, it is preferable that the average thickness of the pattern 3 is thicker than the average thickness of the light-shielding pattern 1.
　パターン３を形成する方法としては、公知の方法を利用することができる。導電性を有するパターン３の材料としては、用途に適した導電性を有する材料を利用することができる。導電性を有するパターン３の材料は、Ｃｕ、又はＣｕの合金を含むことが好ましい。Ｃｕの合金は、Ｃｕと、Ｎｉ、Ｍｏ、Ｔａ、Ｔｉ、Ｖ、Ｃｒ、Ｆｅ、Ｍｎ、Ｃｏ、及びＷよりなる群から選択される少なくとも１種との合金であることが好ましい。上記した材料を用いて形成されるパターン３は、上記した金属元素を含む。パターン３形成工程において得られるパターン３は、Ｃｕからなる導電性パターンであってもよい。
　また、パターン形成性及び得られるパターン３の寸法安定性の観点から、上記遮光性パターン１及び上記パターン３が、同種の材料を含むことが好ましい。例えば、同じ金属元素を含むことがより好ましく、同じ金属、又は、同じ金属元素を含む合金であることが特に好ましい。 As a method for forming the pattern 3, a known method can be used. As the material of the pattern 3 having conductivity, a material having conductivity suitable for an application can be used. The conductive pattern 3 material preferably contains Cu or an alloy of Cu. The alloy of Cu is preferably an alloy of Cu and at least one selected from the group consisting of Ni, Mo, Ta, Ti, V, Cr, Fe, Mn, Co, and W. The pattern 3 formed by using the above-mentioned material contains the above-mentioned metal element. The pattern 3 obtained in the pattern 3 forming step may be a conductive pattern made of Cu.
Further, from the viewpoint of pattern formability and dimensional stability of the obtained pattern 3, it is preferable that the light-shielding pattern 1 and the pattern 3 contain the same kind of material. For example, it is more preferable to contain the same metal element, and it is particularly preferable that the same metal or an alloy containing the same metal element is used.
　遮光性パターン１の上にパターン３を形成する方法としては、公知の方法を利用することができる。パターン３は、めっき法によって形成されてなるパターンであることが好ましい。めっきとしては、公知のめっきを利用することができる。めっきとしては、例えば、電気めっき、及び無電解めっきが挙げられる。めっきは、電気めっきであることが好ましく、電気銅めっきであることがより好ましい。 As a method of forming the pattern 3 on the light-shielding pattern 1, a known method can be used. The pattern 3 is preferably a pattern formed by a plating method. As the plating, known plating can be used. Examples of plating include electroplating and electroless plating. The plating is preferably electroplating, more preferably electrocopper plating.
　電気めっきでは、例えば、シード層として機能することができる遮光性パターン１をカソードとして用い、遮光性パターンの上に金属を積み重ねることで、遮光性パターン１の上に導電性を有するパターン３を形成することができる。 In electroplating, for example, a light-shielding pattern 1 that can function as a seed layer is used as a cathode, and a metal is stacked on the light-shielding pattern to form a conductive pattern 3 on the light-shielding pattern 1. can do.
　電気めっきにおいて使用されるめっき液の成分としては、例えば、水溶性銅塩が挙げられる。水溶性銅塩としては、めっき液の成分として通常使用される水溶性銅塩を用いることができる。水溶性銅塩としては、例えば、無機銅塩、アルカンスルホン酸銅塩、アルカノールスルホン酸銅塩、及び有機酸銅塩よりなる群から選択される少なくとも１種であることが好ましい。無機銅塩としては、例えば、硫酸銅、酸化銅、塩化銅、及び炭酸銅が挙げられる。アルカンスルホン酸銅塩としては、例えば、メタンスルホン酸銅、及びプロパンスルホン酸銅が挙げられる。アルカノールスルホン酸銅塩としては、例えば、イセチオン酸銅、及びプロパノールスルホン酸銅が挙げられる。有機酸銅塩としては、例えば、酢酸銅、クエン酸銅、及び酒石酸銅が挙げられる。 Examples of the components of the plating solution used in electroplating include water-soluble copper salts. As the water-soluble copper salt, a water-soluble copper salt usually used as a component of a plating solution can be used. The water-soluble copper salt is preferably at least one selected from the group consisting of, for example, an inorganic copper salt, an alkane sulfonic acid copper salt, an alkanol sulfonic acid copper salt, and an organic acid copper salt. Examples of the inorganic copper salt include copper sulfate, copper oxide, copper chloride, and copper carbonate. Examples of the alkane sulfonic acid copper salt include copper methane sulfonate and copper propane sulfonate. Examples of the alkanol sulfonate copper salt include copper isethionic acid and copper propanol sulfonate. Examples of the organic acid copper salt include copper acetate, copper citrate, and copper tartrate.
　めっき液は、硫酸を含んでもよい。めっき液が硫酸を含むことで、めっき液のｐＨ、及び硫酸イオン濃度を調整することができる。 The plating solution may contain sulfuric acid. Since the plating solution contains sulfuric acid, the pH of the plating solution and the sulfate ion concentration can be adjusted.
　電気めっきの方法、及び条件は、制限されない。例えば、めっき液を加えためっき槽に現像工程後の透明基材を供給することで、遮光性パターン１の上に導電性を有するパターン３を形成することができる。電気めっきにおいては、例えば、電流密度、及び透明基材の搬送速度を制御することで、導電性を有するパターン３を形成することができる。 The electroplating method and conditions are not limited. For example, by supplying the transparent base material after the developing step to the plating tank to which the plating solution is added, the pattern 3 having conductivity can be formed on the light-shielding pattern 1. In electroplating, for example, by controlling the current density and the transport speed of the transparent substrate, the pattern 3 having conductivity can be formed.
　電気めっきに使用されるめっき液の温度は、一般的に７０℃以下であり、１０℃～４０℃であることが好ましい。電気めっきにおける電流密度は、一般的に０．１Ａ／ｄｍ２～１００Ａ／ｄｍ２であり、０．５Ａ／ｄｍ２～２０Ａ／ｄｍ２であることが好ましい。電流密度を高くすることで導電性パターンの生産性を向上させることができる。電流密度を低くすることで導電性パターンの厚さの均一性を向上させることができる。 The temperature of the plating solution used for electroplating is generally 70 ° C. or lower, preferably 10 ° C. to 40 ° C. The current density in electroplating is generally 0.1 A / dm 2 to 100 A / dm 2 , preferably 0.5 A / dm 2 to 20 A / dm 2. By increasing the current density, the productivity of the conductive pattern can be improved. By lowering the current density, the uniformity of the thickness of the conductive pattern can be improved.
　めっきによる導電性を有するパターン３の形成方法においては、複数の金属を連続してめっきしてもよい。例えば、銅のような金属によって形成されたパターン３においては、反射によって視認性又は美観性の低下が課題となることがある。パターン３の表面の反射率を低減する方法としては、例えば、酸化処理、硫化処理、窒化処理、塩素化処理、黒化層被膜形成、及び黒色めっきが挙げられる。例えば、銅めっき後にクロムめっきを行うことで、パターン３の表面に黒色の材料を含む層を形成することができる。パターン３の表面の反射率を低減する方法は、酸化処理、又は硫化処理であることが好ましい。酸化処理は、より優れた防眩効果を得ることができ、更に、廃液処理の簡易性及び環境安全性の点からも好ましい。 In the method of forming the pattern 3 having conductivity by plating, a plurality of metals may be continuously plated. For example, in the pattern 3 formed of a metal such as copper, deterioration of visibility or aesthetics may be a problem due to reflection. Examples of the method for reducing the reflectance of the surface of the pattern 3 include oxidation treatment, sulfurization treatment, nitriding treatment, chlorination treatment, formation of a blackened layer film, and black plating. For example, by performing chrome plating after copper plating, a layer containing a black material can be formed on the surface of the pattern 3. The method for reducing the reflectance of the surface of the pattern 3 is preferably an oxidation treatment or a sulfurization treatment. The oxidation treatment can obtain a more excellent antiglare effect, and is also preferable from the viewpoint of simplicity of waste liquid treatment and environmental safety.
　パターン３を形成した後、ポストベーク工程を行ってもよい。ポストベーク工程は、未反応の熱硬化成分を完全に熱硬化することで、絶縁信頼性、硬化特性、又はめっき密着性を向上させることができる。加熱温度は、８０℃～２４０℃であることが好ましい。加熱時間は、５分間～１２０分間であることが好ましい。 After forming the pattern 3, the post-baking process may be performed. In the post-baking step, the insulation reliability, the curing property, or the plating adhesion can be improved by completely heat-curing the unreacted thermosetting component. The heating temperature is preferably 80 ° C. to 240 ° C. The heating time is preferably 5 minutes to 120 minutes.
　パターン３を形成した後、パターン３の表面を樹脂層によって保護してもよい。例えば、パターン３を形成した後、導電性パターンの上に樹脂層を形成することによって、パターン３の表面を保護することができる。樹脂層の成分としては、例えば、アクリル樹脂、ポリエステル樹脂、ポリビニルアセタール樹脂層、ポリイミド樹脂、及びエポキシ樹脂が挙げられる。樹脂層の形成方法としては、例えば、塗布、及び熱圧着が挙げられる。 After forming the pattern 3, the surface of the pattern 3 may be protected by a resin layer. For example, after forming the pattern 3, the surface of the pattern 3 can be protected by forming a resin layer on the conductive pattern. Examples of the components of the resin layer include an acrylic resin, a polyester resin, a polyvinyl acetal resin layer, a polyimide resin, and an epoxy resin. Examples of the method for forming the resin layer include coating and thermocompression bonding.
　パターン３の構造は、単層構造、又は多層構造であってもよい。多層構造を有するパターン３の各層の成分は、同一であっても異なってもよい。 The structure of pattern 3 may be a single-layer structure or a multi-layer structure. The components of each layer of the pattern 3 having a multi-layer structure may be the same or different.
　パターン３の厚さは、制限されない。パターン３の厚さは、例えば、用途に応じて決定すればよい。パターン３を配線として用いる場合、パターン３の平均厚さは、例えば、配線に供給する電流の大きさ、及び配線幅に応じて決定すればよい。パターン３の平均厚さは、導電性の観点から、０．５μｍ以上であることが好ましく、１μｍ以上であることがより好ましく、２μｍ以上であることが特に好ましい。更に、パターン３の平均厚さは、３μｍ以上であることが好ましく、５μｍ以上であることがより好ましく、１０μｍ以上であることが特に好ましい。パターン３の平均厚さは、上記透明基材の平均厚さの測定方法に準ずる方法によって測定する。 The thickness of pattern 3 is not limited. The thickness of the pattern 3 may be determined, for example, according to the application. When the pattern 3 is used as the wiring, the average thickness of the pattern 3 may be determined according to, for example, the magnitude of the current supplied to the wiring and the wiring width. From the viewpoint of conductivity, the average thickness of the pattern 3 is preferably 0.5 μm or more, more preferably 1 μm or more, and particularly preferably 2 μm or more. Further, the average thickness of the pattern 3 is preferably 3 μm or more, more preferably 5 μm or more, and particularly preferably 10 μm or more. The average thickness of the pattern 3 is measured by a method according to the method for measuring the average thickness of the transparent substrate.
　パターン３の幅は、細いことが好ましい。具体的に、パターン３の平均幅は、５０μｍ以下であることが好ましく、１０μｍ以下であることがより好ましく、５μｍ以下であることが更に好ましく、２μｍ以下であることが特に好ましい。パターン３の平均幅が５μｍ以下であることで、例えば、タッチパネルのように視認性に敏感な装置におけるパターン３の視認性を低減することができる。パターン３の平均幅は、導電性の観点から、０．１μｍ以上であることが好ましく、０．５μｍ以上であることがより好ましく、０．８μｍ以上であることが特に好ましい。パターン３の平均幅は、上記遮光性パターン１の平均幅の測定方法に準ずる方法によって測定する。 The width of pattern 3 is preferably narrow. Specifically, the average width of the pattern 3 is preferably 50 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, and particularly preferably 2 μm or less. When the average width of the pattern 3 is 5 μm or less, the visibility of the pattern 3 in a device sensitive to visibility such as a touch panel can be reduced. From the viewpoint of conductivity, the average width of the pattern 3 is preferably 0.1 μm or more, more preferably 0.5 μm or more, and particularly preferably 0.8 μm or more. The average width of the pattern 3 is measured by a method according to the method for measuring the average width of the light-shielding pattern 1.
　導電性を有するパターン３の表面抵抗値は、０．２Ω／□未満であることが好ましく、０．１５Ω／□未満であることがより好ましい。導電性を有するパターン３の表面抵抗値は、４探針法によって測定する。パターンサイズが微細で測定が困難な場合には、同一の組成及び厚さの導電層の表面抵抗値を測定してもよい。 The surface resistance value of the conductive pattern 3 is preferably less than 0.2 Ω / □, and more preferably less than 0.15 Ω / □. The surface resistance value of the conductive pattern 3 is measured by the 4-probe method. When the pattern size is fine and difficult to measure, the surface resistance value of the conductive layer having the same composition and thickness may be measured.
　パターン３形成工程において、パターン３と遮光性パターン１との界面は、明確に観察されないことがある。例えば、遮光性パターン１をシード層として用い、パターン３をめっきによって形成する場合、遮光性パターン１とパターン３との界面が明確に観察されないことがある。ただし、パターン３と遮光性パターン１との界面が明確に観察されないことは、本開示の目的を妨げるものではない。 In the pattern 3 forming step, the interface between the pattern 3 and the light-shielding pattern 1 may not be clearly observed. For example, when the light-shielding pattern 1 is used as a seed layer and the pattern 3 is formed by plating, the interface between the light-shielding pattern 1 and the pattern 3 may not be clearly observed. However, the fact that the interface between the pattern 3 and the light-shielding pattern 1 is not clearly observed does not preclude the object of the present disclosure.
