WO2020158316A1 - Photosensitive transfer material, resin pattern production method, circuit wiring production method, touch panel production method, and, film and production method therefor - Google Patents

Photosensitive transfer material, resin pattern production method, circuit wiring production method, touch panel production method, and, film and production method therefor Download PDF

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Publication number
WO2020158316A1
WO2020158316A1 PCT/JP2020/000277 JP2020000277W WO2020158316A1 WO 2020158316 A1 WO2020158316 A1 WO 2020158316A1 JP 2020000277 W JP2020000277 W JP 2020000277W WO 2020158316 A1 WO2020158316 A1 WO 2020158316A1
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Prior art keywords
layer
temporary support
transfer material
photosensitive resin
resin layer
Prior art date
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PCT/JP2020/000277
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French (fr)
Japanese (ja)
Inventor
一真 両角
悠樹 豊嶋
漢那　慎一
宮宅　一仁
Original Assignee
富士フイルム株式会社
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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 JP2020569469A priority Critical patent/JPWO2020158316A1/en
Priority to CN202080010696.XA priority patent/CN113348078A/en
Publication of WO2020158316A1 publication Critical patent/WO2020158316A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • 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
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process

Definitions

  • the present disclosure relates to a photosensitive transfer material, a resin pattern manufacturing method, a circuit wiring manufacturing method, a touch panel manufacturing method, a film, and a manufacturing method thereof.
  • a display device organic electroluminescence (EL) display device, liquid crystal display device, etc.
  • a touch panel such as an electrostatic capacitance type input device, an electrode pattern corresponding to a sensor of a visual recognition part, wiring of a peripheral wiring part and an extraction wiring part
  • a conductive layer pattern such as is provided inside the touch panel.
  • a patterned layer is formed by a small number of steps for obtaining a required pattern shape. Therefore, a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material. On the other hand, a method of developing after exposing through a mask having a desired pattern is widely used.
  • JP-A-2017-78852 describes a positive type dry film resist having a resist layer on a temporary support, in which the total light ray haze of the temporary support is 0.3% or less. There is.
  • Japanese Unexamined Patent Publication No. 2000-221688 discloses a biaxially oriented polyester film in which the content of particles having an average particle size of 0.01 ⁇ m to 5.0 ⁇ m is 80 ppm or less and which does not contain particles having an average particle size of more than 5.0 ⁇ m
  • Japanese Unexamined Patent Publication No. 2000-221688 discloses a biaxially oriented polyester film in which the content of particles having an average particle size of 0.01 ⁇ m to 5.0 ⁇ m is 80 ppm or less and which does not contain particles having an average particle size of more than 5.0 ⁇ m
  • a polyester film for a photoresist for ultrafine wires which is characterized in that it is 1.0% or less.
  • One embodiment according to the present disclosure relates to providing a photosensitive transfer material that achieves both suppression of wrinkling during transport and stability over time after exposure. Further, another embodiment according to the present disclosure relates to providing a method for manufacturing a resin pattern using the above-mentioned photosensitive transfer material, a method for manufacturing circuit wiring, and a method for manufacturing a touch panel. Yet another embodiment according to the present disclosure relates to a film having excellent transparency and a property of suppressing generation of wrinkles during transportation, and a method for manufacturing the film.
  • the present disclosure includes the following aspects. ⁇ 1> a temporary support and a photosensitive resin layer provided on the temporary support, wherein the temporary support has a particle-containing layer containing particles, and the temporary support has a photosensitivity.
  • the surface roughness Ra of the surface opposite to the surface having the resin layer is 0.02 ⁇ m to 0.20 ⁇ m, and the photosensitive resin layer has an acid group protected by an acid-decomposable group.
  • ⁇ 3> The photosensitive transfer material according to ⁇ 1> or ⁇ 2>, wherein the particle-containing layer has a thickness of 10 nm to 100 nm.
  • ⁇ 4> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 3>, wherein the particle-containing layer is provided on only one surface of the temporary support.
  • ⁇ 5> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 4>, wherein the arithmetic average particle diameter of the particles is less than 100 nm.
  • ⁇ 6> Any one of ⁇ 1> to ⁇ 5>, wherein the surface roughness Ra of the surface of the temporary support opposite to the surface having the photosensitive resin layer is 0.05 ⁇ m to 0.10 ⁇ m.
  • the photosensitive transfer material described in 1. ⁇ 7> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 6>, wherein the temporary support has a thickness of more than 18 ⁇ m and 30 ⁇ m or less.
  • ⁇ 8> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 7>, in which the temporary support contains a polyester resin.
  • ⁇ 9> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 8>, wherein the acid group protected by the acid-decomposable group is a carboxy group protected by an acetal-type acid-decomposable group.
  • ⁇ 10> The photosensitive transfer material according to any one of ⁇ 1> to ⁇ 9>, wherein the polymer has an acid value of 10 mgKOH/g or less.
  • the photo-acid generator includes a photo-acid generator that generates an alkylsulfonic acid having 1 to 4 carbon atoms.
  • a step of pattern-exposing the photosensitive resin layer, and a step of developing the exposed photosensitive resin layer to form a resin pattern in this order ⁇ 13>
  • the outermost layer on the side having the photosensitive resin layer with respect to the temporary support in the photosensitive transfer material according to any one of ⁇ 1> to ⁇ 11> is brought into contact with a substrate having a conductive layer.
  • a method of manufacturing circuit wiring which includes a step of etching a conductive layer in this order.
  • a method of manufacturing a touch panel comprising: a step of etching a conductive layer; ⁇ 15> A particle-containing layer containing particles is provided on at least one surface, a haze value is 0.2% or less, and a surface roughness Ra of the surface having the particle-containing layer is 0.02 ⁇ m to 0.
  • a photosensitive transfer material that achieves both suppression of wrinkling during transport and stability over time after exposure. Further, according to another embodiment of the present disclosure, it is possible to provide a method for manufacturing a resin pattern using the photosensitive transfer material, a method for manufacturing circuit wiring, and a method for manufacturing a touch panel. According to still another embodiment of the present disclosure, it is possible to provide a film having excellent transparency and a property of suppressing the generation of wrinkles during transportation, and a manufacturing method thereof.
  • the numerical range represented by “to” means a range including the numerical values before and after “to” as the lower limit value and the upper limit value.
  • “(meth)acryl” represents both acryl and methacryl, or either, and “(meth)acrylate” represents both an acrylate and a methacrylate.
  • the amount of each component in the composition is the sum of the corresponding plurality of substances present in the composition, unless a plurality of substances corresponding to each component are present in the composition. Means quantity.
  • the term “step” is included in the term as long as the intended purpose of the step is achieved, not only when it is an independent step but also when it cannot be clearly distinguished from other steps.
  • the notation in which substitution and non-substitution are not included includes not only those having no substituent but also 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” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
  • the light used for the exposure generally, the bright line spectrum of a mercury lamp, far-ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays (active energy rays) such as electron rays are used.
  • EUV light extreme ultraviolet rays
  • X-rays extreme ultraviolet rays
  • active rays active energy rays
  • the chemical structural formulas in the present specification may be described as simplified structural formulas in which hydrogen atoms are omitted.
  • “mass %” and “weight %” have the same meaning
  • “mass part” and “weight part” have the same meaning.
  • a combination of two or more preferable aspects is a more preferable aspect.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure are columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both manufactured by Tosoh Corporation) unless otherwise specified.
  • the gel permeation chromatography (GPC) analyzer was used to detect the solvent THF (tetrahydrofuran) with a differential refractometer, and the molecular weight was calculated using polystyrene as a standard substance.
  • the photosensitive transfer material according to the present disclosure has a temporary support and a photosensitive resin layer supported by the temporary support, and the temporary support has a particle-containing layer containing particles,
  • the surface roughness Ra of the surface of the temporary support opposite to the surface having the photosensitive resin layer is 0.02 ⁇ m to 0.20 ⁇ m, and the photosensitive resin layer is protected with an acid-decomposable group.
  • a polymer containing a structural unit having an acid group, and a photoacid generator is a positive type photosensitive transfer material having a positive type photosensitive resin layer as described above.
  • the photosensitive resin layer is preferably a chemically amplified positive photosensitive resin layer.
  • the present inventors have found that in conventional photosensitive transfer materials, wrinkles may occur due to stress applied during transportation, and wrinkles are particularly noticeable when transported and transferred by roll-to-roll. It was Further, a polymer containing a constitutional unit having an acid group protected by an acid-decomposable group, and a so-called chemically amplified positive photosensitive resin layer containing a photo-acid generator are exposed to light and developed, A pattern is formed by leaving the exposed part, but due to the diffusion of light at the time of exposure derived from the particles, a small amount of acid is generated even in the non-exposed part, and the acid is diffused, so that the time elapsed after the exposure.
  • the present inventors have found that there is a problem in that the size of the pattern obtained when developed after that is changed.
  • the property that the size of the obtained pattern does not easily change even after development after a lapse of time after exposure is also referred to as “excellent in stability over time after exposure (PED: Post Exposure Delay stability)”. ..
  • PED Post Exposure Delay stability
  • a pattern is formed by curing the exposed portion, but the diffusion distance of the polymerization initiation species is short and the amount of generation is also small. Since the number is small, the problem that the size of the pattern obtained when developing is changed after a lapse of time after exposure does not occur. Therefore, the problem that the size of the pattern obtained when developing is changed after a lapse of time after exposure is a problem peculiar to the chemically amplified positive photosensitive resin layer.
  • the use of the photosensitive transfer material having the above-described configuration suppresses the generation of wrinkles during transportation (also referred to as “wrinkle generation inhibition during transportation”) and after exposure. It was found that a photosensitive transfer material having both stability with time can be obtained.
  • the temporary support has a particle-containing layer containing particles, and the surface opposite to the surface having the photosensitive resin layer of the temporary support. Has a surface roughness Ra of 0.02 ⁇ m to 0.20 ⁇ m, the uneven portion formed by the shape of the particles present on at least one of the surface and the inside of the temporary support has a temporary roughness during transportation.
  • the temporary support is particles.
  • the surface roughness Ra of the surface of the temporary support opposite to the surface having the photosensitive resin layer is 0.02 ⁇ m to 0.20 ⁇ m. It is presumed that the diffusion of light derived from particles during exposure is suppressed, the linearity of the obtained pattern is excellent, the generation and diffusion of acid in the non-exposed portion is suppressed, and the temporal stability after exposure is excellent.
  • the photosensitive transfer material according to the present disclosure has a temporary support, the temporary support has a particle-containing layer containing particles, and the surface of the temporary support on the side having the photosensitive resin layer is The surface roughness Ra of the opposite surface is 0.02 ⁇ m to 0.20 ⁇ m.
  • the above temporary support may have only one layer containing the above-mentioned particle-containing layer or may have two or more layers.
  • the particle-containing layer is provided on only one side of the temporary support, from the viewpoint of wrinkle generation suppression during transport, stability over time after exposure, and linearity of the obtained pattern, or the above temporary support. It is preferably provided on both sides of the support, and more preferably provided on only one side of the temporary support, on the side opposite to the side having the photosensitive resin layer of the temporary support. It is particularly preferable that it is provided only on the surface.
  • Examples of the particles contained in the particle-containing layer include inorganic particles and organic particles.
  • Examples of the inorganic particles include silicon oxide (silica) particles, titanium oxide (titania) particles, zirconium oxide (zirconia) particles, magnesium oxide (magnesia) particles, aluminum oxide (alumina) particles, and the like.
  • Examples of the organic particles include organic resin particles such as acrylic resin particles, polyester particles, polyurethane particles, polycarbonate particles, polyolefin particles, and polystyrene particles.
  • the particles contained in the particle-containing layer are preferably inorganic particles, and more preferably silica particles, from the viewpoint of temporal stability after exposure, and linearity of the obtained pattern. ..
  • the particle-containing layer may contain one kind of particle alone, or may contain two or more kinds of particles.
  • the content of particles in the particle-containing layer is not particularly limited as long as it can satisfy the range of the surface roughness Ra, but from the viewpoint of controllability of the surface roughness, and wrinkle generation suppressing property during transport, It is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass, and 0.5% by mass to 5% by mass with respect to the total mass of the particle-containing layer. Is particularly preferable.
  • the particles in the particle-containing layer may be present inside the particle-containing layer or may be partially exposed on the surface of the particle-containing layer. For example, when the particle-containing layer is provided on the surface of the temporary support opposite to the surface having the photosensitive resin layer, the particles may be exposed on the opposite surface of the temporary support. ..
  • the material other than the particles contained in the particle-containing layer is not particularly limited, and examples thereof include the same materials as the materials of the temporary support described later.
  • the particle-containing layer preferably contains a resin, more preferably contains a resin as the binder polymer, and contains an acrylic resin, from the viewpoints of the controllability of the surface roughness and the property of suppressing the generation of wrinkles during transportation. Is particularly preferable.
  • the particle-containing layer contains a resin different from the resin contained in the temporary support in the part other than the particle-containing layer, from the viewpoint of controllability of surface roughness and wrinkle generation suppressing property during transportation. It is particularly preferable that the particle-containing layer contains an acrylic resin, and the temporary support other than the particle-containing layer contains a polyester resin.
  • the particle-containing layer may contain one type of resin or two or more types of resin.
  • the content of the resin in the particle-containing layer is not particularly limited, but is 10 with respect to the total mass of the particle-containing layer from the viewpoint of controllability of surface roughness and wrinkle suppression during transport.
  • the content is preferably from 9 to 99.9% by mass, more preferably from 20 to 99.5% by mass, further preferably from 50 to 99% by mass, and from 80 to 98% by mass. % Is particularly preferable.
  • the particle-containing layer may contain other compounds than the particles and the resin.
  • examples of other compounds include surfactants and waxes.
  • the particle-containing layer preferably contains a surfactant from the viewpoint of layer thickness uniformity.
  • the surfactant may be anionic, cationic, nonionic (nonionic), or amphoteric, and the preferred surfactant is anionic.
  • anionic surfactants include Rapizole (registered trademark) A-90, A-80, BW-30, B-90, C-70 (all manufactured by NOF Corporation) and NIKKOL (registered trademark).
  • OTP-100 (above, manufactured by Nikko Chemical Co., Ltd.), Kohakul (registered trademark) ON, L-40, Phosphanol (registered trademark) 702 (above, manufactured by Toho Chemical Industry Co., Ltd.), Beaulite (registered trademark) ) A-5000, SSS (above, Sanyo Chemical Industry Co., Ltd.) and the like.
  • the surfactant may be used alone or in combination of two or more kinds.
  • the content of the surfactant is not particularly limited, but is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, based on the total mass of the particle-containing layer. It is more preferably 0.01% by mass to 3% by mass.
  • the particle-containing layer may contain wax from the viewpoint of the coating property of the coating liquid when the particle-containing layer is formed by coating.
  • waxes include plant waxes such as carnauba wax, candelilla wax, rice wax, wax, jojoba oil, palm wax, rosin modified wax, auri curly wax, sugar cane wax, esparto wax, and bark wax; beeswax.
  • Animal waxes such as lanolin, whale wax, ivowa wax, shellac wax; mineral waxes such as montan wax, ozokerite, ceresin wax; petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam; Fischer-Tropsch wax, polyethylene
  • the wax include synthetic hydrocarbon waxes such as wax, oxidized polyethylene wax, polypropylene wax, and oxidized polypropylene wax.
  • the wax may be used alone or in combination of two or more.
  • the content of the wax is not particularly limited, but is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and more preferably 0. 0% by mass based on the total mass of the particle-containing layer. It is more preferably from 01% by mass to 3% by mass.
  • the arithmetic average particle diameter of the above particles is 20 nm to 300 nm from the viewpoints of controllability of surface roughness, suppression of wrinkling during transport, stability over time after exposure, and linearity of the obtained pattern. Is more preferable, 30 nm to 200 nm is more preferable, 40 nm to 120 nm is still more preferable, and 40 nm to 80 nm is particularly preferable. Further, the arithmetic average particle diameter of the above particles is preferably less than 100 nm from the viewpoint of transparency, wrinkle generation suppressing property during transportation, stability over time after exposure, and linearity of the obtained pattern.
  • the arithmetic average particle diameter of the particles is less than 100 nm, light scattering can be suppressed at a high level, so that high transparency can be realized and stability over time after exposure is considered to be excellent. Further, even when the arithmetic mean particle diameter of the particles is less than 100 nm, by disposing a large number of particles on the outermost surface of the film, the surface of the temporary support is opposite to the surface having the photosensitive resin layer. It is considered that the surface roughness Ra of the side surface can be set to 0.02 ⁇ m to 0.2 ⁇ m, and wrinkles during transportation can be further suppressed.
  • the arithmetic mean particle size of the particles in the present disclosure is 400 particles arbitrarily extracted by observing a temporary support at an acceleration voltage of 100 kV using a HT-7700 transmission electron microscope (TEM) manufactured by Hitachi High-Technologies Corporation. It is a value obtained by obtaining the average value (arithmetic average value) of the individual diameters. Note that obviously large aggregates (foreign matter, dust, etc.) are not counted (excluded from the above calculation; that is, not selected as particles).
  • the thickness of the particle-containing layer is preferably 5 nm to 300 nm, more preferably 10 nm to 100 nm, and more preferably 30 nm, from the viewpoint of easy control of the surface roughness and the property of suppressing the generation of wrinkles during transportation. Particularly preferably, it is from about 70 nm.
  • the preferred thickness of the particle-containing layer is the preferred thickness of each particle-containing layer.
  • the thickness of the particle-containing layer can be measured by the following method.
  • the arithmetic mean value of the thicknesses of the particle-containing layers measured at 10 randomly selected points is obtained, and the obtained value is taken as the thickness of the temporary support.
  • the cross-sectional observation image in the thickness direction of the temporary support can be obtained using a scanning electron microscope (SEM) or a laser microscope.
  • the surface of the temporary support on the side opposite to the surface having the photosensitive resin layer (also referred to as “back surface”) has a surface roughness Ra of 0.02 ⁇ m to 0.20 ⁇ m, and wrinkles during transportation are observed. From the viewpoints of generation inhibition, stability with time after exposure, and linearity of the obtained pattern, 0.02 ⁇ m to 0.15 ⁇ m is more preferable, and 0.03 ⁇ m to 0.12 ⁇ m is more preferable. , 0.05 ⁇ m to 0.10 ⁇ m is particularly preferable. Further, when the surface roughness Ra is 0.20 ⁇ m or less, the temporal stability after exposure is good.
  • the surface roughness Ra of the marking is 0.02 ⁇ m or more, it is possible to suppress the generation of wrinkles even when conveyed by roll to roll.
  • the surface roughness Ra of the surface of the temporary support on the side having the photosensitive resin layer is, from the viewpoint of stability with time after exposure and linearity of the obtained pattern, the photosensitive resin of the temporary support. It is preferably smaller than the surface roughness Ra of the surface opposite to the surface having the layer.
  • the surface roughness Ra of the temporary support can be measured by the following method.
  • a three-dimensional optical profiler (New View7300, manufactured by Zygo) is used to obtain the surface profile of the temporary support under the following conditions.
  • the Microscope Application of MetroPro ver 8.3.2 is used as the measurement and analysis software.
  • the Surface Map screen is displayed by the above-mentioned analysis software (MetroPro ver 8.3.2-Microscope Application), and histogram data is obtained in the Surface Map screen.
  • the arithmetic mean roughness is calculated from the obtained histogram data, and the obtained value is defined as the surface roughness Ra.
  • the temporary support preferably has a base material as a material other than the particle-containing layer.
  • the temporary support from the viewpoint of the temporal stability after exposure, and the linearity of the obtained pattern, the temporary support having the particle-containing layer on only one surface of the base material, or the both surfaces of the base material described above, respectively. Preferred are those having a particle-containing layer, and more preferred are those having the above-mentioned particle-containing layer only on one surface of the substrate.
  • the base material include a glass base material and a resin film. Among the above, the resin film is preferable from the viewpoint of strength, flexibility and the like.
  • the temporary support has a multi-layer structure, the above-mentioned glass base material, resin film or the like may be used as the base material.
  • the resin contained in the resin film include cycloolefin polymer, polyester resin, cellulose triacetate, polystyrene resin, and polycarbonate resin.
  • the temporary support preferably contains a polyester resin, more preferably polyethylene terephthalate, from the viewpoints of optical properties, solvent resistance and heat resistance. Further, the temporary support preferably has a polyester resin substrate as the substrate, and more preferably a polyethylene terephthalate substrate, from the viewpoint of optical characteristics, solvent resistance, and heat resistance.
  • the resin film examples include cycloolefin polymer film, polyester resin film, cellulose triacetate film, polystyrene resin film, polycarbonate resin film and the like.
  • the resin film is preferably a polyester resin film, and more preferably a polyethylene terephthalate film, from the viewpoint of optical characteristics, solvent resistance, and heat resistance.
  • the thickness of the temporary support is not particularly limited, but is preferably 5 ⁇ m or more and 50 ⁇ m or less, and more than 18 ⁇ m and 30 ⁇ m or less, from the viewpoint of temporal stability after exposure and linearity of the obtained pattern. It is more preferable that the thickness is 19 ⁇ m or more and 28 ⁇ m or less.
  • the thickness of the temporary support can be measured by the following method.
  • the arithmetic mean value of the thickness of the temporary support measured at 10 randomly selected places is calculated, and the obtained value is defined as the thickness of the temporary support.
  • the cross-sectional observation image in the thickness direction of the temporary support can be obtained using a scanning electron microscope (SEM) or a laser microscope.
  • Examples of commercial products of the temporary support having the particle-containing layer include Lumirror (registered trademark; the same applies hereinafter) 16KS40 (manufactured by Toray Co., Ltd.) and Cosmoshine (registered trademark) A-1517 (manufactured by Toyobo Co., Ltd.). ) And the like.
  • the haze value of the temporary support is preferably 0.8% or less, and more preferably 0.5% or less, from the viewpoint of the temporal stability after exposure and the linearity of the obtained pattern. , 0.3% or less is more preferable, and 0.2% or less is particularly preferable. In particular, when the haze value is 0.2% or less, the temporal stability after exposure is more excellent.
  • the haze value of the temporary support is a value obtained as an average value by measuring the haze value at 10 positions in the surface direction of the temporary support using a haze meter NDH400 (manufactured by Nippon Denshoku Industries Co., Ltd.). is there.
  • the method for producing the temporary support is not limited, and known production methods can be applied as appropriate.
  • the temporary support is a resin film
  • the resin film can be manufactured by a known manufacturing method such as extrusion molding.
  • the thickness of the temporary support may be adjusted by stretching (for example, biaxial stretching) or the like.
  • the particle-containing layer for example, a composition obtained by dispersing or dissolving the components contained in the particle-containing layer in a known solvent such as water, the surface of the temporary support opposite to the side on which the photosensitive resin layer is provided. It is formed by applying to.
  • stretching may be performed after applying the composition.
  • the temporary support preferably contains a biaxially stretched film as a base material, more preferably a biaxially stretched film stretched in two orthogonal drawing directions as a base material, and more preferably as a base material. It is particularly preferable that the temporary support includes a biaxially stretched film stretched in each of the two stretching directions and includes a particle-containing layer stretched in one of the two stretching directions.
  • the method for producing the temporary support is a step of forming a layer containing particles on a uniaxially stretched film stretched in the first stretching direction, and the uniaxially stretched film and the uniaxially stretched film. It is preferable to include a step of stretching the layer containing the particles in a second stretching direction orthogonal to the first stretching direction along the film surface of the uniaxially stretched film.
  • a photosensitive transfer material has a photosensitive resin layer, the photosensitive resin layer is a polymer containing a structural unit having an acid group protected by an acid-decomposable group, and photoacid generation Contains an agent.
  • the photosensitive resin layer in the present disclosure is a positive photosensitive resin layer, and a known positive photosensitive resin layer can be used.
  • the photosensitive resin layer used in the present disclosure is, from the viewpoint of sensitivity and resolution, an acid-decomposable resin, that is, a polymer having a structural unit having an acid group protected by an acid-decomposable group, and a photoacid generator. It is preferably a chemically amplified positive photosensitive resin layer containing an agent.
  • the photo-acid generators such as onium salts and oxime sulfonate compounds described below have an acid generated in response to actinic radiation (actinic rays) as a catalyst for deprotection of the protected acid group in the polymer. Since it acts, the acid generated by the action of one photon contributes to many deprotection reactions, and the quantum yield exceeds 1, which is a large value such as 10 to the power of several. High sensitivity is obtained as a result of such so-called chemical amplification.
  • the photosensitive resin layer is also referred to as a constitutional unit having an acid group protected by an acid-decomposable group (“a constitutional unit A having an acid group protected by an acid-decomposable group”, or simply “constitutional unit A”). .) (“polymer X having a structural unit having an acid group protected by an acid-decomposable group” or simply “polymer X”).
  • the photosensitive resin layer may contain another polymer.
  • the polymer X having the structural unit A and other polymers are collectively referred to as “polymer component”.
  • the acid group protected by the acid-decomposable group in the polymer X undergoes a deprotection reaction due to the action of a catalytic amount of an acid substance such as an acid generated by exposure to be an acid group.
  • This acid group enables the photosensitive resin layer to be dissolved in the developing solution.