＜後露光工程、及び、後加熱工程＞
　本開示に係る構造体の製造方法は、永久膜である樹脂パターン２の強度及び耐久性を向上させる観点から、上記樹脂パターン２に対し後露光及び後加熱の少なくともいずれかを行う工程を更に含むことが好ましい。
　本開示に係る構造体の製造方法は、上記現像工程の後、上記樹脂パターン２を後露光する工程（「後露光工程」ともいう。）を含むことが好ましく、上記パターン３形成工程の後、上記樹脂パターン２を後露光する工程を含むことがより好ましい。
　また、本開示に係る構造体の製造方法は、更に必要に応じて、上記樹脂パターン２を加熱（後加熱）する工程（「後加熱工程」ともいう。）を含んでもよい。
　上記樹脂パターン２は、ネガ型感光性樹脂層Ｎの露光部であるため、上記後露光又は上記後加熱を行うことにより、残存している重合開始剤及び重合性化合物等により、更に重合反応等が進行し、樹脂パターン２の強度、及び、耐熱性、耐光性、耐湿性等の耐久性が向上する。 <Post-exposure process and post-heating process>
The method for producing a structure according to the present disclosure further includes a step of performing at least one of post-exposure and post-heating on the resin pattern 2 from the viewpoint of improving the strength and durability of the resin pattern 2 which is a permanent film. Is preferable.
The method for producing a structure according to the present disclosure preferably includes a step of post-exposure the resin pattern 2 (also referred to as a “post-exposure step”) after the development step, and after the pattern 3 forming step, It is more preferable to include a step of post-exposing the resin pattern 2.
Further, the method for producing a structure according to the present disclosure may further include a step of heating (post-heating) the resin pattern 2 (also referred to as a “post-heating step”), if necessary.
Since the resin pattern 2 is an exposed portion of the negative photosensitive resin layer N, by performing the post-exposure or the post-heating, the remaining polymerization initiator, the polymerizable compound, and the like further cause a polymerization reaction and the like. The strength of the resin pattern 2 and the durability such as heat resistance, light resistance, and moisture resistance are improved.
　後露光工程における露光に使用する光源としては、特に制限はなく、公知の露光光源を用いることができる。除去性の観点から、上記樹脂パターン形成工程と同じ波長の光を含む光源を用いることが好ましい。 The light source used for exposure in the post-exposure step is not particularly limited, and a known exposure light source can be used. From the viewpoint of removability, it is preferable to use a light source containing light having the same wavelength as that in the resin pattern forming step.
　後露光工程における露光量としては、除去性の観点から、５ｍＪ／ｃｍ２～５，０００ｍＪ／ｃｍ２であることが好ましく、１０ｍＪ／ｃｍ２～３，０００ｍＪ／ｃｍ２であることがより好ましく、１００ｍＪ／ｃｍ２～１，５００ｍＪ／ｃｍ２であることが特に好ましい。 The exposure amount in the post-exposure step, from the viewpoint of removability is preferably 5mJ / cm 2 ~ 5,000mJ / cm 2, more preferably 10mJ / cm 2 ~ 3,000mJ / cm 2, and particularly preferably 100mJ / cm 2 ~ 1,500mJ / cm 2.
　後露光工程における露光量としては、除去性の観点から、上記樹脂パターン形成工程における露光量以上であることが好ましく、上記樹脂パターン形成工程における露光量よりも多いことがより好ましい。 From the viewpoint of removability, the exposure amount in the post-exposure step is preferably equal to or more than the exposure amount in the resin pattern forming step, and more preferably larger than the exposure amount in the resin pattern forming step.
　本開示に係る構造体の製造方法は、後加熱工程を、複数回含んでいてもよい。
　後加熱工程における加熱温度及び加熱時間は、特に制限はなく、適宜選択することができる。
　後加熱する方法は、特に制限はなく、公知の方法を用いることができ、例えば、露光装置及び現像装置に備わっている手段で行ってもよいし、ホットプレート等を用いて行ってもよい。 The method for producing a structure according to the present disclosure may include a post-heating step a plurality of times.
The heating temperature and heating time in the post-heating step are not particularly limited and can be appropriately selected.
The method of post-heating is not particularly limited, and a known method can be used. For example, the method may be performed by means provided in the exposure apparatus and the developing apparatus, or may be performed by using a hot plate or the like.
＜その他の工程＞
　本開示に係る構造体の製造方法は、上述した以外の任意の工程（その他の工程）を含んでもよい。その他の工程としては、特に制限はなく、公知の工程が挙げられる。
　また、本開示における樹脂パターン形成工程及びその他の工程の例としては、特開２００６－２３６９６号公報の段落００３５～段落００５１に記載の方法を本開示においても好適に用いることができる。
　また、本開示に係る構造体の製造方法は、得られたパターンを研磨する工程、及び、得られたパターンを洗浄する工程等を含んでいてもよい。
　更に、本開示に係る構造体の製造方法は、後述する各用途に応じた部材を設ける工程等を含んでいてもよい。 <Other processes>
The method for producing a structure according to the present disclosure may include any steps (other steps) other than those described above. The other steps are not particularly limited, and examples thereof include known steps.
Further, as an example of the resin pattern forming step and other steps in the present disclosure, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be preferably used in the present disclosure.
In addition, the method for producing a structure according to the present disclosure may include a step of polishing the obtained pattern, a step of cleaning the obtained pattern, and the like.
Further, the method for manufacturing a structure according to the present disclosure may include a step of providing a member according to each application, which will be described later.
＜＜用途＞＞
　本開示に係る構造体の製造方法によって得られる構造体は、種々の用途に適用することができる。本開示に係る構造体の製造方法によって得られる構造体の用途としては、例えば、タッチセンサー、電磁波シールド、アンテナ、配線基板、及び導電性加熱素子が挙げられる。上記した用途において、本開示に係る構造体の製造方法によって得られる構造体は、例えば、電気伝導体として機能することができる。また、上記した用途において、本開示に係る構造体の製造方法によって得られる構造体は、形成されたパターン（樹脂パターン２及びパターン３等）の特性に応じて種々の機能を発現することができる。 << Applications >>
The structure obtained by the method for producing a structure according to the present disclosure can be applied to various uses. Applications of the structure obtained by the method for manufacturing the structure according to the present disclosure include, for example, a touch sensor, an electromagnetic wave shield, an antenna, a wiring substrate, and a conductive heating element. In the above-mentioned applications, the structure obtained by the method for producing a structure according to the present disclosure can function as, for example, an electric conductor. Further, in the above-mentioned applications, the structure obtained by the method for producing a structure according to the present disclosure can exhibit various functions depending on the characteristics of the formed patterns (resin pattern 2, pattern 3, etc.). ..
＜タッチセンサー＞
　本開示に係るタッチセンサーは、本開示に係る構造体の製造方法によって得られる構造体を有する。本開示に係るタッチセンサーにおいて、上記構造体が有する導電性パターン（例えば、遮光性パターン１及び導電性を有するパターン３等、以下同様）は、例えば、透明電極、又は額縁配線として利用することができる。本開示に係るタッチセンサーの構成要素は、本開示に係る構造体の製造方法によって得られる構造体を含むことを除き、制限されない。上記構造体以外の構成要素としては、公知のタッチセンサーに含まれる構成要素を利用することができる。タッチセンサーについては、例えば、特許第６４８６３４１号公報、及び特開２０１６－１５５９７８号公報に記載されている。上記した公報は、参照により本明細書に取り込まれる。本開示に係るタッチセンサーの製造方法は、本開示に係る構造体の製造方法によって得られる構造体を有するタッチセンサーを製造する方法であれば制限されない。 <Touch sensor>
The touch sensor according to the present disclosure has a structure obtained by the method for manufacturing the structure according to the present disclosure. In the touch sensor according to the present disclosure, the conductive pattern of the structure (for example, the light-shielding pattern 1 and the conductive pattern 3, etc., the same applies hereinafter) can be used as, for example, a transparent electrode or a frame wiring. can. The components of the touch sensor according to the present disclosure are not limited except that the structure obtained by the method for manufacturing the structure according to the present disclosure is included. As a component other than the above structure, a component included in a known touch sensor can be used. The touch sensor is described in, for example, Japanese Patent No. 6486341 and Japanese Patent Application Laid-Open No. 2016-155978. The above publications are incorporated herein by reference. The method for manufacturing a touch sensor according to the present disclosure is not limited as long as it is a method for manufacturing a touch sensor having a structure obtained by the method for manufacturing a structure according to the present disclosure.
＜電磁波シールド＞
　本開示に係る電磁波シールドは、本開示に係る構造体の製造方法によって得られる構造体を有する。本開示に係る電磁波シールドにおいて、上記構造体が有する導電性パターンは、例えば、電磁波シールド体として利用することができる。本開示に係る電磁波シールドの構成要素は、本開示に係る構造体の製造方法によって得られる構造体を含むことを除き、制限されない。上記構造体以外の構成要素としては、公知の電磁波シールドに含まれる構成要素を利用することができる。電磁波シールドについては、例えば、特許第６４８６３８２号公報、及び特開２０１２－１６３９５１号公報に記載されている。上記した公報は、参照により本明細書に取り込まれる。本開示に係る電磁波シールドの製造方法は、本開示に係る構造体の製造方法によって得られる構造体を有する電磁波シールドを製造する方法であれば制限されない。 <Electromagnetic wave shield>
The electromagnetic wave shield according to the present disclosure has a structure obtained by the method for manufacturing the structure according to the present disclosure. In the electromagnetic wave shield according to the present disclosure, the conductive pattern of the structure can be used as, for example, an electromagnetic wave shield body. The components of the electromagnetic wave shield according to the present disclosure are not limited except that the structure obtained by the method for manufacturing the structure according to the present disclosure is included. As a component other than the above structure, a component included in a known electromagnetic wave shield can be used. The electromagnetic wave shield is described in, for example, Japanese Patent No. 6486382 and Japanese Patent Application Laid-Open No. 2012-163951. The above publications are incorporated herein by reference. The method for manufacturing an electromagnetic wave shield according to the present disclosure is not limited as long as it is a method for manufacturing an electromagnetic wave shield having a structure obtained by the method for manufacturing a structure according to the present disclosure.
＜アンテナ＞
　本開示に係るアンテナは、本開示に係る構造体の製造方法によって得られる構造体を有するアンテナである。本開示に係るアンテナにおいて、上記構造体が有する導電性パターンは、例えば、送受信部、又は伝送線路部として利用することができる。本開示に係るアンテナの構成要素は、本開示に係る構造体の製造方法によって得られる構造体を含むことを除き、制限されない。上記構造体以外の構成要素としては、公知のアンテナに含まれる構成要素を利用することができる。アンテナについては、例えば、特開２０１６－２１９９９９号公報に記載されている。上記した公報は、参照により本明細書に取り込まれる。本開示に係るアンテナの製造方法は、本開示に係る構造体の製造方法によって得られる構造体を有するアンテナを製造する方法であれば制限されない。 <Antenna>
The antenna according to the present disclosure is an antenna having a structure obtained by the method for manufacturing the structure according to the present disclosure. In the antenna according to the present disclosure, the conductive pattern of the structure can be used as, for example, a transmission / reception unit or a transmission line unit. The components of the antenna according to the present disclosure are not limited except that the structure obtained by the method for manufacturing the structure according to the present disclosure is included. As a component other than the above structure, a component included in a known antenna can be used. The antenna is described in, for example, Japanese Patent Application Laid-Open No. 2016-219999. The above publications are incorporated herein by reference. The method for manufacturing an antenna according to the present disclosure is not limited as long as it is a method for manufacturing an antenna having a structure obtained by the method for manufacturing a structure according to the present disclosure.
＜配線基板＞