  • the polymer X is preferably an addition polymerization type resin, and more preferably a polymer having a structural unit derived from (meth)acrylic acid or its ester.
  • a structural unit other than the structural unit derived from (meth)acrylic acid or its ester for example, the structural unit derived from a styrene compound, the structural unit derived from a vinyl compound, etc.
  • preferred embodiments of the structural unit A will be described.
  • the polymer component preferably contains a polymer X having a structural unit A having an acid group protected by an acid-decomposable group.
  • a chemically amplified positive photosensitive resin layer having extremely high sensitivity can be obtained.
  • known groups can be used and are not particularly limited. Preferred specific acid groups include a carboxy group and a phenolic hydroxyl group.
  • the acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal-type protecting group such as a 1-alkoxyalkyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group) or an acid that is decomposed by an acid.
  • an acid for example, an acetal-type protecting group such as a 1-alkoxyalkyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group
  • groups having relatively low decomposability for example, tertiary alkyl groups such as tert-butyl group, tertiary alkyloxycarbonyl groups such as tert-butyloxycarbonyl group (carbonic acid ester type protecting group)).
  • the acid-decomposable group is preferably a group having a structure protected in the form of acetal (acetal-type acid-decomposable group) from the viewpoint of sensitivity and resolution.
  • the acid group protected by the acid-decomposable group is more preferably a carboxy group protected by an acetal-type acid-decomposable group from the viewpoint of sensitivity and resolution.
  • the acid-decomposable group is an acid-decomposable group having a molecular weight of 300 or less (for example, 30 to 300) from the viewpoint of suppressing variation in the line width of the conductive wiring when applied to the formation of a conductive pattern. Is preferred.
  • the polymer X contained in the photosensitive resin layer may be only one kind or two or more kinds.
  • the structural unit A having an acid group protected by an acid-decomposable group is preferably a structural unit represented by the following formula A1, formula A2, or formula A3 from the viewpoint of sensitivity and resolution.
  • R 11 and R 12 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 11 and R 12 is an alkyl group or an aryl group, and R 13 is an alkyl group or an aryl group.
  • R 11 or R 12 and R 13 may combine to form a cyclic ether
  • R 14 represents a hydrogen atom or a methyl group
  • X 1 represents a single bond or a divalent linking group.
  • R 15 represents a substituent
  • n represents an integer of 0 to 4.
  • R 21 and R 22 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 21 and R 22 is an alkyl group or an aryl group, and R 23 is an alkyl group or an aryl group.
  • R 21 or R 22 and R 23 may be linked to form a cyclic ether, and R 24 is independently a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group or an aryl group.
  • R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group or an aryl group.
  • R 31 or R 32 and R 33 may combine to form a cyclic ether
  • R 34 represents a hydrogen atom or a methyl group
  • X 0 represents a single bond or a divalent linking group. ..
  • R 31 or R 32 when R 31 or R 32 is an alkyl group, it is preferably an alkyl group having 1 to 10 carbon atoms. When R 31 or R 32 is an aryl group, it is preferably a phenyl group. R 31 and R 32 are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In formula A3, R 33 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Moreover, the alkyl group and the aryl group in R 31 to R 33 may have a substituent.
  • R 31 or R 32 and R 33 may be linked to each other to form a cyclic ether, and R 31 or R 32 and R 33 are preferably linked to each other to form a cyclic ether.
  • the number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
  • X 0 represents a single bond or an arylene group, and is preferably a single bond.
  • the arylene group may have a substituent.
  • the structural unit A represented by the above formula A3 is a structural unit having a carboxy group protected by an acetal-type acid-decomposable group. When the polymer X contains the structural unit A represented by the formula A3, the sensitivity during pattern formation is excellent and the resolution is further excellent.
  • R 34 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the glass transition temperature (Tg) of the polymer X can be further lowered. More specifically, with respect to the total amount of the structural unit A contained in the polymer X, the structural unit in which R 34 in the formula A3 is a hydrogen atom is preferably 20% by mass or more.
  • the content (content ratio: mass ratio) of the structural unit in which R 34 in the formula A3 is a hydrogen atom in the structural unit A is calculated by a conventional method from 13 C-nuclear magnetic resonance spectrum (NMR) measurement. It can be confirmed by the intensity ratio of peak intensity.
  • the acid-decomposable group is preferably a group having a cyclic structure, more preferably a group having a tetrahydrofuran ring or a tetrahydropyran ring structure, and more preferably a tetrahydrofuran ring structure, from the viewpoint of sensitivity.
  • a group is more preferable, and a tetrahydrofuranyl group is particularly preferable.
  • the structural unit A contained in the polymer X may be one type or two or more types.
  • the content of the structural unit A in the polymer X is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 50% by mass, and more preferably 20% by mass to the total mass of the polymer component. It is more preferably from 40% by mass to 40% by mass. Within the above range, the resolution is further improved.
  • the content of the structural units A represents the total content of the two or more structural units A.
  • the content (content ratio: mass ratio) of the structural unit A in the polymer component can be confirmed by the intensity ratio of peak intensities calculated by a conventional method from 13 C-NMR measurement.
  • the polymer X may include a structural unit B having an acid group (also simply referred to as “structural unit B”).
  • the structural unit B is a structural unit having an acid group not protected by an acid-decomposable group, that is, an acid group having no protective group.
  • the acid group in the present specification means a proton dissociative group having a pKa of 12 or less.
  • the pKa of the acid group is preferably 10 or less, more preferably 6 or less.
  • the pKa of the acid group is preferably ⁇ 5 or more.
  • the acid group include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, and a sulfonylimide group. Among them, a carboxy group or a phenolic hydroxyl group is preferable, and a carboxy group is more preferable.
  • the structural unit B contained in the polymer X may be only one type or two or more types.
  • the content of the structural unit B in the polymer X is preferably 0.01% by mass to 20% by mass, and more preferably 0.01% by mass to 10% by mass, based on the total mass of the polymer component. It is more preferably 0.1% by mass to 5% by mass. Within the above range, the resolution becomes better.
  • the content of the structural unit B represents the total content of the two or more structural units B.
  • the content (content ratio: mass ratio) of the structural unit B in the polymer X can be confirmed by an intensity ratio of peak intensities calculated by a conventional method from 13 C-NMR measurement.
  • the polymer X is a range that does not impair the effects of the photosensitive transfer material according to the present disclosure, other than the above-described structural unit A and structural unit B, other structural unit C (also simply referred to as “structural unit C”). It is preferable to include.
  • the monomer forming the structural unit C is not particularly limited, and examples thereof include styrenes, (meth)acrylic acid alkyl ester, (meth)acrylic acid cyclic alkyl ester, (meth)acrylic acid aryl ester, and unsaturated dicarboxylic acid diester.
  • Bicyclo unsaturated compounds maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, groups having an aliphatic cyclic skeleton, other Mention may be made of saturated compounds.
  • the structural unit C By using the structural unit C and adjusting at least one of the type and content thereof, various properties of the polymer X can be adjusted. In particular, by including the structural unit C, the Tg, acid value and hydrophilicity/hydrophobicity of the polymer X can be easily adjusted.
  • the polymer X may include only one type of the structural unit C or may include two or more types.
  • the structural unit C is specifically styrene, ⁇ -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, methyl (meth)acrylate, (meth)acrylic.
  • Ethyl acid n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth) 2-Hydroxypropyl acrylate, benzyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth)acrylate, etc.
  • a structural unit formed by polymerizing compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623 can be mentioned.
  • the structural unit C preferably contains a structural unit having a basic group.
  • the basic group include groups having a nitrogen atom such as an aliphatic amino group, an aromatic amino group, and a nitrogen-containing heteroaromatic ring group, and an aliphatic amino group is preferable.
  • the aliphatic amino group may be any of a primary amino group, a secondary amino group, or a tertiary amino group, but from the viewpoint of resolution, a secondary amino group or a secondary amino group, or It is preferably a tertiary amino group.
  • the monomer forming the structural unit having a basic group include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2-(dimethylamino)ethyl methacrylate, and acrylic acid 2 ,2,6,6-Tetramethyl-4-piperidyl, 2,2,6,6-Tetramethyl-4-piperidyl methacrylate, 2,2,6,6-Tetramethyl-4-piperidyl acrylate, Methacrylic acid 2-(diethylamino)ethyl, 2-(dimethylamino)ethyl acrylate, 2-(diethylamino)ethyl acrylate, N-(3-dimethylamino)propyl methacrylate, N-(3-dimethylamino)propyl acrylate, N-(3-diethylamino)propyl methacrylate, N-(3-diethylamino)propyl acrylate, 2-(diisopropy
  • a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton is preferable from the viewpoint of improving the electrical characteristics of the resulting transfer material.
  • the monomer that forms these structural units include styrene, ⁇ -methylstyrene, dicyclopentanyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and Examples thereof include benzyl (meth)acrylate, and cyclohexyl (meth)acrylate is preferably used.
  • (meth)acrylic acid alkyl ester is preferable from the viewpoint of adhesion.
  • alkyl (meth)acrylate having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of adhesion.
  • Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.
  • the content of the structural unit C is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less, based on the total mass of the polymer component.
  • the lower limit is preferably 10% by mass or more, and more preferably 20% by mass or more. Within the above range, the resolution and adhesiveness are further improved.
  • the content of the structural unit C represents the total content of the two or more structural units C.
  • the polymer X in the present disclosure is not limited to the following examples.
  • the ratio of the structural units and the weight average molecular weight in the following exemplified compounds are appropriately selected to obtain preferable physical properties.
  • the glass transition temperature (Tg) of the polymer X in the present disclosure is preferably 90° C. or lower, more preferably 20° C. or higher and 60° C. or lower, and 30° C. or higher and 50° C. or lower. More preferably,
  • the FOX formula As a method of adjusting the Tg of the polymer in the present disclosure to the preferable range described above, for example, from the Tg of the homopolymer of each structural unit of the target polymer and the mass ratio of each structural unit, the FOX formula is It is possible to control the Tg of the desired polymer using the guidelines.
  • the FOX formula will be described below. Tg of the homopolymer of the first structural unit contained in the polymer is Tg1, the mass fraction of the copolymer of the first structural unit is W1, and Tg of the homopolymer of the second structural unit is Tg2.
  • Tg0(K) of the copolymer containing the first constitutional unit and the second constitutional unit is calculated according to the following formula. It is possible to estimate.
  • FOX formula: 1/Tg0 (W1/Tg1)+(W2/Tg2)
  • a copolymer having a desired Tg can be obtained by adjusting the type and mass fraction of each structural unit contained in the copolymer using the above-mentioned FOX formula. It is also possible to adjust the Tg of the polymer by adjusting the weight average molecular weight of the polymer.
  • the acid value of the polymer X is preferably 0 mgKOH/g or more and 50 mgKOH/g or less, more preferably 0 mgKOH/g or more and 20 mgKOH/g or less, and 0 mgKOH/g or more and 10 mgKOH/g. It is even more preferably g or less. Further, the acid value of the polymer X is preferably 10 mgKOH/g or less from the viewpoint of the temporal stability after exposure and the linearity of the obtained pattern.
  • the acid value of the polymer in the present disclosure represents the mass of potassium hydroxide required to neutralize the acidic component per 1 g of the polymer.
  • the solution is neutralized and titrated with a 0.1 mol/L sodium hydroxide aqueous solution at 25°C.
  • the acid value is calculated by the following formula.
  • A 56.11 ⁇ Vs ⁇ 0.1 ⁇ f/w
  • f titer of 0.1 mol/L sodium hydroxide aqueous solution
  • w mass of measurement sample (g) (solid content conversion)
  • the molecular weight of the polymer X is preferably 60,000 or less in terms of polystyrene equivalent weight average molecular weight. When the weight average molecular weight of the polymer X is 60,000 or less, it is possible to realize the transfer at a low temperature (for example, 130° C. or less) when transferring the transfer material.
  • the weight average molecular weight of the polymer X is preferably 2,000 to 60,000, more preferably 3,000 to 50,000, and more preferably 10,000 to 20 from the viewpoint of suppressing development residues. It is particularly preferable that it is 1,000.
  • the ratio (dispersion degree) of the number average molecular weight and the weight average molecular weight of the polymer X is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.
  • the weight average molecular weight of the polymer in the present disclosure can be measured by GPC (gel permeation chromatography), and various commercially available devices can be used as the measuring device. A known measurement technique can be used.
  • the weight average molecular weight is measured by gel permeation chromatography (GPC) using HLC (registered trademark)-8220 GPC (manufactured by Tosoh Corporation) as a measuring device and TSKgel (registered trademark) Super HZM-M (4) as a column.
  • GPC gel permeation chromatography
  • THF tetrahydrofuran
  • the measurement conditions are as follows: the sample concentration is 0.2 mass %, the flow rate is 0.35 ml/min, the sample injection amount is 10 ⁇ L, and the measurement temperature is 40° C., using a differential refractive index (RI) detector. be able to.
  • the calibration curve is “standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A-5000”, It can be manufactured using any of the seven samples of “A-2500” and “A-1000”.
  • the production method (synthesis method) of the polymer X is not particularly limited, but, for example, a monomer for forming the structural unit A, and, if necessary, a monomer for forming the structural unit B and a structural unit C are given. It can be synthesized by polymerizing with a polymerization initiator in an organic solvent containing a monomer for forming a. It can also be synthesized by a so-called polymer reaction.
  • the photosensitive resin layer in the present disclosure preferably contains the polymer component in a ratio of 50% by mass to 99.9% by mass with respect to the total mass of the photosensitive resin layer, 70 It is more preferable that the content is in the range of mass% to 98 mass %.
  • the photosensitive resin layer preferably contains the polymer X in a proportion of 50% by mass to 99.9% by mass, and 70% by mass with respect to the total mass of the photosensitive resin layer. More preferably, it is contained in a proportion of about 98% by mass.
  • the photosensitive resin layer contains, as a polymer component, a structural unit having an acid group protected by an acid-decomposable group, in addition to the polymer X, as long as the effect of the photosensitive transfer material according to the present disclosure is not impaired.
  • the polymer may be further included (also referred to as "other polymer”).
  • the polymer component in the present disclosure means the polymer including the polymer X and other polymers added as necessary.
  • the compound applicable to the below-mentioned crosslinking agent, dispersant, and surfactant shall not be included in the polymer component.
  • the content of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less, based on all polymer components. It is more preferably 20% by mass or less.
  • the photosensitive resin layer may include only one type of other polymer, or may include two or more types thereof.
  • polyhydroxystyrene can be used, and commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, manufactured by Sartomer).
  • SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F aboveve, manufactured by Sartomer.
  • ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 all manufactured by Toagosei Co., Ltd.
  • Joncryl 690, Joncr. , Joncryl 67, and Joncryl 586 can also be used.
  • the photosensitive resin layer contains a photo-acid generator.
  • the photo-acid generator used in the present disclosure is a compound capable of generating an acid when irradiated with an actinic ray such as an ultraviolet ray, a deep ultraviolet ray, an X-ray or an electron beam.
  • the photo-acid generator used in the present disclosure is preferably a compound that reacts with an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm to generate an acid, but its chemical structure is not limited.
  • a photo-acid generator which is not directly sensitive to actinic rays having a wavelength of 300 nm or more, when used in combination with a sensitizer, it is a compound which is sensitive to actinic rays having a wavelength of 300 nm or more and generates an acid. It can be preferably used in combination.
  • the photoacid generator used in the present disclosure is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and a pKa of 2 or less. Particularly preferred are photoacid generators that generate the above acid.
  • the lower limit of pKa is not particularly limited, but is preferably -10.0 or more, for example.
  • the photo-acid generator contains a photo-acid generator capable of generating an alkylsulfonic acid having 1 to 4 carbon atoms from the viewpoints of stability over time after exposure, linearity of the obtained pattern, and suppression of development residue. Is preferable, and it is more preferable to include a photoacid generator that generates an alkylsulfonic acid having 1 to 4 carbon atoms and a photoacid generator that generates an arylsulfonic acid.
  • the photoacid generator that generates the alkylsulfonic acid is a photoacid generator that generates methanesulfonic acid (mesyl acid) from the viewpoints of temporal stability after exposure, linearity of the obtained pattern, and development residue suppression. Is preferred. Further, the photoacid generator that generates the arylsulfonic acid generates p-toluenesulfonic acid (tosylic acid) from the viewpoints of stability with time after exposure, linearity of the obtained pattern, and suppression of development residue. It is preferably a photoacid generator.
  • a photoacid generator that generates an acid with a pKa of 4.0 or less, a photoacid generator that generates an acid with a pKa of 3.0 or less, or a photoacid generator that generates an acid with a pKa of 2.0 or less. If so, a relatively strong acid will be generated.
  • Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.
  • Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. Of these, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.
  • the ionic photoacid generator described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.
  • nonionic photoacid generator examples include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.
  • the photo-acid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion.
  • Specific examples of the trichloromethyl-s-triazines, diazomethane compounds and imidosulfonate compounds include the compounds described in paragraphs 0083 to 0088 of JP 2011-221494A.
  • oxime sulfonate compound those described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 can be preferably used.
  • the photo-acid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and more preferably contains oxime sulfonate compounds. ..
  • examples of preferable photoacid generators include photoacid generators having the following structures.
  • the photosensitive resin layer may contain one photoacid generator alone, or may contain two or more photoacid generators. From the viewpoint of sensitivity and resolution, the content of the photo-acid generator in the photosensitive resin layer is preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer, and 0 It is more preferably from 0.5% by mass to 5% by mass.
  • the above-mentioned photosensitive resin layer in the present disclosure can contain other additives in addition to the polymer X, the photo-acid generator and the solvent, if necessary.
  • additives known ones can be used, and examples thereof include a plasticizer, a sensitizer, a heterocyclic compound, an alkoxysilane compound, a basic compound, a rust preventive, and a surfactant.
  • plasticizer, sensitizer, heterocyclic compound and alkoxysilane compound include those described in paragraphs 0097 to 0119 of International Publication No. 2018/179640.
  • the photosensitive resin layer in the photosensitive transfer material according to the present disclosure may contain a solvent.
  • the solvent may remain.
  • the content of the solvent in the photosensitive resin layer is preferably 5% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less, based on the total mass of the photosensitive resin layer. More preferable.
  • the photosensitive resin layer preferably further contains a basic compound.
  • the basic compound can be arbitrarily selected and used from the basic compounds used in the chemically amplified resist. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include the compounds described in paragraphs 0204 to 0207 of JP 2011-221494 A, the contents of which are incorporated herein.
  • As the basic compound N-cyclohexyl-N'-[2-(4-morpholinyl)ethyl]thiourea (CMTU) can be preferably used. Further, examples of commercially available CMTU include those manufactured by Toyo Kasei Co., Ltd.
  • a benzotriazole compound is preferable from the viewpoints of stability over time after exposure, linearity of the obtained pattern, and suppression of development residue.
  • the benzotriazole compound is not limited as long as it has a benzotriazole skeleton, and a known benzotriazole compound can be used.
  • benzotriazole compound examples include 1,2,3-benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, 5-carboxybenzotriazole, 1-(hydroxymethyl)-1H -Benzotriazole, 1-acetyl-1H-benzotriazole, 1-aminobenzotriazole, 9-(1H-benzotriazol-1-ylmethyl)-9H-carbazole, 1-chloro-1H-benzotriazole, 1-(2- Pyridinyl)benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-ethylbenzotriazole, 1-(1'-hydroxyethyl)benzotriazole, 1-(2'-hydroxyethyl)benzotriazole, 1-propyl Benzotriazole, 1-(1'-hydroxypropyl)benzotriazole, 1-(2'-hydroxypropyl)benzotriazole,
  • the photosensitive resin layer may contain one basic compound alone, or may contain two or more basic compounds.
  • the content of the basic compound is preferably 0.001% by mass to 5% by mass, and more preferably 0.005% by mass to 3% by mass, based on the total mass of the photosensitive resin layer. ..
  • the photosensitive resin layer preferably contains a surfactant from the viewpoint of thickness uniformity.
  • the surfactant include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants.
  • a preferred surfactant is a nonionic surfactant.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. ..
  • the surfactant for example, the surfactants described in paragraphs 0120 to 0125 of International Publication No. 2018/179640 can be used.
  • a commercially available product of the surfactant for example, Megafac F-552 or F-554 (above, manufactured by DIC Corporation) can be used.
  • the surfactants described in Paragraph 0017 of Japanese Patent No. 4502784 and Paragraph 0060 to Paragraph 0071 of Japanese Patent Laid-Open No. 2009-237362 can be used.
  • the photosensitive resin layer may contain one type of surfactant alone, or may contain two or more types of surfactants.
  • the content of the surfactant is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive resin layer. ..
  • the photosensitive resin layer in the present disclosure as other additives, metal oxide particles, antioxidants, dispersants, acid multiplying agents, development accelerators, conductive fibers, colorants, thermal radical polymerization initiation
  • additives such as agents, thermal acid generators, UV absorbers, thickeners, cross-linking agents, and organic or inorganic suspending agents can be further added. Preferred embodiments of these components are described in paragraphs 0165 to 0184 of JP-A-2014-85643, and the contents of this publication are incorporated herein.
  • the average thickness of the photosensitive resin layer is preferably 0.5 ⁇ m to 20 ⁇ m.
  • the average thickness of the photosensitive resin layer is more preferably 0.8 ⁇ m to 15 ⁇ m, and particularly preferably 1.0 ⁇ m to 10 ⁇ m.
  • the method for measuring the average thickness of each layer in the present disclosure is performed by observing a cross section in a direction perpendicular to the surface direction of the transfer material with a scanning electron microscope (SEM), measuring the layer thickness at 10 points or more, and averaging the measured values. Including the value as the average thickness.
  • SEM scanning electron microscope
  • the photosensitive resin layer in the present disclosure can be formed by preparing, coating and drying a photosensitive resin composition containing a component used for forming the photosensitive resin layer and a solvent. It is also possible to prepare a composition by dissolving each component in advance in a solvent and then mixing the obtained solutions at a predetermined ratio.
  • the composition prepared as described above may be filtered using, for example, a filter having a pore size of 0.2 ⁇ m to 30 ⁇ m.
  • the photosensitive resin composition according to the present disclosure can be formed by applying the photosensitive resin composition onto a temporary support or a cover film and drying it.
  • the coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, inkjet coating and the like. Further, the photosensitive resin layer may be formed on the intermediate layer or other layers described below on the temporary support or the cover film.
  • the photosensitive resin composition preferably contains a component used for forming the photosensitive resin layer and a solvent.
  • a photosensitive resin layer can be preferably formed by adding a solvent to each component to adjust the viscosity, and applying and drying.
  • solvent known solvents can be used, and for example, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 can be used.
  • the solvent having a vapor pressure at 20° C. of 1 kPa or more and 16 kPa or less described in paragraph 0014 of JP-A-2018-177889 can be preferably used.
  • the solvent that can be used in the present disclosure may be used alone or in combination of two kinds.
  • the content of the solvent when applying the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. It is more preferably from about 900 parts by mass.
  • the photosensitive transfer material according to the present disclosure preferably has an intermediate layer.
  • the intermediate layer preferably contains the polymer described below.
  • the intermediate layer can include a polymer.
  • the polymer used for the intermediate layer is preferably a water-soluble resin or an alkali-soluble resin.
  • water-soluble means that the solubility in 100 g of water having a pH of 7.0 at 22° C. is 0.1 g or more
  • alkali-soluble means 1 mass of sodium carbonate at 22° C. %, the solubility in 100 g of the aqueous solution is 0.1 g or more.
  • the term "water-soluble or alkali-soluble” may be either water-soluble or alkali-soluble, or water-soluble and alkali-soluble. The solubility of the polymer in 100 g of water having a pH of 7.0 at 22° C.
  • the water-soluble resin is preferably 1 g or more, more preferably 5 g or more.
  • the water-soluble resin include cellulose resins, polyvinyl alcohol resins, polyvinylpyrrolidone resins, acrylamide resins, (meth)acrylate resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and resins such as copolymers thereof.
  • a cellulose resin is preferable, and at least one resin selected from the group consisting of hydroxypropyl cellulose and hydroxypropylmethyl cellulose is more preferable.
  • an alkali-soluble acrylic resin is preferable, and an acrylic resin having an acid group which may form a salt is more preferable.
  • the intermediate layer may contain one kind of polymer alone, or may contain two or more kinds of polymers. From the viewpoint of adhesiveness, the content of the polymer is preferably 20% by mass to 100% by mass, more preferably 50% by mass to 100% by mass, based on the total mass of the intermediate layer.
  • the intermediate 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 contains a pH-sensitive dye whose maximum absorption wavelength changes with pH.
  • the maximum absorption wavelength changes means that a dye in a colored state is decolored, a dye in a decolored state is colored, and a dye in a colored state is changed to a coloring state of another hue. It may refer to any of the aspects.
  • the pH-sensitive dye is more preferably a latent dye that is decolorized by the acid generated from the photo-acid generator.
  • the method for measuring the maximum absorption wavelength in the present disclosure is to measure a transmission spectrum in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) at 25° C. in an atmosphere of air.
  • UV3100 manufactured by Shimadzu Corporation
  • the wavelength at which the light intensity becomes a minimum (maximum absorption wavelength) shall be measured.
  • Examples of dyes that are decolorized by exposure include leuco compounds, diphenylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.