　本開示に係る配線基板は、本開示に係る構造体の製造方法によって得られる構造体を有する。本開示に係る配線基板において、上記構造体が有する導電性パターンは、例えば、プリント配線板の配線として利用することができる。本開示に係る配線基板の構成要素は、本開示に係る構造体の製造方法によって得られる構造体を含むことを除き、制限されない。上記構造体以外の構成要素としては、公知の配線基板に含まれる構成要素を利用することができる。配線基板については、例えば、特許第５７７４６８６号公報、及び特開２０１７－２０４５３８号公報に記載されている。上記した公報は、参照により本明細書に取り込まれる。本開示に係る配線基板の製造方法は、本開示に係る構造体の製造方法によって得られる構造体を有する配線基板を製造する方法であれば制限されない。 <Wiring board>
The wiring board according to the present disclosure has a structure obtained by the method for manufacturing the structure according to the present disclosure. In the wiring board according to the present disclosure, the conductive pattern of the structure can be used, for example, as wiring for a printed wiring board. The components of the wiring board according to the present disclosure are not limited except that the components obtained by the method for manufacturing the structure according to the present disclosure are included. As a component other than the above structure, a component included in a known wiring board can be used. The wiring board is described in, for example, Japanese Patent No. 5774686 and Japanese Patent Application Laid-Open No. 2017-204538. The above publications are incorporated herein by reference. The method for manufacturing a wiring board according to the present disclosure is not limited as long as it is a method for manufacturing a wiring board having a structure obtained by the method for manufacturing a structure according to the present disclosure.
＜導電性加熱素子＞
　本開示に係る導電性加熱素子は、本開示に係る構造体の製造方法によって得られる構造体を有する。本開示に係る導電性加熱素子において、上記構造体が有する導電性パターンは、例えば、発熱体として利用することができる。本開示に係る導電性加熱素子の構成要素は、本開示に係る構造体の製造方法によって得られる構造体を含むことを除き、制限されない。上記構造体以外の構成要素としては、公知の導電性加熱素子に含まれる構成要素を利用することができる。導電性加熱素子については、例えば、特開特許第６４８６３８２号公報に記載されている。上記した公報は、参照により本明細書に取り込まれる。本開示に係る導電性加熱素子の製造方法は、本開示に係る構造体の製造方法によって得られる構造体を有する導電性加熱素子を製造する方法であれば制限されない。 <Conductive heating element>
The conductive heating element according to the present disclosure has a structure obtained by the method for producing the structure according to the present disclosure. In the conductive heating element according to the present disclosure, the conductive pattern of the structure can be used as a heating element, for example. The components of the conductive heating element according to the present disclosure are not limited except that the structure obtained by the method for producing the structure according to the present disclosure is included. As a component other than the above structure, a component included in a known conductive heating element can be used. The conductive heating element is described in, for example, Japanese Patent Application Laid-Open No. 6486382. The above publications are incorporated herein by reference. The method for manufacturing a conductive heating element according to the present disclosure is not limited as long as it is a method for manufacturing a conductive heating element having a structure obtained by the method for manufacturing a structure according to the present disclosure.
（構造体）
　本開示に係る構造体は、透明基材と、上記透明基材の上に配置された遮光性パターン１と、上記透明基材の上で上記遮光性パターン１に隣接して配置され、かつ、上記透明基材に接する樹脂パターン２と、上記遮光性パターン１と上記樹脂パターン２とによって画定される領域にパターン３とを有し、上記遮光性パターン１の平均厚さが、２μｍ以下であり、上記樹脂パターン２の平均厚さが、２μｍを超え、上記遮光性パターン１の平均厚さよりも上記パターン３の平均厚さのほうが厚く、上記樹脂パターン２を永久膜として有する。上記態様によれば、形態異常の発生が低減された導電性パターンを有する構造体が提供される。
　また、本開示に係る構造体は、本開示に係る構造体の製造方法により製造された構造体であることが好ましい。 (Structure)
The structure according to the present disclosure is arranged adjacent to the transparent base material, the light-shielding pattern 1 arranged on the transparent base material, and the light-shielding pattern 1 on the transparent base material, and It has a resin pattern 2 in contact with the transparent substrate, a pattern 3 in a region defined by the light-shielding pattern 1 and the resin pattern 2, and the average thickness of the light-shielding pattern 1 is 2 μm or less. The average thickness of the resin pattern 2 exceeds 2 μm, the average thickness of the pattern 3 is thicker than the average thickness of the light-shielding pattern 1, and the resin pattern 2 is a permanent film. According to the above aspect, a structure having a conductive pattern in which the occurrence of morphological abnormalities is reduced is provided.
Further, the structure according to the present disclosure is preferably a structure manufactured by the method for manufacturing the structure according to the present disclosure.
　本開示に係る構造体における透明基材、遮光性パターン１、樹脂パターン２、及び、パターン３における好ましい態様は、上記以外は、上述した本開示に係る構造体の製造方法における透明基材、遮光性パターン１、樹脂パターン２、及び、パターン３における好ましい態様と同様である。 Other than the above, preferred embodiments of the transparent base material, the light-shielding pattern 1, the resin pattern 2, and the pattern 3 in the structure according to the present disclosure are the transparent base material and the light-shielding material in the above-described method for producing the structure according to the present disclosure. This is the same as the preferred embodiment of the sex pattern 1, the resin pattern 2, and the pattern 3.
　本開示に係る構造体Ａについて図２を参照して説明する。図２は、本開示に係る構造体の一例を示す概略断面図である。図２に示される構造体２００は、透明基材１１と、パターン２１（遮光性パターン１）と、樹脂パターン４１（樹脂パターン２）と、パターン５１（パターン３）とを有する。遮光性パターン２１は、透明基材１１の上に配置されている。遮光性パターン２１は、透明基材１１に接している。ただし、遮光性パターン２１は、他の層（不図示）を介して透明基材１１に接してもよい。樹脂パターン４１は、透明基材１１の上で遮光性パターン２１の隣に配置され、かつ、透明基材１１に接している。また、パターン５１は、遮光性パターン２１上、かつ樹脂パターン４１の間に配置されている。 The structure A according to the present disclosure will be described with reference to FIG. FIG. 2 is a schematic cross-sectional view showing an example of the structure according to the present disclosure. The structure 200 shown in FIG. 2 has a transparent base material 11, a pattern 21 (light-shielding pattern 1), a resin pattern 41 (resin pattern 2), and a pattern 51 (pattern 3). The light-shielding pattern 21 is arranged on the transparent base material 11. The light-shielding pattern 21 is in contact with the transparent base material 11. However, the light-shielding pattern 21 may come into contact with the transparent base material 11 via another layer (not shown). The resin pattern 41 is arranged on the transparent base material 11 next to the light-shielding pattern 21 and is in contact with the transparent base material 11. Further, the pattern 51 is arranged on the light-shielding pattern 21 and between the resin patterns 41.
　以下、実施例により本開示を詳細に説明する。ただし、本開示は、以下の実施例に制限されるものではない。 Hereinafter, the present disclosure will be described in detail by way of examples. However, the present disclosure is not limited to the following examples.
＜アクリル酸テトラヒドロフラン－２－イル（ＡＴＨＦ）の合成＞
　３つ口フラスコにアクリル酸（７２．１ｇ、１．０ｍｏｌ）、ヘキサン（７２．１ｇ）を加え２０℃に冷却した。カンファースルホン酸（７．０ｍｇ、０．０３ｍｍｏｌ）、２－ジヒドロフラン（７７．９ｇ、１．０ｍｏｌ）を滴下した後に、２０℃±２℃で１．５時間撹拌した後、３５℃まで昇温して２時間撹拌した。ヌッチェにキョーワード２００（ろ過材、水酸化アルミニウム粉末、協和化学工業（株）製）、キョーワード１０００（ろ過材、ハイドロタルサイト系粉末、協和化学工業（株）製）の順に敷き詰めた後、反応液をろ過することでろ過液を得た。得られたろ過液にヒドロキノンモノメチルエーテル（ＭＥＨＱ、１．２ｍｇ）を加えた後、４０℃で減圧濃縮することで、アクリル酸テトラヒドロフラン－２－イル（ＡＴＨＦ）１４０．８ｇを無色油状物として得た（収率９９．０％）。 <Synthesis of tetrahydrofuran-2-yl (ATHF) acrylate>
Acrylic acid (72.1 g, 1.0 mol) and hexane (72.1 g) were added to the three-necked flask and cooled to 20 ° C. After adding camphorsulfonic acid (7.0 mg, 0.03 mmol) and 2-dihydrofuran (77.9 g, 1.0 mol), the mixture was stirred at 20 ° C. ± 2 ° C. for 1.5 hours and then heated to 35 ° C. And stirred for 2 hours. After laying Kyoward 200 (filter material, aluminum hydroxide powder, manufactured by Kyowa Chemical Industry Co., Ltd.) and Kyoward 1000 (filter material, hydrotalcite powder, manufactured by Kyowa Chemical Industry Co., Ltd.) on Nutche in this order, A filtered solution was obtained by filtering the reaction solution. Hydroquinone monomethyl ether (MEHQ, 1.2 mg) was added to the obtained filtrate and then concentrated under reduced pressure at 40 ° C. to obtain 140.8 g of tetrahydrofuran-2-yl acrylate (ATHF) as a colorless oil. (Yield 99.0%).
＜重合体Ａ－１の合成＞
　３つ口フラスコにＰＧＭＥＡ（７５．０ｇ）を入れ、窒素雰囲気下において９０℃に昇温した。ＡＴＨＦ（４０．０ｇ）、ＡＡ（２．０ｇ）、ＥＡ（２０．０ｇ）、ＭＭＡ（２２．０ｇ）、ＣＨＡ（１６．０ｇ）、Ｖ－６０１（４．０ｇ）、及びＰＧＭＥＡ（７５．０ｇ）を含む溶液を、９０℃±２℃に維持した３つ口フラスコ溶液中に２時間かけて滴下した。滴下終了後，９０℃±２℃にて２時間撹拌することで、重合体Ａ－１（固形分濃度４０．０質量％）を得た。重合体Ａ－１における各構成単位の含有量を表１に示す。重合体Ａ－１の酸価は、１５．６ｍｇＫＯＨ／ｇである。
　なお、上記略号はそれぞれ、以下の化合物を表す。
　「ＡＡ」：アクリル酸（東京化成工業（株）製）
　「ＣＨＡ」：アクリル酸シクロヘキシル（東京化成工業（株）製）
　「ＥＡ」：アクリル酸エチル（東京化成工業（株）製）
　「ＭＭＡ」：メタクリル酸メチル（東京化成工業（株）製）
　「ＰＧＭＥＡ」：プロピレングリコールモノメチルエーテルアセテート（昭和電工（株）製）
　「Ｖ－６０１」：２，２’－アゾビス（２－メチルプロピオン酸）ジメチル（富士フイルム和光純薬工業（株）製） <Synthesis of polymer A-1>
PGMEA (75.0 g) was placed in a three-necked flask, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. ATHF (40.0 g), AA (2.0 g), EA (20.0 g), MMA (22.0 g), CHA (16.0 g), V-601 (4.0 g), and PGMEA (75.0 g) ) Was added dropwise to a three-necked flask solution maintained at 90 ° C. ± 2 ° C. over 2 hours. After completion of the dropping, the mixture was stirred at 90 ° C. ± 2 ° C. for 2 hours to obtain polymer A-1 (solid content concentration: 40.0% by mass). Table 1 shows the content of each structural unit in the polymer A-1. The acid value of polymer A-1 is 15.6 mgKOH / g.
The above abbreviations represent the following compounds, respectively.
"AA": Acrylic acid (manufactured by Tokyo Chemical Industry Co., Ltd.)
"CHA": Cyclohexyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
"EA": Ethyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
"MMA": Methyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
"PGMEA": Propylene glycol monomethyl ether acetate (manufactured by Showa Denko KK)
"V-601": 2,2'-azobis (2-methylpropionate) dimethyl (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
＜重合体Ａ－２の合成＞
　下記に従ってモノマーの使用量を変更したこと以外は、重合体Ａ－１と同様の方法で重合体Ａ－２を含む溶液（固形分濃度：４０．０質量％）を得た。重合体Ａ－２の重量平均分子量は、６０，０００であった。
　（１）スチレン：５２．０ｇ
　（２）メタクリル酸：２９．０ｇ
　（３）メタクリル酸メチル：１９．０ｇ <Synthesis of polymer A-2>
A solution containing the polymer A-2 (solid content concentration: 40.0% by mass) was obtained in the same manner as the polymer A-1 except that the amount of the monomer used was changed according to the following. The weight average molecular weight of the polymer A-2 was 60,000.
(1) Styrene: 52.0 g
(2) Methacrylic acid: 29.0 g
(3) Methyl methacrylate: 19.0 g
＜重合体Ａ－３の合成＞
　重合体Ａ－１の合成で使用したモノマー（スチレン、メタクリル酸、及びメタクリル酸メチル）を下記のモノマーに変更したこと以外は、重合体Ａ－１と同様の方法で重合体Ａ－３を含む溶液（固形分濃度：４０．０質量％）を得た。重合体Ａ－３の重量平均分子量は、４０，０００であった。
　（１）メタクリル酸ベンジル：８１．０ｇ
　（２）メタクリル酸：１９．０ｇ <Synthesis of polymer A-3>
Polymer A-3 is contained in the same manner as in polymer A-1, except that the monomers (styrene, methacrylic acid, and methyl methacrylate) used in the synthesis of polymer A-1 are changed to the following monomers. A solution (solid content concentration: 40.0% by mass) was obtained. The weight average molecular weight of the polymer A-3 was 40,000.
(1) Benzyl methacrylate: 81.0 g
(2) Methacrylic acid: 19.0 g
＜ネガ型感光性樹脂組成物の調製＞
　表１の記載に従って選択した成分を混合した後、メチルエチルケトンを加えることによって、ネガ型感光性樹脂組成物ＮＲ１～ＮＲ６（固形分濃度：２５質量％）を調製した。 <Preparation of negative photosensitive resin composition>
After mixing the components selected according to the description in Table 1, negative type photosensitive resin compositions NR1 to NR6 (solid content concentration: 25% by mass) were prepared by adding methyl ethyl ketone.
Figure JPOXMLDOC01-appb-T000003
 
Figure JPOXMLDOC01-appb-T000003
 
　なお、表１における各成分欄の数値の単位は、質量部である。
　また、以下に、表１に記載の略号の詳細を示す。
　ＢＰＥ－５００：エトキシ化ビスフェノールＡジメタクリレート（エチレンオキサイド１０モル付加）、新中村化学工業（株）製
　ＢＰＥ－２００：エトキシ化ビスフェノールＡジメタクリレート（エチレンオキサイド４モル付加）、新中村化学工業（株）製
　Ｍ－２７０：ポリプロピレングリコールジアクリレート、東亞合成（株）製
　Ａ－ＴＭＰＴ：トリメチロールプロパントリアクリレート、新中村化学工業（株）製
　ＳＲ－４５４：エトキシ化トリメチロールプロパントリアクリレート（エチレンオキサイド３モル付加）、アルケマ社製
　ＳＲ－５０２：エトキシ化トリメチロールプロパントリアクリレート（エチレンオキサイド９モル付加）、アルケマ社製
　Ａ－９３００－ＣＬ１：ε－カプロラクトン変性トリス－（２－アクリロキシエチル）イソシアヌレート、新中村化学工業（株）製
　Ｂ－ＣＩＭ：光ラジカル発生剤（光重合開始剤）、Ｈａｍｐｆｏｒｄ社製、２－（２－クロロフェニル）－４，５－ジフェニルイミダゾール二量体
　ＳＢ－ＰＩ　７０１：増感剤、４，４’－ビス（ジエチルアミノ）ベンゾフェノン、三洋貿易（株）製
　ＣＢＴ－１：防錆剤、カルボキシベンゾトリアゾール、城北化学工業（株）製
　ＴＤＰ－Ｇ：重合禁止剤、フェノチアジン、川口化学工業（株）製
　Ｉｒｇａｎｏｘ２４５：重合禁止剤、ヒンダードフェノール系化合物、ＢＡＳＦ社製
　Ｆ－５５２：フッ素系界面活性剤、メガファック　Ｆ５５２、ＤＩＣ（株）製 The unit of the numerical value in each component column in Table 1 is a mass part.
The details of the abbreviations shown in Table 1 are shown below.
BPE-500: ethoxylated bisphenol A dimethacrylate (addition of 10 mol of ethylene oxide), manufactured by Shin-Nakamura Chemical Industry Co., Ltd. BPE-200: ethoxylated bisphenol A dimethacrylate (addition of 4 mol of ethylene oxide), Shin-Nakamura Chemical Industry Co., Ltd. M-270: Polypropylene glycol diacrylate, A-TMPT: Trimethylol propantriacrylate, SR-454: Trimethylol propantriacrylate ethoxylated (ethylene oxide 3) (Molar addition), SR-502 manufactured by Alchema: Trimethylol propantriacrylate ethoxylated (addition of 9 mol of ethylene oxide), A-9300-CL1: ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate manufactured by Alchema , Shin-Nakamura Chemical Industry Co., Ltd. B-CIM: Photoradical generator (photopolymerization initiator), Hampford, 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer SB-PI 701: Sensitizer, 4,4'-bis (diethylamino) benzophenone, manufactured by Sanyo Trading Co., Ltd. CBT-1: rust preventive, carboxybenzotriazole, manufactured by Johoku Chemical Industry Co., Ltd. TDP-G: polymerization inhibitor, phenothiazine, Irganox 245 manufactured by Kawaguchi Chemical Industry Co., Ltd .: polymerization inhibitor, hindered phenol compound, F-552 manufactured by BASF, fluorosurfactant, Megafuck F552, manufactured by DIC Co., Ltd.
＜ポジ型感光性樹脂組成物ＰＲ１の調製＞
　下記表２に示す組成に従って秤量した重合体Ａ－１、光酸発生剤Ｂ－１、界面活性剤Ｃ－１及び塩基性化合物Ｄ－１と、ＰＧＭＥＡと、を混合することによって、固形分濃度１０質量％の混合物を得た。孔径０．２μｍのポリテトラフルオロエチレン製フィルターを用いて、上記混合物をろ過することによって、ポジ型感光性樹脂組成物ＰＲ１を得た。 <Preparation of positive photosensitive resin composition PR1>
By mixing PGMEA with polymer A-1, photoacid generator B-1, surfactant C-1, and basic compound D-1, weighed according to the composition shown in Table 2 below, the solid content concentration A 10% by mass mixture was obtained. The above mixture was filtered using a filter made of polytetrafluoroethylene having a pore size of 0.2 μm to obtain a positive photosensitive resin composition PR1.
Figure JPOXMLDOC01-appb-T000004
 
Figure JPOXMLDOC01-appb-T000004
 
　なお、表２における各成分欄の数値の単位は、質量部である。
　また、以下に、表２に記載の上述した以外の各成分の詳細を示す。 The unit of the numerical value in each component column in Table 2 is a mass part.
In addition, the details of each component other than those described above shown in Table 2 are shown below.
　光酸発生剤Ｂ－１は、下記構造を有する化合物（特開２０１３－４７７６５号公報の段落０２２７に記載の化合物、段落０２２７に記載の方法に従って合成した。）である。 The photoacid generator B-1 is a compound having the following structure (the compound described in paragraph 0227 of JP2013-47765A, synthesized according to the method described in paragraph 0227).
Figure JPOXMLDOC01-appb-C000005
 
Figure JPOXMLDOC01-appb-C000005
 
　界面活性剤Ｃ－１は、下記構造を有する化合物である。 Surfactant C-1 is a compound having the following structure.
Figure JPOXMLDOC01-appb-C000006
 
Figure JPOXMLDOC01-appb-C000006
 
　塩基性化合物Ｄ－１は、下記構造を有する化合物である。 Basic compound D-1 is a compound having the following structure.
Figure JPOXMLDOC01-appb-C000007
 
Figure JPOXMLDOC01-appb-C000007
 
＜ネガ型感光性樹脂組成物Ｎ１～Ｎ８の調製＞
　表３又は表４の記載に従って選択した成分を混合した後、１－メトキシ－２－プロピルアセテートとメチルエチルケトンの１：１（質量比）混合溶剤を加えることによって、ネガ型感光性樹脂組成物Ｎ１～Ｎ８（固形分濃度：２９質量％）を調製した。 <Preparation of Negative Photosensitive Resin Compositions N1 to N8>
After mixing the components selected according to the description in Table 3 or Table 4, the negative photosensitive resin compositions N1 to are added by adding a 1: 1 (mass ratio) mixed solvent of 1-methoxy-2-propyl acetate and methyl ethyl ketone. N8 (solid content concentration: 29% by mass) was prepared.
Figure JPOXMLDOC01-appb-T000008
 