  • leuco compounds are preferable as the dye from the viewpoint of visibility.
  • the leuco compound include triarylmethane-based (eg, triphenylmethane-based), spiropyran-based, fluorane-based, diphenylmethane-based, rhodamine lactam-based, indolylphthalide-based, leucoauramine-based leuco compounds.
  • leuco compounds having a triarylmethane skeleton are preferable, and triphenylmethane dyes are more preferable.
  • the leuco compound preferably has a lactone ring, a sultin ring, or a sultone ring, and a lactone ring, a sultin ring, or a compound in which the sultone ring is opened or closed, and has a sultone ring.
  • the dye is preferably a water-soluble compound from the viewpoint of preventing defects due to precipitation of the dye.
  • the solubility of the dye in 100 g of water having a pH of 7.0 at 22° C. is preferably 1 g or more, more preferably 5 g or more.
  • the intermediate layer may include one type of dye alone, or may include two or more types of dye. From the viewpoint of visibility, the content of the dye in the intermediate layer is preferably 0.01% by mass to 10% by mass, and is 0.5% by mass to 5% by mass, based on the total mass of the intermediate layer. It is more preferable that the content is 1.0% by mass to 3.0% by mass.
  • the intermediate layer preferably contains a surfactant from the viewpoint of thickness uniformity.
  • a surfactant having a fluorine atom any of a surfactant having a fluorine atom, a surfactant having a silicon atom, and a surfactant having neither a fluorine atom nor a silicon atom can be used.
  • the surfactant is preferably a surfactant having a fluorine atom from the viewpoint of suppressing the generation of streaks in the photosensitive resin layer and the intermediate layer, and the adhesiveness, and a perfluoroalkyl group and a polyalkyleneoxy group. It is more preferable that the surfactant has a group.
  • any of anionic, cationic, nonionic (nonionic) or amphoteric can be used, but the preferred surfactant is a nonionic surfactant.
  • the surfactant preferably has a solubility of 1 g or more in 100 g of water at 25° C. from the viewpoint of suppressing the precipitation of the surfactant.
  • the intermediate layer may include one type of surfactant alone, or may include two or more types of surfactant.
  • the content of the surfactant in the intermediate layer is 0.05% by mass to 2.% with respect to the total mass of the intermediate layer from the viewpoints of suppressing the generation of streaks in the photosensitive resin layer and the intermediate layer and adhering. It is preferably 0% by mass, more preferably 0.1% by mass to 1.0% by mass, and particularly preferably 0.2% by mass to 0.5% by mass.
  • the intermediate layer may include an inorganic filler.
  • the inorganic filler in the present disclosure is not particularly limited. Examples thereof include silica particles, aluminum oxide particles and zirconium oxide particles, and silica particles are more preferable. From the viewpoint of transparency, particles having a small particle size are preferable, and particles having an average particle size of 100 nm or less are more preferable. For example, if it is a commercially available product, Snowtex (registered trademark) is preferably used.
  • the volume fraction of the particles in the intermediate layer (volume ratio of the particles in the intermediate layer) is 5% to 90% with respect to the total volume of the intermediate layer from the viewpoint of adhesion between the intermediate layer and the photosensitive layer. It is preferably 10% to 80%, more preferably 20% to 60%.
  • the intermediate layer may contain a pH adjuster.
  • the pH adjusting agent in the present disclosure is not particularly limited. Examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, organic amines, organic ammonium salts and the like. Sodium hydroxide is preferred from the viewpoint of water solubility. From the viewpoint of adhesiveness between the photosensitive resin layer and the intermediate layer, organic ammonium salts are preferable.
  • the average thickness of the intermediate layer is preferably 0.3 ⁇ m to 10 ⁇ m, and more preferably 0.3 ⁇ m to 5 ⁇ m, from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer and pattern formability. It is particularly preferably 0.3 ⁇ m to 2 ⁇ m. Further, the average thickness of the intermediate layer is preferably thinner than the average thickness of the photosensitive resin layer.
  • the intermediate layer can have two or more layers.
  • the average thickness of each layer is not particularly limited as long as it is within the above range, but of the two or more layers in the intermediate layer, the average of the layers closest to the photosensitive resin layer.
  • the thickness is preferably 0.3 ⁇ m to 10 ⁇ m, more preferably 0.3 ⁇ m to 5 ⁇ m, and particularly preferably 0.3 ⁇ m to 2 ⁇ m, from the viewpoints of the adhesiveness between the intermediate layer and the photosensitive resin layer and the pattern formability. ..
  • the intermediate layer in the present disclosure can be formed by preparing a composition for forming an intermediate layer containing a component used for forming the intermediate layer and a water-soluble solvent, coating and drying the composition. It is also possible to prepare a composition by dissolving each component in advance in a solvent and then mixing the obtained solutions in a predetermined ratio.
  • the composition prepared as described above may be filtered using a filter having a pore size of 3.0 ⁇ m.
  • the intermediate layer can be formed on the temporary support by applying the intermediate layer-forming composition to the temporary support and drying the composition.
  • the coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, inkjet coating and the like.
  • the intermediate layer forming composition preferably contains a component used for forming the intermediate layer and a water-soluble solvent.
  • a water-soluble solvent is contained in each component to adjust the viscosity, and the intermediate layer can be suitably formed by coating and drying.
  • water-soluble solvent a known water-soluble solvent can be used, and examples thereof include water and alcohols having 1 to 6 carbon atoms, and water is preferable.
  • the alcohol having 1 to 6 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, and n-hexanol. Among them, it is preferable to use at least one selected from the group consisting of methanol, ethanol, n-propanol, and isopropanol.
  • the photosensitive transfer material according to the present disclosure preferably has a cover film on the surface of the photosensitive transfer material opposite to the surface on which the temporary support is provided.
  • the cover film include a resin film and paper, and a resin film is particularly preferable from the viewpoint of strength and flexibility.
  • the resin film include polyethylene film, polypropylene film, polyethylene terephthalate film, cellulose triacetate film, polystyrene film and polycarbonate film. Among them, polyethylene film, polypropylene film and polyethylene terephthalate film are preferable.
  • the average thickness of the cover film is not particularly limited, and one having a thickness of 1 ⁇ m to 2 mm is preferable.
  • the photosensitive transfer material according to the present disclosure may have a layer other than those described above (hereinafter, also referred to as “other layer”).
  • the other layer include a contrast enhancement layer and a thermoplastic resin layer.
  • paragraph 0134 of International Publication No. 2018/179640 regarding a preferred embodiment of the thermoplastic resin layer, paragraphs 0189 to 0193 of JP-A-2014-85643, and further other layers are preferred. Aspects are described in paragraphs 0194 to 0196 of JP-A-2014-85643, respectively, and the contents of this publication are incorporated herein.
  • the photosensitive transfer material 100 shown in FIG. 1 comprises a temporary support 12, a transfer layer 14 formed by stacking a photosensitive resin layer 14-1 and an intermediate layer 14-2, and a cover film 16 stacked in this order.
  • transfer layer refers to both the laminated photosensitive resin layer and the intermediate layer.
  • the method for manufacturing the photosensitive transfer material according to the present disclosure is not particularly limited, and a known manufacturing method such as a known method for forming each layer can be used.
  • the method for producing the photosensitive transfer material according to the present disclosure includes a step of applying an intermediate layer-forming composition on a temporary support and drying the intermediate layer to form an intermediate layer, and a photosensitive resin composition on the intermediate layer.
  • a preferable method is a method including a step of applying and drying to form a photosensitive resin layer.
  • the method for producing a photosensitive transfer material according to the present disclosure preferably further includes a step of providing a cover film on the photosensitive resin layer after the step of forming the photosensitive resin layer.
  • the method for producing a resin pattern according to the present disclosure is not particularly limited as long as it is a method for producing a resin pattern using the photosensitive transfer material according to the present disclosure, but the temporary support in the photosensitive transfer material according to the present disclosure is not particularly limited.
  • a step of bringing the outermost layer on the side having the photosensitive resin layer into contact with the substrate and attaching them hereinafter, sometimes referred to as “attaching step”
  • exposing step a step of pattern-exposing the photosensitive resin layer
  • exposure step a step of developing the exposed photosensitive resin layer to form a pattern
  • developer step a step of developing the exposed photosensitive resin layer to form a pattern.
  • the substrate in the method for producing a resin pattern according to the present disclosure is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on its surface.
  • the method for manufacturing the circuit wiring according to the present disclosure may be a method using the photosensitive transfer material according to the present disclosure, but a photosensitive resin layer is formed on the temporary support of the photosensitive transfer material according to the present disclosure.
  • a step of bonding the outermost layer on the side having the conductive layer to a substrate having a conductive layer hereinafter, also referred to as “bonding step”), and pattern-exposing the photosensitive resin layer in the bonded photosensitive transfer material.
  • a step of forming a resin pattern by developing at least the pattern-exposed photosensitive resin layer, and a step of etching the substrate in a region where the resin pattern is not arranged (hereinafter referred to as "etching step”).
  • etching step a step of etching the substrate in a region where the resin pattern is not arranged.
  • the substrate in the circuit wiring manufacturing method according to the present disclosure is preferably a substrate having the conductive layer on its surface.
  • the circuit wiring manufacturing method preferably includes a mode in which four steps of the bonding step, the exposure step, the development step, and the etching step are set as one set and repeated a plurality of times. Furthermore, since the substrate can be reused (reworked) as described below, the method for manufacturing circuit wiring according to the present disclosure includes four steps of the bonding step, the exposure step, the development step, and the etching step. After that, a preferable mode is one in which the exposure step is performed on the resin pattern, and the developing step and the etching step are further performed.
  • the above-mentioned photosensitive resin layer is of a positive type, which leaves an area not irradiated with actinic rays as an image.
  • the above-mentioned photosensitive resin layer by irradiating with actinic rays, for example, in order to increase the solubility of the exposed parts by using a photosensitizer which is irradiated with the actinic rays to generate an acid, the exposed parts and unexposed parts are exposed at the time of pattern exposure. If none of the parts are cured and the obtained pattern shape is defective, the substrate can be reused (reworked) by exposing the entire surface.
  • WO 2006/190405 the contents of which are incorporated herein.
  • the method for producing a resin pattern according to the present disclosure, or the method for producing a circuit wiring according to the present disclosure provides the outermost layer on the side having a photosensitive resin layer with respect to the temporary support in the photosensitive transfer material according to the present disclosure. It is preferable to include a step (bonding step) of bringing the substrate, preferably a substrate having a conductive layer, into contact with each other for bonding. In the laminating step, it is preferable to perform pressure bonding so that the conductive layer and the outermost layer on the side having the photosensitive resin layer with respect to the temporary support in the photosensitive transfer material according to the present disclosure come into contact with each other. ..
  • the patterned photosensitive resin layer after exposure and development can be preferably used as an etching resist when etching the conductive layer.
  • the method for pressure-bonding the substrate and the photosensitive transfer material is not particularly limited, and known transfer methods and laminating methods can be used.
  • the sticking of the photosensitive transfer material to the substrate is preferably performed by stacking the outermost layer of the photosensitive transfer material on the side having the photosensitive resin layer on the substrate and applying pressure and heating with a roll or the like.
  • a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of improving productivity can be used.
  • the method of manufacturing circuit wiring according to the present disclosure is preferably performed by a roll-to-roll method.
  • the base material forming the substrate is preferably a resin film.
  • the roll-to-roll method will be described below.
  • the roll-to-roll method uses a substrate that can be wound and unwound as a substrate, and unwinds the substrate or a structure including the substrate before any step included in the method for manufacturing circuit wiring ( Also referred to as "winding step") and a step of winding a structure including a base material or a substrate after any step (also referred to as “winding step”). (Preferably, all steps or all steps other than the heating step) are performed while a structure including a base material or a substrate is being conveyed.
  • the unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and known methods may be used in the manufacturing method to which the roll-to-roll method is applied.
  • the substrate used in the present disclosure is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface of the base material.
  • the substrate having a conductive layer may have a conductive layer on a base material such as glass, silicon, or a film, and any layer may be formed if necessary.
  • the substrate is preferably transparent.
  • the refractive index of the base material is preferably 1.50 to 1.52.
  • the base material may be composed of a translucent base material such as a glass base material, and a tempered glass typified by Corning's gorilla glass can be used.
  • the materials used in JP 2010-86684 A, JP 2010-152809 A and JP 2010-257492 A can be preferably used.
  • a resin film base material is used as the base material, it is more preferable to use a base material having small optical distortion and a base material having high transparency.
  • Specific examples of the material include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.
  • the substrate having the conductive layer on the base material is preferably a film base material from the viewpoint of manufacturing by a roll-to-roll method.
  • the base material is particularly preferably a sheet-shaped resin composition.