Figure JPOXMLDOC01-appb-T000008
 
Figure JPOXMLDOC01-appb-T000009
 
Figure JPOXMLDOC01-appb-T000009
 
　なお、表３及び表４における各成分の含有量の数値の単位は、質量部である。
　また、以下に、表３に記載の各成分の詳細を示す。
－エチレン性不飽和化合物－
　Ｍ－１：Ａ－ＮＯＤ－Ｎ（１，９－ノナンジオールジアクリレート、新中村化学工業（株）製）
　Ｍ－２：ジペンタエリスリトールヘキサアクリレート（Ａ－ＤＰＨ、新中村化学工業（株）製）
　Ｍ－３：Ａ－ＤＣＰ（トリシクロデカンジメタノールジアクリレート、新中村化学工業（株）製）
　Ｍ－４：アロニックス　ＴＯ－２３４９（カルボン酸基を有する多官能エチレン性不飽和化合物、東亞合成（株）製）
　Ｍ－５：ウレタンアクリレート８ＵＸ－０１５Ａ（大成ファインケミカル（株）製） The unit of the numerical value of the content of each component in Tables 3 and 4 is the mass part.
In addition, the details of each component shown in Table 3 are shown below.
-Ethylene unsaturated compound-
M-1: A-NOD-N (1,9-nonanediol diacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
M-2: Dipentaerythritol hexaacrylate (A-DPH, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
M-3: A-DCP (tricyclodecanedimethanol diacrylate, manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
M-4: Aronix TO-2349 (polyfunctional ethylenically unsaturated compound having a carboxylic acid group, manufactured by Toagosei Co., Ltd.)
M-5: Urethane acrylate 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.)
－アルカリ可溶性高分子－
　Ｐ－１：下記に示す樹脂、スチレン由来の構成単位（Ｓｔ）／ジシクロペンタニルメタクリレート由来の構成単位（ＤＣＰＭＡ）／メタクリル酸由来の構成単位（ＭＡＡ）／メタクリル酸由来の構成単位にグリシジルメタクリレートを付加してなる構成単位（ＧＭＡ－ＭＡＡ）＝４１．０／１５．２／２３．９／１９．９（ｍｏｌ％）、Ｍｗ＝１７，０００） -Alkali-soluble polymer-
P-1: The following resin, styrene-derived structural unit (St) / dicyclopentanyl methacrylate-derived structural unit (DCPMA) / methacrylic acid-derived structural unit (MAA) / methacrylic acid-derived structural unit glycidyl methacrylate (GMA-MAA) = 41.0 / 15.2 / 23.9 / 19.9 (mol%), Mw = 17,000)
－光重合開始剤－
　Ｄ－１：１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］エタノン－１－（Ｏ－アセチルオキシム）（Ｉｒｇａｃｕｒｅ　ＯＸＥ－０２、ＢＡＳＦ社製）
　Ｄ－２：２－メチル－１－（４－メチルチオフェニル）－２－モルフォリノプロパン－１－オン（Ｉｒｇａｃｕｒｅ　９０７、ＢＡＳＦ社製）
　Ｄ－３：Ｂ－ＣＩＭ（光ラジカル発生剤（光重合開始剤）、Ｈａｍｐｆｏｒｄ社製、２－（２－クロロフェニル）－４，５－ジフェニルイミダゾール二量体）：０．８９質量部 -Photopolymerization initiator-
D-1: 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] ethanone-1- (O-acetyloxime) (Irgacure OXE-02, manufactured by BASF)
D-2: 2-Methyl-1- (4-Methylthiophenyl) -2-morpholinopropane-1-one (Irgacure 907, manufactured by BASF)
D-3: B-CIM (photoradical generator (photopolymerization initiator), manufactured by Hampford, 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer): 0.89 parts by mass
－熱架橋性化合物－
　Ｅ－１：デュラネートＷＴ３２－Ｂ７５Ｐ（ブロックイソシアネート化合物、旭化成ケミカルズ（株）製）：１２．５０部 -Thermal crosslinkable compound-
E-1: Duranate WT32-B75P (blocked isocyanate compound, manufactured by Asahi Kasei Chemicals Co., Ltd.): 12.50 parts
－その他の成分－
　ＡＤ－１：水素供与性化合物（Ｎ－フェニルグリシン、純正化学（株）製）
　ＡＤ－２：スチレン／無水マレイン酸＝４：１（モル比）の共重合体（ＡＤ－２、ＳＭＡ　ＥＦ－４０、酸無水物価１．９４ｍｍｏｌ／ｇ、重量平均分子量１０，５００、Ｃｒａｙ　Ｖａｌｌｅｙ社製）
　ＡＤ－３：フッ素系界面活性剤（メガファック　Ｆ５５１Ａ、ＤＩＣ（株）製）
　ＡＤ－４：増感剤（４，４’－ビス（ジエチルアミノ）ベンゾフェノン、ＳＢ－ＰＩ　７０１、三洋貿易（株）製）
　ＡＤ－５：色素（ロイコクリスタルバイオレット、山田化学工業（株）製）
　ＡＤ－６：重合禁止剤（フェノチアジン、川口化学工業（株）製ＴＤＰ－Ｇ）
　ＡＤ－７：防錆剤（カルボキシベンゾトリアゾール、城北化学工業（株）製ＣＢＴ－１）
　ＡＤ－８：フッ素系界面活性剤（メガファック　Ｆ５５２、ＤＩＣ（株）製） -Other ingredients-
AD-1: Hydrogen donating compound (N-phenylglycine, manufactured by Junsei Chemical Co., Ltd.)
AD-2: Styrene / maleic anhydride = 4: 1 (molar ratio) copolymer (AD-2, SMA EF-40, acid anhydride price 1.94 mmol / g, weight average molecular weight 10,500, Cray Valley) Made)
AD-3: Fluorosurfactant (Mega Fvck F551A, manufactured by DIC Corporation)
AD-4: Sensitizer (4,5'-bis (diethylamino) benzophenone, SB-PI 701, manufactured by Sanyo Trading Co., Ltd.)
AD-5: Dye (Leuko Crystal Violet, manufactured by Yamada Chemical Co., Ltd.)
AD-6: Polymerization inhibitor (phenothiazine, TDP-G manufactured by Kawaguchi Chemical Industry Co., Ltd.)
AD-7: Rust inhibitor (carboxybenzotriazole, CBT-1 manufactured by Johoku Chemical Industry Co., Ltd.)
AD-8: Fluorine-based surfactant (Mega Fvck F552, manufactured by DIC Corporation)
（実施例１）
＜感光性転写材料（ドライフィルム）１の作製＞
　仮支持体としてＰＥＴフィルム（東レ（株）製ルミラー１６ＫＳ４０、厚さ：１６μｍ：算術平均粗さＲａ：０．０２μｍ）を用意した。仮支持体の表面に、スリット状ノズルを用いて塗布幅が１．０ｍであり、かつ、乾燥後の厚さが表５に記載された値となるようにネガ型感光性樹脂組成物ＮＲ１を塗布した。形成されたネガ型感光性樹脂組成物ＮＲ１の塗膜を９０℃で１００秒間かけて乾燥することで、レジスト層を形成した。形成されたレジスト層の表面に、カバーフィルムとしてポリエチレンフィルム（タマポリ（株）、ＧＦ－８１８、厚さ：１９μｍ）を圧着することで、感光性転写材料１を作製した。得られた感光性転写材料１を巻き取ることで、ロール形態の感光性転写材料１を作製した。 (Example 1)
<Preparation of photosensitive transfer material (dry film) 1>
As a temporary support, a PET film (Lumirror 16KS40 manufactured by Toray Industries, Inc., thickness: 16 μm: arithmetic average roughness Ra: 0.02 μm) was prepared. A negative photosensitive resin composition NR1 was applied to the surface of the temporary support using a slit-shaped nozzle so that the coating width was 1.0 m and the thickness after drying was the value shown in Table 5. It was applied. A resist layer was formed by drying the coating film of the formed negative photosensitive resin composition NR1 at 90 ° C. for 100 seconds. A photosensitive transfer material 1 was prepared by pressure-bonding a polyethylene film (Tamapoli Co., Ltd., GF-818, thickness: 19 μm) as a cover film on the surface of the formed resist layer. By winding the obtained photosensitive transfer material 1, a roll-shaped photosensitive transfer material 1 was produced.
＜遮光性パターン１（銅パターン）の形成＞
　厚さが１００μｍのポリエチレンテレフタレート（ＰＥＴ）フィルムの上に、厚さが０．０５μｍの銅層をスパッタリングによって形成することで、銅層付きＰＥＴフィルムを作製した。感光性転写材料１からカバーフィルムを剥離した後、銅層付きＰＥＴフィルムに感光性転写材料１を貼り合わせた。貼り合わせ工程は、ロール温度を１００℃、線圧を１．０ＭＰａ、線速度を１．０ｍ／分とする条件で行った。次いで、フォトマスクを介して高圧水銀灯露光機（（株）大日本科研製ＭＡＰ－１２００Ｌ、主波長：３６５ｎｍ）を用いて光を照射して、レジスト層を露光した。仮支持体を剥離した後、レジスト層を、液温が２５℃の炭酸ナトリウム水溶液を用いて３０秒間のシャワー現像をすることによって樹脂パターン（ライン／スペース＝５．５μｍ／４．５μｍ）を形成した。エッチング液（関東化学（株）製Ｃｕ－０２）を用いて、樹脂パターンで覆われていない銅層をエッチングした。剥離液（１０質量％水酸化ナトリウム水溶液）を用いて、残存する樹脂パターンを除去した。以上の手順によって、銅パターン（ライン／スペース＝５μｍ／５μｍ）付きＰＥＴフィルムを作製した。銅パターンは、遮光性パターン１として機能する。遮光性パターン１の平均厚さを表５に示す。 <Formation of light-shielding pattern 1 (copper pattern)>
A PET film with a copper layer was produced by forming a copper layer having a thickness of 0.05 μm on a polyethylene terephthalate (PET) film having a thickness of 100 μm by sputtering. After peeling the cover film from the photosensitive transfer material 1, the photosensitive transfer material 1 was attached to the PET film with a copper layer. The bonding step was performed under the conditions that the roll temperature was 100 ° C., the linear pressure was 1.0 MPa, and the linear velocity was 1.0 m / min. Next, the resist layer was exposed by irradiating light with a high-pressure mercury lamp exposure machine (MAP-1200L manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm) via a photomask. After peeling off the temporary support, the resist layer is shower-developed for 30 seconds with an aqueous sodium carbonate solution having a liquid temperature of 25 ° C. to form a resin pattern (line / space = 5.5 μm / 4.5 μm). bottom. The copper layer not covered with the resin pattern was etched with an etching solution (Cu-02 manufactured by Kanto Chemical Co., Inc.). The residual resin pattern was removed using a stripping solution (10 mass% sodium hydroxide aqueous solution). By the above procedure, a PET film with a copper pattern (line / space = 5 μm / 5 μm) was produced. The copper pattern functions as the light-shielding pattern 1. Table 5 shows the average thickness of the light-shielding pattern 1.
＜感光性転写材料２の作製＞
　仮支持体としてＰＥＴフィルム（東レ（株）製ルミラー１６ＫＳ４０、厚さ：１６μｍ：算術平均粗さＲａ：０．０２μｍ）を用意した。仮支持体の表面に、スリット状ノズルを用いて塗布幅が１．０ｍであり、かつ、乾燥後の厚さが表５に記載された値となるようにネガ型感光性樹脂組成物Ｎ１を塗布した。形成されたネガ型感光性樹脂組成物Ｎ１の塗膜を９０℃で１００秒間かけて乾燥した。 <Preparation of photosensitive transfer material 2>
As a temporary support, a PET film (Lumirror 16KS40 manufactured by Toray Industries, Inc., thickness: 16 μm: arithmetic average roughness Ra: 0.02 μm) was prepared. A negative photosensitive resin composition N1 was applied to the surface of the temporary support using a slit-shaped nozzle so that the coating width was 1.0 m and the thickness after drying was the value shown in Table 5. It was applied. The coating film of the formed negative photosensitive resin composition N1 was dried at 90 ° C. for 100 seconds.
　その後、カバーフィルムとしてポリエチレンフィルム（タマポリ（株）、ＧＦ－８１８、厚さ：１９μｍ）を圧着することで、感光性転写材料２を作製した。得られた感光性転写材料２を巻き取ることで、ロール形態の感光性転写材料２を作製した。 After that, a polyethylene film (Tamapoli Co., Ltd., GF-818, thickness: 19 μm) was pressure-bonded as a cover film to prepare a photosensitive transfer material 2. By winding up the obtained photosensitive transfer material 2, a roll-shaped photosensitive transfer material 2 was produced.
＜パターン３（銅パターン）の形成＞
　感光性転写材料２からカバーフィルムを剥離した後、銅パターン付きＰＥＴフィルムと感光性転写材料２とを貼り合わせた。貼り合わせ工程は、ロール温度を１００℃、線圧を１．０ＭＰａ、線速度を１．０ｍ／分とする条件で行った。得られた積層体は、ＰＥＴフィルム、銅パターン（遮光性パターン１）、ネガ型感光性樹脂層Ｎ、及び仮支持体をこの順で有する。ＰＥＴフィルムの銅パターン（遮光性パターン１）に対向する面とは反対側の面に対して高圧水銀灯露光機（（株）大日本科研製ＭＡＰ－１２００Ｌ、主波長：３６５ｎｍ）を用いて光を照射した。露光量は７０ｍＪ／ｃｍ２とした。仮支持体を剥離した後、ネガ型感光性樹脂層Ｎを液温が２５℃の炭酸ナトリウム水溶液を用いて３０秒間のシャワー現像をすることによって、樹脂パターン２を形成した。銅パターン（遮光性パターン１）のスペース部（すなわち、溝）は、樹脂パターン２によって埋められた。樹脂パターン２の平均厚さを表２に示す。樹脂パターン２によって覆われていない銅パターン（遮光性パターン１）の上に、電気銅めっきにより銅を析出させ、導電性を有するパターン３を形成した。電気銅めっきにおける電流密度は、１．８ＡＳＤであった。電気銅めっきにおける処理時間は、６分間であった。電気銅めっき後のＰＥＴフィルムを１３０℃で３０分間加熱した。以上の手順によって、銅パターン（ライン（Ｌ）／スペース（Ｓ）＝５μｍ／５μｍ）を有する構造体を作製した。電気銅めっきにより析出した銅パターン（導電性を有するパターン３）の平均厚さを表５に示す。 <Formation of pattern 3 (copper pattern)>
After peeling the cover film from the photosensitive transfer material 2, the PET film with a copper pattern and the photosensitive transfer material 2 were bonded together. The bonding step was performed under the conditions that the roll temperature was 100 ° C., the linear pressure was 1.0 MPa, and the linear velocity was 1.0 m / min. The obtained laminate has a PET film, a copper pattern (light-shielding pattern 1), a negative photosensitive resin layer N, and a temporary support in this order. Light is emitted to the surface of the PET film opposite to the surface facing the copper pattern (light-shielding pattern 1) using a high-pressure mercury lamp exposure machine (MAP-1200L manufactured by Dainippon Kaken Co., Ltd., main wavelength: 365 nm). Irradiated. The exposure amount was 70 mJ / cm 2 . After peeling off the temporary support, the negative type photosensitive resin layer N was shower-developed for 30 seconds with an aqueous sodium carbonate solution having a liquid temperature of 25 ° C. to form a resin pattern 2. The space portion (that is, the groove) of the copper pattern (light-shielding pattern 1) was filled with the resin pattern 2. Table 2 shows the average thickness of the resin pattern 2. Copper was deposited by electrolytic copper plating on a copper pattern (light-shielding pattern 1) not covered by the resin pattern 2 to form a conductive pattern 3. The current density in electrolytic copper plating was 1.8 ASD. The processing time in electrolytic copper plating was 6 minutes. The PET film after electrolytic copper plating was heated at 130 ° C. for 30 minutes. By the above procedure, a structure having a copper pattern (line (L) / space (S) = 5 μm / 5 μm) was produced. Table 5 shows the average thickness of the copper pattern (conducting pattern 3) precipitated by electrolytic copper plating.
（実施例２～１３）
　基材の種類及び厚み、遮光性パターン１の厚み（平均厚さ）、遮光性パターン１を形成する感光性樹脂組成物の種類、感光性樹脂組成物の乾燥塗布厚（レジスト層の厚み）、遮光性パターン１の形状、感光性パターン１を形成時の露光方法（仮支持体の剥離の有無を含む）、ネガ型感光性樹脂層Ｎの形成方法及び使用したネガ型感光性組成物、その他の層の種類、パターン３の厚み（平均厚さ）、並びに、硬化処理の有無を表５の記載に従って適宜変更したこと以外は、実施例１と同様の手順によって、銅パターンを有する構造体を作製した。電気銅めっきによって析出させる銅の平均厚さは、処理時間を延ばすことで大きくすることができる。 (Examples 2 to 13)
Type and thickness of base material, thickness of light-shielding pattern 1 (average thickness), type of photosensitive resin composition forming light-shielding pattern 1, dry coating thickness of photosensitive resin composition (thickness of resist layer), The shape of the light-shielding pattern 1, the exposure method at the time of forming the photosensitive pattern 1 (including the presence or absence of peeling of the temporary support), the method of forming the negative photosensitive resin layer N, the negative photosensitive composition used, and the like. A structure having a copper pattern was prepared by the same procedure as in Example 1 except that the type of the layer, the thickness (average thickness) of the pattern 3, and the presence or absence of the curing treatment were appropriately changed according to the description in Table 5. Made. The average thickness of copper deposited by electrolytic copper plating can be increased by extending the treatment time.
　なお、実施例２においては、使用する基材として、厚さ１００μｍのポリイミド（ＰＩ）フィルムを使用し、更に、パターン３を形成後、高圧水銀灯露光機（（株）大日本科研製ＭＡＰ－１２００Ｌ、主波長：３６５ｎｍ）を用いて１，０００ｍＪ／ｃｍ２の露光量の光を照射して後露光を行った。 In Example 2, a polyimide (PI) film having a thickness of 100 μm was used as the base material to be used, and after pattern 3 was formed, a high-pressure mercury lamp exposure machine (MAP-1200L manufactured by Dainippon Kaken Co., Ltd.) was used. , Main wavelength: 365 nm) was used to irradiate light with an exposure amount of 1,000 mJ / cm 2 to perform post-exposure.
　実施例３においては、使用する基材として、厚さ１００μｍのポリシクロオレフィン（ＣＯＰ）フィルム上に、厚さ０．１μｍの酸化インジウムスズ（ＩＴＯ）膜がスパッタ法で形成された基材（ＣＯＰ／ＩＴＯ）上に、厚さ０．０３μｍの銅層をスパッタ法で形成することにより、銅層付きの基材を準備した。
　また、実施例３では、ネガ型感光性樹脂組成物Ｎ１の代わりに、以下のネガ型感光性樹脂組成物Ｎ１上に、高屈折率層を積層したＮ１０を形成した。
　仮支持体としてＰＥＴフィルム（東レ（株）製ルミラー１６ＫＳ４０、厚さ：１６μｍ：算術平均粗さＲａ：０．０２μｍ）を用意した。仮支持体の表面に、スリット状ノズルを用いて塗布幅が１．０ｍであり、かつ、乾燥後の厚さが３μｍとなるようにネガ型感光性樹脂組成物Ｎ１を塗布した。形成されたネガ型感光性樹脂組成物Ｎ１の塗膜を９０℃で１００秒間かけて乾燥することで、ネガ型感光性樹脂層Ｎを形成した。
　次に、上記のネガ型感光性樹脂層Ｎ上に、スリット状ノズルを用いて、下記の処方２０１からなるオーバーコート層用塗布液（組成物Ｎ９）を、乾燥後の厚みが０．２μｍの厚みになるように調整して塗布し、４０℃から９５℃の温度勾配をもつ熱風対流式乾燥機で乾燥して溶剤を除去し、感光性層に直接接して配置されたオーバーコート層（ＯＣ層）を形成した。オーバーコート層の屈折率は、２５℃において波長５５０ｎｍで１．６８であった。
　ここで、処方２０１は、酸基を有する樹脂と、アンモニア水溶液を用いて調製しており、酸基を有する樹脂はアンモニア水溶液で中和され、酸基を有する樹脂のアンモニウム塩を含む水系樹脂組成物であるオーバーコート層用塗布液を調製した。 In Example 3, as the base material to be used, a base material (COP) in which an indium tin oxide (ITO) film having a thickness of 0.1 μm is formed by a sputtering method on a polycycloolefin (COP) film having a thickness of 100 μm. A base material with a copper layer was prepared by forming a copper layer having a thickness of 0.03 μm on / ITO) by a sputtering method.
Further, in Example 3, instead of the negative photosensitive resin composition N1, N10 in which a high refractive index layer was laminated was formed on the following negative photosensitive resin composition N1.
As a temporary support, a PET film (Lumirror 16KS40 manufactured by Toray Industries, Inc., thickness: 16 μm: arithmetic average roughness Ra: 0.02 μm) was prepared. The negative photosensitive resin composition N1 was applied to the surface of the temporary support using a slit-shaped nozzle so that the coating width was 1.0 m and the thickness after drying was 3 μm. The negative-type photosensitive resin layer N was formed by drying the coating film of the formed negative-type photosensitive resin composition N1 at 90 ° C. for 100 seconds.
Next, on the negative photosensitive resin layer N described above, a coating liquid (composition N9) for an overcoat layer composed of the following formulation 201 was applied using a slit-shaped nozzle to a thickness of 0.2 μm after drying. The overcoat layer (OC) is arranged so that it has a thickness, is applied, dried with a hot air convection dryer having a temperature gradient of 40 ° C. to 95 ° C. to remove the solvent, and is arranged in direct contact with the photosensitive layer. Layer) was formed. The refractive index of the overcoat layer was 1.68 at a wavelength of 550 nm at 25 ° C.
Here, Formulation 201 is prepared using a resin having an acid group and an aqueous ammonia solution. The resin having an acid group is neutralized with the aqueous ammonia solution, and an aqueous resin composition containing an ammonium salt of the resin having an acid group. A coating solution for the overcoat layer, which is a product, was prepared.
－オーバーコート用塗布液：処方２０１（水系樹脂組成物）－
・アクリル樹脂（ＺＢ－０１５Ｍ、富士フイルムファインケミカル（株）製、メタクリル酸／メタクリル酸アリルの共重合樹脂、重量平均分子量２．５万、組成比（モル比）＝２０／８０、固形分５．００％、アンモニア水溶液）：４．９２部
・カルボン酸基を有する多官能エチレン性不飽和化合物（アロニックス　ＴＯ－２３４９、東亞合成（株）製）：０．０４部
・ＺｒＯ２粒子（ナノユースＯＺ－Ｓ３０Ｍ、固形分３０．５％、メタノール６９．５％、屈折率が２．２、平均粒径：約１２ｎｍ、日産化学工業（株）製）：４．３４部
・防錆剤（ベンゾトリアゾール誘導体、ＢＴ－ＬＸ、城北化学工業（株）製）：０．０３部
・界面活性剤（フッ素系界面活性剤、メガファックＦ４４４、ＤＩＣ（株）製）：０．０１部
・蒸留水：２４．８３部
・メタノール：６５．８３部 -Coating liquid for overcoating: Formulation 201 (water-based resin composition)-
Acrylic resin (ZB-015M, manufactured by Fujifilm Fine Chemicals Co., Ltd., methacrylic acid / allyl methacrylate copolymer resin, weight average molecular weight 25,000, composition ratio (molar ratio) = 20/80, solid content 5. 00%, aqueous ammonia): 4.92 parts, polyfunctional ethylenically unsaturated compound having a carboxylic acid group (Aronix TO-2349, manufactured by Toa Synthetic Co., Ltd.): 0.04 parts, ZrO 2 particles (Nano Youth OZ- S30M, solid content 30.5%, methanol 69.5%, refractive acid 2.2, average particle size: about 12 nm, manufactured by Nissan Chemical Industry Co., Ltd .: 4.34 parts, rust preventive (benzotriazole derivative) , BT-LX, manufactured by Johoku Chemical Industry Co., Ltd.): 0.03 parts ・ Surfactant (fluorine-based surfactant, Megafuck F444, manufactured by DIC Co., Ltd.): 0.01 parts ・ Distilled water: 24. 83 parts, methanol: 65.83 parts
　形成されたオーバーコート層の表面に、カバーフィルムとしてポリエチレンフィルム（タマポリ（株）製、ＧＦ－８１８、厚さ：１９μｍ）を圧着することで、感光性転写材料２を作製した。得られた感光性転写材料２を巻き取ることで、ロール形態の感光性転写材料２を作製した。 A photosensitive transfer material 2 was prepared by pressure-bonding a polyethylene film (manufactured by Tamapoli Co., Ltd., GF-818, thickness: 19 μm) as a cover film on the surface of the formed overcoat layer. By winding up the obtained photosensitive transfer material 2, a roll-shaped photosensitive transfer material 2 was produced.
　また、実施例４においては、直接描画式露光装置（ビアメカニクス（株）製、ＤＥ－１ＤＨ、主波長４０５ｎｍ）を用いて直接描画式露光（ＤＩ露光）方法により露光した。
　更に、実施例７においては、感光転写材料をラミネートした基材を、４インチシリコンウエハー上にテープで固定した後、（株）ニコン製ｉ線ステッパー（ＮＳＲ－２００９ｉ９Ｃ）を用いて、縮小投影露光を行い、更に、パターン３を形成後、１４５℃で２０分間加熱を行った。
　また、実施例９及び１０においては、感光性転写材料１を用いず、表５に記載のポジ型感光性樹脂組成物ＰＲ１を塗布し、９０℃で１００秒間かけて乾燥し、表５に記載の厚さのレジスト層を形成した。
　更に、実施例８及び１１においては、感光性転写材料２を用いず、表５に記載のネガ型感光性樹脂組成物を塗布し、９０℃で１００秒間かけて乾燥し、表５に記載の厚さのネガ型感光性樹脂層Ｎを形成した。 Further, in Example 4, exposure was performed by a direct drawing exposure (DI exposure) method using a direct drawing exposure apparatus (manufactured by Via Mechanics, Ltd., DE-1DH, main wavelength 405 nm).
Further, in Example 7, a base material laminated with a photosensitive transfer material is fixed on a 4-inch silicon wafer with a tape, and then reduced projection exposure is performed using an i-wire stepper (NSR-2009i9C) manufactured by Nikon Corporation. After forming the pattern 3, heating was performed at 145 ° C. for 20 minutes.
Further, in Examples 9 and 10, the positive photosensitive resin composition PR1 shown in Table 5 was applied without using the photosensitive transfer material 1, dried at 90 ° C. for 100 seconds, and shown in Table 5. A resist layer having the same thickness was formed.
Further, in Examples 8 and 11, the negative photosensitive resin composition shown in Table 5 was applied without using the photosensitive transfer material 2, dried at 90 ° C. for 100 seconds, and shown in Table 5. A negative photosensitive resin layer N having a thickness was formed.
　実施例１２においては、遮光性パターン１を、下記のように形成した。
　ＰＥＴフィルム（東洋紡（株）製コスモシャインＡ４３００、厚さ：７５μｍ）を用意した。モノクロインクジェットプリンターＰＸ－Ｋ１００（セイコーエプソン（株）製）のインクカートリッジ中のインクを銀ナノインク（（株）Ｃ－ＩＮＫ製ＤｒｙＣｕｒｅ　Ａｇ－Ｊ）に移し替えたプリンターを用意した。このプリンターに対し、プリンタドライバーを介した印刷操作を行うことにより、配線パターンを形成した後、６０℃２分間加熱した。銀配線パターン（ライン／スペース＝５０μｍ／５０μｍ）付きＰＥＴフィルムを作製した。
　また、樹脂パターン２を形成後、下記のように銅パターン３を形成した。
　無電解銅めっき液（奥野製薬工業（株）製ＡＲＧカッパー）を取扱説明書に記載の手順に従い、Ｃｕめっき浴を作製した後、４５℃の恒温槽に入れて温調した。めっき浴に、基板を含浸させることにより、無電解めっきにより、銅パターンを形成した。 In Example 12, the light-shielding pattern 1 was formed as follows.
A PET film (Cosmo Shine A4300 manufactured by Toyobo Co., Ltd., thickness: 75 μm) was prepared. A printer was prepared in which the ink in the ink cartridge of the monochrome inkjet printer PX-K100 (manufactured by Seiko Epson Corporation) was transferred to silver nano ink (DryCure Ag-J manufactured by C-INK Co., Ltd.). A wiring pattern was formed by performing a printing operation on this printer via a printer driver, and then the printer was heated at 60 ° C. for 2 minutes. A PET film with a silver wiring pattern (line / space = 50 μm / 50 μm) was produced.
Further, after forming the resin pattern 2, the copper pattern 3 was formed as shown below.
An electroless copper plating solution (ARG copper manufactured by Okuno Pharmaceutical Industry Co., Ltd.) was prepared in a Cu plating bath according to the procedure described in the instruction manual, and then placed in a constant temperature bath at 45 ° C. for temperature control. A copper pattern was formed by electroless plating by impregnating the plating bath with a substrate.
　実施例１３においては、遮光性パターン１を、下記のように形成した。
　厚さが１００μｍのポリイミド（ＰＩ）フィルムに、感光性転写材料１からカバーフィルムを剥離した後、銅層付きＰＥＴフィルムに感光性転写材料１を貼り合わせた。上記貼り合わせは、ロール温度を１００℃、線圧を１．０ＭＰａ、線速度を１．０ｍ／分とする条件で行った。次いで、マスクレス描画装置（ハイデルベルグ社製ＤＷＬ６６＋、主波長：４０５ｎｍ）を用いて光を照射して、レジスト層を露光した。仮支持体を剥離した後、レジスト層を、液温が２５℃の炭酸ナトリウム水溶液を用いて３０秒間のシャワー現像をすることによって樹脂パターン（ライン／スペース＝１５μｍ／１５μｍ）を形成した。次いで、スパッタリングによってレジストパターン間と、レジストパターン上に銅層を形成した後、剥離液（１０質量％トリエチルアミン水溶液）を用いて、樹脂パターン及び樹脂パターン上の銅層を除去した。以上の手順によって、銅パターン（ライン／スペース＝１５μｍ／１５μｍ）付きＰＩフィルムを作製した。銅パターンは、遮光性パターン１として機能する。
　また、その他の操作については、樹脂パターン２の現像において、現像液として、２．３８質量％水酸化テトラメチルアンモニウム（ＴＭＡＨ）水溶液を使用した以外は、実施例１と同様にして行った。 In Example 13, the light-shielding pattern 1 was formed as follows.
After peeling the cover film from the photosensitive transfer material 1 on a polyimide (PI) film having a thickness of 100 μm, the photosensitive transfer material 1 was attached to a PET film with a copper layer. The above bonding was performed under the conditions that the roll temperature was 100 ° C., the linear pressure was 1.0 MPa, and the linear velocity was 1.0 m / min. Next, the resist layer was exposed by irradiating light with a maskless drawing apparatus (DWL66 + manufactured by Heidelberg, main wavelength: 405 nm). After peeling off the temporary support, the resist layer was shower-developed for 30 seconds with an aqueous sodium carbonate solution having a liquid temperature of 25 ° C. to form a resin pattern (line / space = 15 μm / 15 μm). Next, after forming a copper layer between the resist patterns and on the resist pattern by sputtering, the resin pattern and the copper layer on the resin pattern were removed using a stripping solution (10 mass% triethylamine aqueous solution). By the above procedure, a PI film with a copper pattern (line / space = 15 μm / 15 μm) was produced. The copper pattern functions as the light-shielding pattern 1.
Other operations were carried out in the same manner as in Example 1 except that a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution was used as the developing solution in the development of the resin pattern 2.
（比較例１）
　「パターン３（銅パターン）の形成」の項で説明した工程において、光の照射方法を変更したこと以外は、実施例１と同様の手順によって、銅パターンを有する構造体の作製を試みた。具体的に、ＰＥＴフィルム、銅パターン（遮光性パターン）、ネガ型感光性樹脂層Ｎ、及び仮支持体をこの順で有する積層体において、仮支持体のネガ型感光性樹脂層Ｎが配置された面とは反対側の面にフォトマスクを接触させた後、フォトマスクを介してネガ型感光性樹脂層Ｎに光を照射した。しかしながら、光を照射する工程において、ＰＥＴフィルムの収縮に起因して生じたと考えられる銅パターン（遮光性パターン）の位置ずれが観察されたため、フォトマスクの開口部の位置と銅パターン（遮光性パターン）のスペース部との位置合わせが困難であった。この結果、銅パターン（遮光性パターン）のスペース部に樹脂パターンを形成することができなかった。 (Comparative Example 1)
In the step described in the section of "Formation of pattern 3 (copper pattern)", an attempt was made to produce a structure having a copper pattern by the same procedure as in Example 1 except that the light irradiation method was changed. Specifically, in a laminate having a PET film, a copper pattern (light-shielding pattern), a negative photosensitive resin layer N, and a temporary support in this order, the negative photosensitive resin layer N of the temporary support is arranged. After the photomask was brought into contact with the surface opposite to the surface, the negative photosensitive resin layer N was irradiated with light via the photomask. However, in the process of irradiating light, a misalignment of the copper pattern (light-shielding pattern), which is considered to be caused by the shrinkage of the PET film, was observed, so that the position of the opening of the photomask and the copper pattern (light-shielding pattern) were observed. ) Was difficult to align with the space. As a result, the resin pattern could not be formed in the space portion of the copper pattern (light-shielding pattern).
＜評価＞
［パターンの形成性］
　光学顕微鏡を用いて、得られたパターン３を有する構造体の任意の１００視野を観察した。各視野の範囲は、２００μｍ×２００μｍとした。パターン３において異常部が観察された視野の数に基づき、以下の基準に従って、導電性パターンの形成性を評価した。異常部とは、パターン３において割れ、剥がれ、欠け等の形態異常が観察された部分をいう。評価結果を表５に示す。
　Ａ：異常部が観察された視野の数は２０未満である。
　Ｂ：異常部が観察された視野の数は２０以上である。 <Evaluation>
[Pattern formation]
Using an optical microscope, any 100 fields of view of the structure having the obtained pattern 3 were observed. The range of each field of view was 200 μm × 200 μm. Based on the number of visual fields in which the abnormal portion was observed in pattern 3, the formability of the conductive pattern was evaluated according to the following criteria. The abnormal portion refers to a portion in which morphological abnormalities such as cracking, peeling, and chipping are observed in the pattern 3. The evaluation results are shown in Table 5.
A: The number of visual fields in which the abnormal part is observed is less than 20.
B: The number of visual fields in which the abnormal portion is observed is 20 or more.
Figure JPOXMLDOC01-appb-T000010
 