  • the conductive layer formed on the base material examples include any conductive layer used for general circuit wiring or touch panel wiring.
  • the conductive layer at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer is selected from the viewpoints of conductivity and thin wire forming property.
  • Preferred examples include:
  • the conductive layer is more preferably a metal layer, and particularly preferably a copper layer or a silver layer.
  • the substrate may have one conductive layer or two or more conductive layers. In the case of two or more layers, it is preferable to have conductive layers of different materials. Examples of the material of the conductive layer include metals and conductive metal oxides.
  • Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au.
  • Examples of the conductive metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO 2 . It should be noted that “conductivity” in the present disclosure means that the volume resistivity is less than 1 ⁇ 10 6 ⁇ cm. The volume resistivity is preferably less than 1 ⁇ 10 4 ⁇ cm.
  • At least one conductive layer of the plurality of conductive layers preferably contains a conductive metal oxide.
  • the conductive layer is preferably an electrode pattern corresponding to the sensor of the visual recognition part used in the capacitive touch panel or a wiring of the peripheral extraction part.
  • the method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure preferably includes a step (exposure step) of pattern-exposing the photosensitive resin layer after the bonding step.
  • the detailed arrangement and specific size of the pattern are not particularly limited.
  • a display device for example, a touch panel
  • At least a part is preferably a fine wire of 100 ⁇ m or less, and more preferably a fine wire of 70 ⁇ m or less.
  • the light source used for exposure may be appropriately selected and used as long as it irradiates light in a wavelength range capable of exposing the photosensitive resin layer (for example, 365 nm, 405 nm, etc.).
  • a wavelength range capable of exposing the photosensitive resin layer for example, 365 nm, 405 nm, etc.
  • Specific examples include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).
  • the exposure dose is preferably 5 mJ/cm 2 to 200 mJ/cm 2 , and more preferably 10 mJ/cm 2 to 100 mJ/cm 2 .
  • pattern exposure may be performed after peeling the temporary support from the photosensitive resin layer, pattern exposure is performed via the temporary support before peeling the temporary support, and then the temporary support is peeled. You may. In order to prevent the contamination of the mask due to the contact between the photosensitive resin layer and the mask and to avoid the influence of foreign matter attached to the mask on the exposure, it is preferable to perform the pattern exposure without peeling the temporary support.
  • the pattern exposure may be exposure through a mask or direct exposure using a laser or the like.
  • a method of manufacturing a resin pattern according to the present disclosure, or a method of manufacturing a circuit wiring according to the present disclosure includes a step of developing the exposed photosensitive resin layer after the exposing step to form a resin pattern (developing step). ) Is preferably included.
  • the photosensitive transfer material has an intermediate layer
  • the exposed intermediate layer is removed together with the exposed photosensitive resin layer in the developing step.
  • the intermediate layer in the unexposed area may also be removed in the form of being dissolved or dispersed in the developing solution.
  • the developer is not particularly limited as long as it can remove the non-image part of the photosensitive resin layer, and known developers such as the developer described in JP-A-5-72724 can be used. ..
  • the developing solution is preferably a developing solution in which the exposed portion (positive type) of the photosensitive resin layer has a dissolution type developing behavior.
  • an alkaline aqueous solution-based developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol/L (liter) to 5 mol/L is preferable.
  • the developer may further contain a water-soluble organic solvent, a surfactant and the like. Examples of the developer preferably used in the present disclosure include the developers described in paragraph 0194 of WO 2015/093271.
  • the development method is not particularly limited, and may be paddle development, shower development, shower and spin development, dip development, or the like.
  • Explaining shower development here the exposed portion can be removed by spraying a developing solution onto the photosensitive resin layer after exposure with a shower. Further, after the development, it is preferable to remove a development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like.
  • the liquid temperature of the developer is preferably 20°C to 40°C.
  • the method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure further includes a post-baking step of heat-treating a pattern including a photosensitive resin layer obtained by development. Good.
  • the post-baking heating is preferably performed in an environment of 8.1 kPa to 121.6 kPa, more preferably 50.66 kPa or more. On the other hand, it is more preferably performed in an environment of 111.46 kPa or less, and particularly preferably in an environment of 101.3 kPa or less.
  • the post-baking temperature is preferably 80°C to 250°C, more preferably 110°C to 170°C, and particularly preferably 130°C to 150°C.
  • the post-baking time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes. Post-baking may be performed in an air environment or a nitrogen substitution environment.
  • the resin pattern manufacturing method according to the present disclosure may further include other steps such as a post exposure step.
  • the circuit wiring manufacturing method according to the present disclosure may include other steps such as a post-exposure step before the etching step described below.
  • the circuit wiring manufacturing method according to the present disclosure preferably includes a step (etching step) of etching the substrate in a region where the resin pattern is not arranged.
  • the pattern formed from the photosensitive resin layer in the developing step is used as an etching resist to etch the conductive layer.
  • known methods such as the method described in paragraphs 0048 to 0054 of JP 2010-152155 A, a method by dry etching such as a known plasma etching and the like can be applied.
  • an etching method a generally used wet etching method in which an object to be etched is immersed in an etching solution can be used.
  • an acidic type or alkaline type etching solution may be appropriately selected according to the object of etching.
  • the acidic type etching solution include an aqueous solution of an acidic component such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid alone, a mixed aqueous solution of an acidic component and a salt of ferric chloride, ammonium fluoride, potassium permanganate, or the like. To be done.
  • the acidic component a component obtained by combining a plurality of acidic components may be used.
  • an aqueous solution of an alkali component alone such as sodium hydroxide, potassium hydroxide, ammonia, an organic amine, a salt of an organic amine such as tetramethylammonium hydroxide, an alkali component and potassium permanganate, etc. Examples include mixed aqueous solutions of salts.
  • a component obtained by combining a plurality of alkaline components may be used as the alkaline component.
  • the temperature of the etching solution is not particularly limited, but it is preferably 45° C. or lower.
  • the resin pattern used as an etching mask (etching pattern) in the present disclosure preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45° C. or lower.
  • the resin pattern has such resistance, the photosensitive resin layer is prevented from peeling off during the etching process, and the portion where the photosensitive resin layer does not exist is selectively etched.
  • a cleaning process for cleaning the etched substrate and a drying process for drying the cleaned substrate may be performed, if necessary.
  • a step of removing the resin pattern (removal step).
  • the removing step is not particularly limited and may be performed as necessary, but is preferably performed after the etching step.
  • the method of removing the remaining photosensitive resin layer is not particularly limited, but a method of removing it by a chemical treatment can be mentioned, and it is particularly preferable to use a removing liquid.
  • the method for removing the photosensitive resin layer is preferably at 30° C. to 80° C., more preferably at 50° C. to 80° C., and the substrate having the photosensitive resin layer or the like is immersed in the removing solution for 1 minute to 30 minutes while stirring. There is a method.
  • the removing liquid examples include inorganic alkali components such as sodium hydroxide and potassium hydroxide, or organic alkalis such as primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.
  • a removing solution obtained by dissolving the components in water, dimethyl sulfoxide, N-methylpyrrolidone or a mixed solution thereof can be used.
  • a removing solution may be used to remove by a spray method, a shower method, a paddle method, or the like.
  • the circuit wiring manufacturing method preferably includes a step of exposing the entire surface of the photosensitive resin layer (also referred to as “entire surface exposure step”) before the removing step. Further, if necessary, a step of heating the above-mentioned photosensitive resin layer which is entirely exposed (also referred to as “heating step”) may be included. The whole surface exposure step and the heating step are preferably performed after the etching step and before the removal step.
  • the heating step can further improve the reaction rate of the photoacid generator and the reaction rate of the generated acid with the positive photosensitive resin, and as a result, the removal performance. Is improved.
  • the light source used for the exposure in the whole surface exposure process 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 that emits light having the same wavelength as that in the exposure step.
  • Exposure amount in the overall exposure step is preferably 5mJ / cm 2 ⁇ 1,000mJ / cm 2, more preferably 10mJ / cm 2 ⁇ 800mJ / cm 2, 100mJ / cm Particularly preferably, it is 2 to 500 mJ/cm 2 .
  • the exposure amount in the whole surface exposure process is preferably equal to or more than the exposure amount in the above exposure process, and more preferably more than the exposure amount in the above exposure process.
  • the circuit wiring manufacturing method according to the present disclosure may include any step (other steps) other than the above.
  • the following steps may be mentioned, but the present invention is not limited to these steps.
  • the exposure step, the development step, and other steps in the present disclosure the methods described in paragraphs 0035 to 0051 of JP 2006-23696 A can also be suitably used in the present disclosure.
  • ⁇ Cover film peeling process>> A method of manufacturing a resin pattern according to the present disclosure, or a method of manufacturing a circuit wiring according to the present disclosure, in a case where the photosensitive transfer material according to the present disclosure has a cover film, a step of peeling the cover film of the photosensitive transfer material. (It may be referred to as a “cover film peeling step”).
  • the method of peeling off the cover film is not limited, and a known method can be applied.
  • the circuit wiring manufacturing method can include a step of performing a process of reducing the visible light reflectance of some or all of the plurality of conductive layers on the base material.
  • the treatment for lowering the visible light reflectance include oxidation treatment.
  • the visible light reflectance can be reduced by blackening by oxidizing copper into copper oxide.
  • the treatment for reducing the visible light reflectance see paragraphs 0017 to 0025 of JP-A-2014-150118, and paragraphs 0041, 0042, 0048 and 0058 of JP-A-2013-206315. There is a description, and the content of this publication is incorporated herein.
  • the circuit wiring manufacturing method preferably also includes a step of forming an insulating film on the formed circuit wiring and a step of forming a new conductive layer on the insulating film.
  • the step of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be used.
  • an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
  • a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.
  • the circuit wiring manufacturing method uses a substrate having a plurality of conductive layers on both surfaces of a base material, and forms a circuit sequentially or simultaneously on the conductive layers formed on both surfaces of the base material. Is also preferable. With such a configuration, it is possible to form the touch panel circuit wiring in which the first conductive pattern is formed on one surface of the substrate and the second conductive pattern is formed on the other surface. It is also preferable that the touch panel circuit wiring having such a configuration is formed from both sides of the base material by roll-to-roll.
  • the circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure can be applied to various devices.
  • the device provided with the circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure is, for example, an input device or the like, preferably a touch panel, and more preferably a capacitance type touch panel.
  • the input device can be applied to display devices such as organic EL display devices and liquid crystal display devices.
  • the method for manufacturing the touch panel according to the present disclosure may be a method that uses the photosensitive transfer material according to the present disclosure, but a side having a photosensitive resin layer with respect to the temporary support in the photosensitive transfer material according to the present disclosure.
  • bonding step pattern exposing the photosensitive resin layer (exposure step), and developing the exposed photosensitive resin layer.
  • exposure step pattern exposing the photosensitive resin layer
  • developing step a step of forming a resin pattern
  • etching step etching the substrate in an area where the resin pattern is not arranged
  • the method for manufacturing a touch panel In the method for manufacturing a touch panel according to the present disclosure, specific aspects of each step, and embodiments such as the order of performing each step are as described in the above-mentioned “method for manufacturing circuit wiring”. The preferred embodiment is also the same.
  • a known touch panel manufacturing method can be referred to other than the above.
  • the touch panel manufacturing method according to the present disclosure may include any step (other steps) other than the above.
  • FIGS. 2 and 3 An example of a mask pattern used in the method for manufacturing the touch panel according to the present disclosure is shown in FIGS. 2 and 3.
  • pattern A the pattern shown in FIG. 2
  • pattern B the pattern shown in FIG. 3
  • SL and G are non-image portions (light shielding portions)
  • DL is alignment.
  • This is a hypothetical view of the matching frame.
  • the method for manufacturing a touch panel according to the present disclosure for example, by exposing the photosensitive resin layer through the mask having the pattern A shown in FIG. 2, the circuit wiring having the pattern A corresponding to SL and G is formed.
  • Touch panel can be manufactured. Specifically, it can be prepared by the method shown in FIG. 1 of WO 2016/0190405.
  • G is a portion where a transparent electrode (touch panel electrode) is formed
  • SL is a portion where the wiring of the peripheral extraction portion is formed.
  • the touch panel according to the present disclosure is a touch panel including at least circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure. Further, the touch panel according to the present disclosure preferably has at least a transparent substrate, an electrode, and an insulating layer or a protective layer.
  • the detection method in the touch panel according to the present disclosure may be any known method such as a resistance film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Of these, the capacitance method is preferable.
  • the touch panel type a so-called in-cell type (for example, those described in FIGS. 5, 6, 7, and 8 of Japanese Patent Publication No.
  • Examples of the touch panel according to the present disclosure include those described in paragraph 0229 of JP-A-2017-120345.