Figure JPOXMLDOC01-appb-T000010
 
　なお、表５の実施例３の使用したネガ型感光性組成物欄におけるＮ９は、オーバーコート塗布液（組成物Ｎ９）を示す。
　表５に記載の結果から、実施例１～実施例１３の構造体の製造方法は、比較例１の構造体の製造方法に比べて、形態異常の発生が低減されたパターンを形成できることがわかる。 In addition, N9 in the negative type photosensitive composition column used in Example 3 of Table 5 indicates an overcoat coating liquid (composition N9).
From the results shown in Table 5, it can be seen that the method for producing the structure of Examples 1 to 13 can form a pattern in which the occurrence of morphological abnormalities is reduced as compared with the method for producing the structure of Comparative Example 1. ..
　２０２０年４月３０日に出願された日本国特許出願２０２０－０８０７１６号の開示は、その全体が参照により本明細書に取り込まれる。
　本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書に参照により取り込まれる。 The disclosure of Japanese Patent Application No. 2020-080716 filed on April 30, 2020 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.
　１０，１１：透明基材
　１０ａ：被露光面
　２０，２１：遮光性パターン（遮光性パターン１）
　３０：ネガ型感光性樹脂層（ネガ型感光性樹脂層Ｎ）
　３０ａ：露光部
　４０，４１：樹脂パターン（樹脂パターン２）
　５０，５１：パターン（パターン３）
　１００：積層体
　２００：構造体 10, 11: Transparent base material 10a: Exposed surface 20, 21: Light-shielding pattern (light-shielding pattern 1)
30: Negative type photosensitive resin layer (negative type photosensitive resin layer N)
30a: Exposed parts 40, 41: Resin pattern (resin pattern 2)
50, 51: Pattern (Pattern 3)
100: Laminated body 200: Structure

Claims (17)