  • the film according to the present disclosure has a particle-containing layer containing particles on at least one surface, has a haze value of 0.2% or less, and has a surface roughness Ra of the surface having the particle-containing layer of 0. It is from 0.02 ⁇ m to 0.20 ⁇ m.
  • the use of the film according to the present disclosure is not particularly limited.
  • the film according to the present disclosure can be preferably used as a protective film, a release film, or a temporary support for a photosensitive transfer material, and can be particularly preferably used as a temporary support for a photosensitive transfer material.
  • the film according to the present disclosure is a novel film, has a small haze value, is excellent in transparency, and, as described in the temporary support in the photosensitive transfer material according to the present disclosure, suppresses wrinkling during transport. Have sex.
  • the conventional film those described in JP-A-2017-78852 or JP-A-2000-221688 are known, but the film described in JP-A-2017-78852 is not suitable for transporting. The generation of wrinkles could not be suppressed sufficiently. Further, the film described in JP-A-2000-221688 has insufficient transparency, and it is not possible to achieve both transparency and wrinkle suppression during transport. Further, Japanese Patent Laid-Open No. 2000-221688 does not describe any positive photosensitive transfer material.
  • the details of the configuration of the preferred embodiment of the film according to the present disclosure are the same as the details of the configuration of the preferred embodiment of the temporary support in the photosensitive transfer material according to the present disclosure, except for the embodiments described later.
  • the film according to the present disclosure preferably contains a polyester resin, more preferably polyethylene terephthalate, from the viewpoint of optical properties, solvent resistance, and heat resistance.
  • the film according to the present disclosure is preferably a polyester resin film, more preferably a polyethylene terephthalate film, from the viewpoint of optical properties, solvent resistance and heat resistance.
  • the film according to the present disclosure is preferably a stretched film, and more preferably a biaxially stretched film, from the viewpoint of exhibiting the effect of transparency and the property of suppressing the generation of wrinkles during transportation.
  • the method for producing a film according to the present disclosure is not particularly limited, on the uniaxially stretched film stretched in the first stretching direction, a step of forming a layer containing particles, and the uniaxially stretched film and the uniaxially stretched film.
  • a layer containing the particles formed on a stretched film is preferably a manufacturing method including a step of stretching in a second stretching direction orthogonal to the first stretching direction along the film surface of the uniaxially stretched film.
  • the manufacturing method includes a step of stretching the contained layer in the second stretching direction orthogonal to the first stretching direction along the film surface of the uniaxially stretched polyethylene terephthalate film.
  • the stretching ratio and the stretching temperature during the stretching are not particularly limited, and a known stretching method can be referred to if desired.
  • the method for producing a film according to the present disclosure may further include a step of uniaxially stretching an unstretched film to produce a uniaxially stretched film before the step of forming the layer containing the particles. Further, the method for producing a film according to the present disclosure may further include steps other than the above.
  • Coating solution 1 was applied to one surface of a polyester film used as a substrate by the following method, and stretched under the following conditions to prepare a temporary support.
  • Coating liquid 1 was obtained by mixing the components in the amounts shown below. After preparation of the coating liquid 1 and before coating, the coating liquid 1 is filtered with a filter having a pore size of 6 ⁇ m (F20, manufactured by Mare Filter Systems Co., Ltd.) and membrane degassing (2 ⁇ 6 radial flow superphobic, polypore). (Manufactured by KK).
  • a haze meter NDH400 manufactured by Nippon Denshoku Industries Co., Ltd. was used to measure the haze value at 10 positions in the surface direction of the temporary support, and the average value was obtained.
  • Production Example 2 A temporary support of Production Example 2 was obtained in the same manner as in Production Example 1 except that the bar at the time of applying the coating liquid 1 was adjusted and the film thickness after film formation was changed to 60 nm.
  • a temporary support of Production Example 3 was obtained in the same manner as Production Example 1 except that the film thickness after the film was changed to 50 nm.
  • Production Example 5 A temporary support of Production Example 5 was obtained in the same manner as Production Example 1 except that the thickness of the unstretched film extruded from the die was changed to 4/5 times.
  • a polyester film to be used as a substrate is prepared by the following method, and one side of the polyester film is coated with the coating liquid 2 for forming a particle-containing layer and stretched.
  • ⁇ Coating liquid 2 for forming particle-containing layer The components were mixed in the following formulation to obtain a coating liquid 2 for forming a particle-containing layer. After the coating liquid 2 was prepared and before coating, filtration with a 6 ⁇ m filter (F20, manufactured by Mare Filter Systems Co., Ltd.) and membrane degassing (2 ⁇ 6 radial flow superphobic, manufactured by Polypore Co., Ltd.) were performed.
  • a 6 ⁇ m filter F20, manufactured by Mare Filter Systems Co., Ltd.
  • membrane degassing 2 ⁇ 6 radial flow superphobic, manufactured by Polypore Co., Ltd.
  • -Acrylic polymer AS-563A, manufactured by Daicel Finechem Ltd., solid content 27.5% by mass
  • 167 parts-Nonionic surfactant Naaloacty CL95, manufactured by Sanyo Chemical Industry Co., Ltd., solid content 100% by mass
  • 0.7 part-anionic surfactant rapizole A-90, manufactured by NOF CORPORATION, solid content 1% by weight diluted with water
  • Carbodiimide compound Carbodilite V-02-L2, Nisshinbo Co., Ltd., solid content 10 mass% diluted with water
  • 20.9 parts Matting agent sica particles: Snowtex XL, manufactured by Nissan Chemical Industries, Ltd., solid content 40% by mass: 2.8 parts, matting agent (Aerosil OX50, manufactured by Nippon Aerosil Co., Ltd., solid
  • Production Example 7 A temporary support of Production Example 7 was obtained in the same manner as in Production Example 1 except that silica particles were not used in the preparation of the coating liquid 1.
  • ⁇ Production Example 8> The silica particles of the coating liquid 1 are changed to Snowtex MP-2040 (silica particles, manufactured by Nissan Kagaku Co., Ltd., solid content 40 mass%, arithmetic mean particle size 200 nm), and the coating liquid is applied on both sides.
  • a temporary support of Production Example 8 was obtained in the same manner as in Production Example 1 except that the bar at the time of adjustment was adjusted to change the film thickness after film formation to 100 nm.
  • B-1 The following compound B-2: The following compound C-1: 1,2,3-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) C-2: N-cyclohexyl-N'-[2-(4-morpholinyl)ethyl]thiourea (CMTU, manufactured by Toyo Kasei Co., Ltd.) E-1: F-554, perfluoroalkyl group-containing nonionic surfactant (manufactured by DIC Corporation) F-1: 9,10-dibutoxyanthracene
  • Example 1 The photosensitive resin composition 1 was applied to the side opposite to the surface having the particle-containing layer of the temporary support produced in Production Example 1 using a slit nozzle so that the dry film thickness was 3.0 ⁇ m. Then, it was dried in a convection oven at 100° C. for 2 minutes, and finally a polyethylene film (OSM-N, manufactured by Tredegar Co., Ltd.) was pressure-bonded as a protective film to prepare a photosensitive transfer material (dry film resist) of Example 1.
  • OSM-N polyethylene film
  • Example 2 ⁇ Preparation of Composition 1 for Intermediate Layer> Each component was mixed so as to have the following composition to prepare a composition 1 for intermediate layer.
  • the composition 1 for intermediate layer was slit-coated on the temporary support prepared in Production Example 1 to a dry film thickness of 2.4 ⁇ m, and dried in a convection oven at 100° C. for 2 minutes.
  • the photosensitive resin composition 1 was applied onto this intermediate layer using a slit nozzle so that the dry film thickness was 3.0 ⁇ m. Then, it was dried in a convection oven at 100° C. for 2 minutes, and finally a polyethylene film (OSM-N manufactured by Tredegar Co., Ltd.) was pressure-bonded as a protective film to prepare a photosensitive transfer material of Example 2.
  • Examples 3 to 6 and 13 In the same manner as in Example 2 except that the temporary supports prepared in Production Examples 2 to 6 were used in place of the temporary supports prepared in Production Example 1, the same processes as in Examples 3 to 6 and Example 13 were performed. Each photosensitive transfer material was prepared.
  • Example 7 The photosensitive transfer material of Example 7 was prepared in the same manner as in Example 2 except that a 16 ⁇ m thick polyester film 16KS40 (manufactured by Toray Industries, Inc.) was used instead of the temporary support prepared in Production Example 1. It was made.
  • the polyester film 16KS40 has a particle-containing layer on both sides of the film, and the arithmetic average particle diameter of the particles contained in the particle-containing layer on the surface on which the intermediate layer and the like are formed is 50 nm and the other surface.
  • the arithmetic average particle diameter of the particles contained in the particle-containing layer was 400 nm.
  • Example 8 to 12 Photosensitive transfer materials of Examples 8 to 12 were produced in the same manner as in Example 2 except that the above-mentioned photosensitive resin compositions 2 to 6 were used instead of the photosensitive resin composition 1.
  • Example 14 The sensitization of Example 14 was performed in the same manner as in Example 2 except that a polyester film having a thickness of 16 ⁇ m, Cosmoshine A-1517 (manufactured by Toyobo Co., Ltd.) was used in place of the temporary support produced in Production Example 1. A sex transfer material was prepared. The polyester film Cosmoshine A-1517 has a particle-containing layer on one surface of the film.
  • Comparative Example 1 The photosensitive transfer material of Comparative Example 1 was prepared in the same manner as in Example 2 except that the temporary support prepared in Production Example 7 having no particle-containing layer was used in place of the temporary support prepared in Production Example 1. Obtained.
  • Comparative example 2 A photosensitive transfer material of Comparative Example 2 was obtained in the same manner as in Example 2 except that the temporary support produced in Production Example 8 was used in place of the temporary support produced in Production Example 1.
  • the protective film is peeled from the photosensitive transfer material of each Example or Comparative Example, and the photosensitive resin material and the copper layer are in contact with the photosensitive transfer material obtained by peeling the protective film on the circuit forming substrate having a copper layer on one surface. So that the photosensitive resin layer, the intermediate layer in the case of having an intermediate layer, and the temporary support are laminated on the copper layer under the conditions of 100° C., a speed of 4 m/min, and a linear pressure of 0.6 MPa. A laminated body was prepared.
  • This laminated body is exposed to a contact pattern using a photomask provided with a line-and-space wiring pattern having a line width of 6 ⁇ m (width ratio of opening:light-shielding portion is 1:1) without peeling the temporary support.
  • a high pressure mercury lamp having an i-line (365 nm) as a main exposure wavelength was used.
  • After peeling the temporary support from the laminated body after exposure it was developed by shower development for 40 seconds using a 1.0% by mass sodium carbonate aqueous solution at 25° C., and washed with water to obtain a resin pattern.
  • the copper layer was etched using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Inc.) to obtain a copper wiring board.
  • the obtained circuit wiring was used as the circuit wiring of each Example or Comparative Example.
  • the evaluations A to C are preferable, the evaluations A and B are more preferable, and the evaluation A is particularly preferable.
  • a tensile force photosensitive transfer material tension
  • a copper layer were applied in the direction opposite to the laminating direction of the photosensitive transfer material as shown in FIG. 4 according to the following conditions.
  • a tensile force base material tension with copper layer
  • both sides of the base material with copper layer are applied at 100° C., 4 m/min, and linear pressure of 0.6 MPa Laminated to.
  • Base material tension with copper layer 125 N/m
  • Photosensitive transfer material tension 75 N/m FIG.
  • FIG. 4 is a schematic cross-sectional view of the laminating apparatus used in the examples.
  • the photosensitive transfer materials 24a and 24b from which the protective film has been peeled off are laminated on both sides of the copper layer-attached base material 22 by a pair of laminating rolls 26 to form a laminate 28. It is wound by the winding roll 30.
  • the photosensitive transfer materials 24a and 24b from which the protective film has been peeled are respectively subjected to the photosensitive transfer material tensions in the directions T1 and T2 opposite to the laminating direction, and the copper layer base material 22 is opposite to the laminating direction.
  • the substrate tension with the copper layer is applied in the direction T3.
  • the photosensitive transfer materials 24a and 24b are transported by the transport rolls 32a and 32b, respectively, and the laminated body after lamination is transported by the transport rolls 32c and 32d.
  • the obtained laminated body was placed on a flat surface, and the height of the floating (the portion raised from the surroundings) from the flat surface was measured as the height of wrinkles.
  • C Wrinkle height is 4 mm or more and less than 6 mm
  • D Wrinkle height is 6 mm or more Evaluation A or B is preferable, Evaluation A is particularly preferable.
  • PED Post Exposure Delay stability
  • the stability over time after exposure was evaluated as follows.