  1. 　透明基材と、前記透明基材の上に配置された遮光性パターン１と、前記透明基材及び前記遮光性パターン１の上に配置され、かつ、前記透明基材に接するネガ型感光性樹脂層Ｎと、を有する積層体を準備する工程、
    　前記透明基材の前記遮光性パターン１が設けられている面とは反対側の面から前記ネガ型感光性樹脂層Ｎの一部に光を照射する工程、
    　光を照射された前記ネガ型感光性樹脂層Ｎを現像することで、前記透明基材上に樹脂パターン２を形成する工程、並びに、
    　前記遮光性パターン１と前記樹脂パターン２とによって画定される領域にパターン３を形成する工程を含み、
    　得られる構造体が、前記樹脂パターン２を永久膜として有する
    　構造体の製造方法。     A transparent base material, a light-shielding pattern 1 arranged on the transparent base material, and a negative photosensitive resin arranged on the transparent base material and the light-shielding pattern 1 and in contact with the transparent base material. A step of preparing a laminate having a layer N,
    A step of irradiating a part of the negative photosensitive resin layer N with light from a surface of the transparent substrate opposite to the surface on which the light-shielding pattern 1 is provided.
    A step of forming the resin pattern 2 on the transparent substrate by developing the negative photosensitive resin layer N irradiated with light, and
    The step of forming the pattern 3 in the region defined by the light-shielding pattern 1 and the resin pattern 2 is included.
    A method for producing a structure in which the obtained structure has the resin pattern 2 as a permanent film.
  2. 　前記遮光性パターン１が、金属を含む請求項１に記載の構造体の製造方法。 The method for manufacturing a structure according to claim 1, wherein the light-shielding pattern 1 contains a metal.
  3. 　前記パターン３が、導電性を有する請求項１又は請求項２に記載の構造体の製造方法。 The method for manufacturing a structure according to claim 1 or 2, wherein the pattern 3 has conductivity.
  4. 　前記パターン３が、めっき法によって形成されてなるパターンである請求項１～請求項３のいずれか１項に記載の構造体の製造方法。 The method for manufacturing a structure according to any one of claims 1 to 3, wherein the pattern 3 is a pattern formed by a plating method.
  5. 　前記遮光性パターン１及び前記パターン３が、同種の材料を含む請求項１～請求項４のいずれか１項に記載の構造体の製造方法。 The method for producing a structure according to any one of claims 1 to 4, wherein the light-shielding pattern 1 and the pattern 3 contain the same kind of material.
  6. 　前記ネガ型感光性樹脂層Ｎが、アルカリ可溶性高分子、エチレン性不飽和化合物、及び、光重合開始剤を含む請求項１～請求項５のいずれか１項に記載の構造体の製造方法。 The method for producing a structure according to any one of claims 1 to 5, wherein the negative photosensitive resin layer N contains an alkali-soluble polymer, an ethylenically unsaturated compound, and a photopolymerization initiator.
  7. 　前記エチレン性不飽和化合物が、３官能以上のエチレン性不飽和化合物を含む請求項６に記載の構造体の製造方法。 The method for producing a structure according to claim 6, wherein the ethylenically unsaturated compound contains a trifunctional or higher functional ethylenically unsaturated compound.
  8. 　前記エチレン性不飽和化合物が、ジシクロペンタニル構造又はジシクロペンテニル構造を有するジ（メタ）アクリレート化合物を含む請求項６又は請求項７に記載の構造体の製造方法。 The method for producing a structure according to claim 6 or 7, wherein the ethylenically unsaturated compound contains a di (meth) acrylate compound having a dicyclopentanyl structure or a dicyclopentenyl structure.
  9. 　前記ネガ型感光性樹脂層Ｎが、多官能エポキシ樹脂、ヒドロキシ基含有化合物、及び、光カチオン重合開始剤を含む請求項１～請求項５のいずれか１項に記載の構造体の製造方法。 The method for producing a structure according to any one of claims 1 to 5, wherein the negative photosensitive resin layer N contains a polyfunctional epoxy resin, a hydroxy group-containing compound, and a photocationic polymerization initiator.
  10. 　前記ネガ型感光性樹脂層Ｎが、金属酸化抑制剤を含む請求項１～請求項９のいずれか１項に記載の構造体の製造方法。 The method for producing a structure according to any one of claims 1 to 9, wherein the negative photosensitive resin layer N contains a metal oxidation inhibitor.
  11. 　透明基材の一方の面に遮光性層を形成する工程、
    　遮光性層上にフォトレジスト層を形成する工程、
    　前記フォトレジスト層を露光及び現像してレジストパターンを形成する工程、並びに、
    　前記遮光性層をエッチングし前記遮光性パターン１を形成する工程を更に含む請求項１～請求項１０のいずれか１項に記載の構造体の製造方法。     A process of forming a light-shielding layer on one surface of a transparent substrate,
    A process of forming a photoresist layer on a light-shielding layer,
    A step of exposing and developing the photoresist layer to form a resist pattern, and
    The method for producing a structure according to any one of claims 1 to 10, further comprising a step of etching the light-shielding layer to form the light-shielding pattern 1.
  12. 　前記遮光性パターン１の平均厚さよりも前記パターン３の平均厚さのほうが厚い請求項１～請求項１１のいずれか１項に記載の構造体の製造方法。 The method for manufacturing a structure according to any one of claims 1 to 11, wherein the average thickness of the pattern 3 is thicker than the average thickness of the light-shielding pattern 1.
  13. 　前記透明基材が、透明フィルム基材である請求項１～請求項１２のいずれか１項に記載の構造体の製造方法。 The method for producing a structure according to any one of claims 1 to 12, wherein the transparent base material is a transparent film base material.
  14. 　前記樹脂パターン２に対し後露光及び後加熱の少なくともいずれかを行う工程を更に含む請求項１～請求項１３のいずれか１項に記載の構造体の製造方法。 The method for producing a structure according to any one of claims 1 to 13, further comprising a step of performing at least one of post-exposure and post-heating on the resin pattern 2.
  15. 　前記ネガ型感光性樹脂層Ｎが、感光性転写材料により形成されてなる層である請求項１～請求項１４のいずれか１項に記載の構造体の製造方法。 The method for producing a structure according to any one of claims 1 to 14, wherein the negative photosensitive resin layer N is a layer formed of a photosensitive transfer material.
  16. 　得られる構造体が、タッチセンサー、電磁波シールド、アンテナ、配線基板、導電性加熱素子、及び、視野角制御フィルムよりなる群から選ばれる１種の構造体である請求項１～請求項１５のいずれか１項に記載の構造体の製造方法。 Any of claims 1 to 15, wherein the obtained structure is one type of structure selected from the group consisting of a touch sensor, an electromagnetic wave shield, an antenna, a wiring substrate, a conductive heating element, and a viewing angle control film. The method for producing a structure according to item 1.
  17. 　透明基材と、
    　前記透明基材の上に配置された遮光性パターン１と、
    　前記透明基材の上で前記遮光性パターン１に隣接して配置され、かつ、前記透明基材に接する樹脂パターン２と、
    　前記遮光性パターン１と前記樹脂パターン２とによって画定される領域にパターン３とを有し、
    　前記遮光性パターン１の平均厚さが、２μｍ以下であり、
    　前記樹脂パターン２の平均厚さが、２μｍを超え、
    　前記遮光性パターン１の平均厚さよりも前記パターン３の平均厚さのほうが厚く、
    　前記樹脂パターン２を永久膜として有する
    　構造体。     With a transparent base material
    The light-shielding pattern 1 arranged on the transparent substrate and
    A resin pattern 2 arranged adjacent to the light-shielding pattern 1 on the transparent substrate and in contact with the transparent substrate,
    The pattern 3 is provided in a region defined by the light-shielding pattern 1 and the resin pattern 2.
    The average thickness of the light-shielding pattern 1 is 2 μm or less.
    The average thickness of the resin pattern 2 exceeds 2 μm,
    The average thickness of the pattern 3 is thicker than the average thickness of the light-shielding pattern 1.
    A structure having the resin pattern 2 as a permanent film.
PCT/JP2021/016684 2020-04-30 2021-04-26 Method for manufacturing structure, and structure WO2021221025A1 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2022518063A JPWO2021221025A1 (en) 2020-04-30 2021-04-26
CN202180031425.7A CN115486211A (en) 2020-04-30 2021-04-26 Method for manufacturing structure and structure
KR1020227037777A KR20220162158A (en) 2020-04-30 2021-04-26 Structure manufacturing method, and structure

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2020-080716 2020-04-30
JP2020080716 2020-04-30

Publications (1)

Publication Number Publication Date
WO2021221025A1 true WO2021221025A1 (en) 2021-11-04

Family

ID=78374086

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2021/016684 WO2021221025A1 (en) 2020-04-30 2021-04-26 Method for manufacturing structure, and structure

Country Status (5)

Country Link
JP (1) JPWO2021221025A1 (en)
KR (1) KR20220162158A (en)
CN (1) CN115486211A (en)
TW (1) TW202208988A (en)
WO (1) WO2021221025A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI829194B (en) * 2022-03-04 2024-01-11 中國大陸商長鑫存儲技術有限公司 Preparation method for semiconductor structure and same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05183259A (en) * 1991-12-27 1993-07-23 Ibiden Co Ltd Manufacture of high density printed wiring board
JPH0731399B2 (en) * 1984-12-21 1995-04-10 三菱化学株式会社 Photopolymerizable composition
JP2000265087A (en) * 1999-03-11 2000-09-26 Mikuni Color Ltd Method for forming metal pattern
JP2010267652A (en) * 2009-05-12 2010-11-25 Hitachi Cable Ltd Printed wiring board and method for manufacturing the same
JP2014193961A (en) * 2013-03-28 2014-10-09 Hitachi Chemical Co Ltd Method of producing resist film, electric wiring board, optical waveguide and photoelectricity composite board
JP2018501656A (en) * 2014-12-16 2018-01-18 アトテック・ドイチュラント・ゲーエムベーハーＡｔｏｔｅｃｈ Ｄｅｕｔｓｃｈｌａｎｄ Ｇｍｂｈ Fine wire manufacturing method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0731399B2 (en) * 1984-12-21 1995-04-10 三菱化学株式会社 Photopolymerizable composition
JPH05183259A (en) * 1991-12-27 1993-07-23 Ibiden Co Ltd Manufacture of high density printed wiring board
JP2000265087A (en) * 1999-03-11 2000-09-26 Mikuni Color Ltd Method for forming metal pattern
JP2010267652A (en) * 2009-05-12 2010-11-25 Hitachi Cable Ltd Printed wiring board and method for manufacturing the same
JP2014193961A (en) * 2013-03-28 2014-10-09 Hitachi Chemical Co Ltd Method of producing resist film, electric wiring board, optical waveguide and photoelectricity composite board
JP2018501656A (en) * 2014-12-16 2018-01-18 アトテック・ドイチュラント・ゲーエムベーハーＡｔｏｔｅｃｈ Ｄｅｕｔｓｃｈｌａｎｄ Ｇｍｂｈ Fine wire manufacturing method

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI829194B (en) * 2022-03-04 2024-01-11 中國大陸商長鑫存儲技術有限公司 Preparation method for semiconductor structure and same

Also Published As

Publication number Publication date
CN115486211A (en) 2022-12-16
TW202208988A (en) 2022-03-01
JPWO2021221025A1 (en) 2021-11-04
KR20220162158A (en) 2022-12-07

Similar Documents

Publication Publication Date Title
CN113412289B (en) Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board
WO2021221025A1 (en) Method for manufacturing structure, and structure
WO2021033451A1 (en) Photosensitive transfer member, circuit wiring-manufacturing method, and touch panel-manufacturing method
US20230007784A1 (en) Method of manufacturing conductive pattern, touch sensor, electromagnetic wave shield, antenna, wiring board, conductive heating element, and structure
CN113678062A (en) Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, and method for producing touch panel
CN115768838B (en) Composition, transfer film, method for producing laminate, method for producing circuit wiring, and method for producing electronic device
WO2021176811A1 (en) Photosensitive transfer material, and production method for circuit wiring
TW202212379A (en) Composition, transfer film, method for producing laminate, method for producing wiring line, and method for producing electrical device
JP2021128178A (en) Method for producing resin pattern, method for manufacturing circuit wiring, method for manufacturing touch panel, and photosensitive transfer member
WO2022044557A1 (en) Photomask, exposure method, method for manufacturing resin pattern, and method for manufacturing photomask
WO2021176812A1 (en) Photosensitive transfer material, and production method for circuit wiring
WO2023119998A1 (en) Method for producing laminate having conductor pattern, photosensitive composition, and transfer film
CN115729045A (en) Method for manufacturing laminate having conductor pattern, and transfer film
CN115685684A (en) Photosensitive composition, photosensitive composition layer, transfer film, and method for producing laminate having conductor pattern
CN115685672A (en) Transfer film and method for manufacturing laminate having conductor pattern
CN115729044A (en) Method for manufacturing laminate having conductor pattern, and transfer film
TW202311049A (en) Transfer film, method for producing laminate having conductor pattern
JP2023043527A (en) Photosensitive composition, transfer film, and manufacturing method of laminate having conductor pattern
CN115685701A (en) Transfer film, method for manufacturing laminate having conductor pattern, and photosensitive composition
CN116149139A (en) Photosensitive composition, transfer film, pattern forming method, and method for manufacturing circuit wiring
CN115485621A (en) Photosensitive transfer material, method for producing resin pattern, method for producing circuit wiring, and method for producing touch panel
JP2023035807A (en) Method for producing laminate having conductive pattern and transfer film
CN115701857A (en) Composition, dried product, cured product, transfer film, method for producing transfer film, and method for forming pattern
CN116670588A (en) Photosensitive transfer material, method for producing resin pattern, method for producing laminate, method for producing circuit wiring, and method for producing electronic device
CN116601566A (en) Photosensitive transfer material, method for producing resin pattern, method for producing laminate, method for producing circuit wiring, and method for producing electronic device

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21796059

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022518063

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20227037777

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21796059

Country of ref document: EP

Kind code of ref document: A1