  • the pattern-exposed roll-shaped laminate was aged for 3 hours or 24 hours in an environment of a temperature of 23° C. and a humidity of 55%.
  • the time described after “PED” means the elapsed time from the exposure to the start of development.
  • development was performed according to the production of the resin pattern to form a resin pattern.
  • the resolution pattern of the obtained resin pattern was observed and evaluated with an optical microscope. The line width of a 6 ⁇ m line and space resolution pattern was measured.
  • the amount of change in the line width of the resin pattern formed in 24 hours of PED was evaluated with respect to the line width of the resin pattern formed in 3 hours of PED.
  • the evaluations A to C are preferable, the evaluations A and B are more preferable, and the evaluation A is particularly preferable.
  • D Variation of line width Value is 2.0 ⁇ m or more and less than 3.0 ⁇ m
  • E Line width fluctuation value is 3.0 ⁇ m or more
  • the photosensitive transfer materials of Examples 1 to 14 were evaluated as C or higher in any of the evaluation items of wrinkle generation suppressing property during transport and PED, and the photosensitive transfer materials of Comparative Examples 1 and 2 were obtained. Compared with the above, it can be seen that both the suppression of wrinkle generation during transport and the stability over time after exposure are achieved. Further, it can be seen from Table 3 above that the photosensitive transfer materials of Examples 1 to 14 are excellent in the linearity of the obtained patterns and the linearity of the circuit wiring patterns produced.
  • Example 101 On a PET substrate having a thickness of 100 ⁇ m, ITO was deposited as a second conductive layer to a thickness of 150 nm by sputtering, and copper was deposited thereon as a first conductive layer to a thickness of 200 nm by a vacuum deposition method. And used as a circuit forming substrate. On the copper layer, the photosensitive transfer material obtained in Example 1 was peeled off from the protective film and bonded to a substrate (laminating roll temperature 100° C., linear pressure 0.8 MPa, linear velocity 3.0 m/min. ) And a laminated body. The obtained laminated body was subjected to contact pattern exposure using a photomask provided with a pattern A shown in FIG.
  • Example 2 having a configuration in which conductive layer pads were connected in one direction without peeling off the temporary support.
  • a high pressure mercury lamp having an i-line (365 nm) as a main exposure wavelength was used for the exposure.
  • the temporary support was peeled off, developed and washed with water to obtain pattern A.
  • the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.).
  • ITO-02 ITO etching solution
  • a substrate in which both copper and ITO were drawn in the pattern A was obtained.
  • the same temporary support as in Example 1 was laminated as a protective layer on the remaining resist.
  • Example 102 In the same manner as in Example 101, after obtaining the substrate on which the pattern A was drawn, the protective film was peeled off the photosensitive transfer material obtained in Example 1 onto the remaining resist to obtain the example. The pieces were reattached under the same conditions as 101. In the aligned state, pattern exposure is performed using a photomask provided with an opening for pattern B without peeling the temporary support, and then the temporary support is peeled off, and development and washing are performed to obtain pattern B. It was Then, the copper wiring was etched under the same conditions as in Example 101, and the remaining photosensitive resin layer was peeled off to obtain a circuit wiring board having a conductive pattern. When the obtained circuit wiring board was observed with a microscope, there was no peeling or chipping, and it was a clean pattern.
  • Example 103 Circuit wiring in the same manner as in Example 101 except that the photosensitive resin composition 7 was used in place of the photosensitive resin composition 1, and a laser beam (exposure main wavelength: 405 nm) was used in place of the high-pressure mercury lamp during exposure. A substrate was obtained. When the obtained circuit wiring board was observed with a microscope, there was no peeling or chipping, and it was a clean pattern.

Abstract

This photosensitive transfer material comprises a temporary support and a photosensitive resin layer provided on the temporary support, wherein: the temporary support has a particle-containing layer containing particles; the surface roughness on the surface of the temporary support facing away from the surface on the side having the photosensitive resin layer is 0.02 μm to 0.20 μm; and the photosensitive resin layer contains a photoacid generator, and a polymer containing a constituent unit having an acid group protected by an acid decomposable group. Also provided are: a resin pattern production method, a circuit wiring production method, and a touch panel production method, which use the transfer material; and a film having a particle-containing layer, a haze value of 0.2% or less, and a surface roughness Ra on the surface of the side having the particle-containing layer of 0.02 μm to 0.20 μm, as well as a production method therefor.

Description

感光性転写材料、樹脂パターンの製造方法、回路配線の製造方法、タッチパネルの製造方法、並びに、フィルム及びその製造方法Photosensitive transfer material, resin pattern manufacturing method, circuit wiring manufacturing method, touch panel manufacturing method, film and manufacturing method thereof
　本開示は、感光性転写材料、樹脂パターンの製造方法、回路配線の製造方法、タッチパネルの製造方法、並びに、フィルム及びその製造方法に関する。 The present disclosure relates to a photosensitive transfer material, a resin pattern manufacturing method, a circuit wiring manufacturing method, a touch panel manufacturing method, a film, and a manufacturing method thereof.
　静電容量型入力装置などのタッチパネルを備えた表示装置（有機エレクトロルミネッセンス（ＥＬ）表示装置及び液晶表示装置など）では、視認部のセンサーに相当する電極パターン、周辺配線部分及び取り出し配線部分の配線などの導電層パターンがタッチパネル内部に設けられている。 2. Description of the Related Art In a display device (organic electroluminescence (EL) display device, liquid crystal display device, etc.) equipped with a touch panel such as an electrostatic capacitance type input device, an electrode pattern corresponding to a sensor of a visual recognition part, wiring of a peripheral wiring part and an extraction wiring part A conductive layer pattern such as is provided inside the touch panel.
　一般的にパターン化した層の形成には、必要とするパターン形状を得るための工程数が少ないといったことから、感光性転写材料を用いて任意の基板上に設けた感光性樹脂組成物の層に対して、所望のパターンを有するマスクを介して露光した後に現像する方法が広く使用されている。 Generally, a patterned layer is formed by a small number of steps for obtaining a required pattern shape. Therefore, a layer of a photosensitive resin composition provided on an arbitrary substrate using a photosensitive transfer material. On the other hand, a method of developing after exposing through a mask having a desired pattern is widely used.
　また、従来の感光性転写材料としては、特開２０１７－７８８５２号公報に記載されたものが知られている。
　特開２０１７－７８８５２号公報には、仮支持体上にレジスト層を有するポジ型ドライフィルムレジストであり、上記仮支持体の全光線ヘイズが０．３％以下であるドライフィルムレジストが記載されている。 Further, as a conventional photosensitive transfer material, a material described in JP-A-2017-78852 is known.
JP-A-2017-78852 describes a positive type dry film resist having a resist layer on a temporary support, in which the total light ray haze of the temporary support is 0.3% or less. There is.
　更に、従来のフォトレジスト用ポリエステルフィルムとしては、特開２０００－２２１６８８号公報に記載されたものが知られている。
　特開２０００－２２１６８８号公報には、平均粒径０．０１μｍ～５．０μｍの粒子の含有量が８０ｐｐｍ以下であり、平均粒径５．０μｍを超える粒子を含有しない二軸配向ポリエステルフィルムの一方の面に、平均粒径０．０１～５．０μｍの粒子を含有する、厚さ０．１～１．０μｍの樹脂層を積層したポリエステルフィルムであって、上記ポリエステルフィルムのヘーズ（ＪＩＳ Ｋ７１０５に準拠して測定）が１．０％以下であることを特徴とする極細線用フォトレジスト用ポリエステルフィルムが記載されている。 Further, as a conventional polyester film for photoresist, one described in JP-A-2000-221688 is known.
Japanese Unexamined Patent Publication No. 2000-221688 discloses a biaxially oriented polyester film in which the content of particles having an average particle size of 0.01 μm to 5.0 μm is 80 ppm or less and which does not contain particles having an average particle size of more than 5.0 μm Is a polyester film in which a resin layer having a thickness of 0.1 to 1.0 μm, containing particles having an average particle diameter of 0.01 to 5.0 μm, is laminated on the surface of the polyester film. A polyester film for a photoresist for ultrafine wires, which is characterized in that it is 1.0% or less.
　本開示に係る一実施形態は、搬送時のシワの発生の抑制と、露光後の経時安定性とを両立した感光性転写材料を提供することに関する。
　また、本開示に係る他の一実施形態は、上記感光性転写材料を用いた樹脂パターンの製造方法、回路配線の製造方法、及び、タッチパネルの製造方法を提供することに関する。
　本開示に係る更に他の一実施形態は、透明性、及び、搬送時のシワ発生抑制性に優れるフィルム及びその製造方法を提供することに関する。 One embodiment according to the present disclosure relates to providing a photosensitive transfer material that achieves both suppression of wrinkling during transport and stability over time after exposure.
Further, another embodiment according to the present disclosure relates to providing a method for manufacturing a resin pattern using the above-mentioned photosensitive transfer material, a method for manufacturing circuit wiring, and a method for manufacturing a touch panel.
Yet another embodiment according to the present disclosure relates to a film having excellent transparency and a property of suppressing generation of wrinkles during transportation, and a method for manufacturing the film.
　本開示には、以下の態様が含まれる。
＜１＞　仮支持体と、上記仮支持体上に設けられた感光性樹脂層とを有し、上記仮支持体が、粒子を含有する粒子含有層を有し、上記仮支持体の感光性樹脂層を有する側の面とは反対側の面の表面粗さＲａが、０．０２μｍ～０．２０μｍであり、上記感光性樹脂層が、酸分解性基で保護された酸基を有する構成単位を含有する重合体、及び、光酸発生剤を含有する感光性転写材料。
＜２＞　上記仮支持体のヘーズ値が、０．２％以下である＜１＞に記載の感光性転写材料。
＜３＞　上記粒子含有層の厚さが、１０ｎｍ～１００ｎｍである＜１＞又は＜２＞に記載の感光性転写材料。
＜４＞　上記粒子含有層が、上記仮支持体の片面のみに設けられている＜１＞～＜３＞のいずれか１つに記載の感光性転写材料。
＜５＞　上記粒子の算術平均粒径が、１００ｎｍ未満である＜１＞～＜４＞のいずれか１つに記載の感光性転写材料。
＜６＞　上記仮支持体の感光性樹脂層を有する側の面とは反対側の面の表面粗さＲａが、０．０５μｍ～０．１０μｍである＜１＞～＜５＞のいずれか１つに記載の感光性転写材料。
＜７＞　上記仮支持体の厚さが、１８μｍを超え３０μｍ以下である＜１＞～＜６＞のいずれか１つに記載の感光性転写材料。
＜８＞　上記仮支持体が、ポリエステル樹脂を含む＜１＞～＜７＞のいずれか１つに記載の感光性転写材料。
＜９＞　上記酸分解性基で保護された酸基が、アセタール型酸分解性基で保護されたカルボキシ基である＜１＞～＜８＞のいずれか１つに記載の感光性転写材料。
＜１０＞　上記重合体の酸価が、１０ｍｇＫＯＨ／ｇ以下である＜１＞～＜９＞のいずれか１つに記載の感光性転写材料。
＜１１＞　上記光酸発生剤が、炭素数１～４のアルキルスルホン酸を発生する光酸発生剤を含む＜１＞～＜１０＞のいずれか１つに記載の感光性転写材料。
＜１２＞　＜１＞～＜１１＞のいずれか１つに記載の感光性転写材料における上記仮支持体に対して感光性樹脂層を有する側の最外層を基板に接触させて貼り合わせる工程と、上記感光性樹脂層をパターン露光する工程と、露光された上記感光性樹脂層を現像して樹脂パターンを形成する工程と、をこの順に含む樹脂パターンの製造方法。
＜１３＞　＜１＞～＜１１＞のいずれか１つに記載の感光性転写材料における上記仮支持体に対して上記感光性樹脂層を有する側の最外層を、導電層を有する基板に接触させて貼り合わせる工程と、上記感光性樹脂層をパターン露光する工程と、露光された上記感光性樹脂層を現像して樹脂パターンを形成する工程と、上記樹脂パターンが配置されていない領域における上記導電層をエッチング処理する工程と、をこの順に含む回路配線の製造方法。
＜１４＞　＜１＞～＜１１＞のいずれか１つに記載の感光性転写材料における上記仮支持体に対して上記感光性樹脂層を有する側の最外層を、導電層を有する基板に接触させて貼り合わせる工程と、上記感光性樹脂層をパターン露光する工程と、露光された上記感光性樹脂層を現像して樹脂パターンを形成する工程と、上記樹脂パターンが配置されていない領域における上記導電層をエッチング処理する工程と、をこの順に含むタッチパネルの製造方法。
＜１５＞　粒子を含有する粒子含有層を少なくとも片面に有し、ヘーズ値が、０．２％以下であり、上記粒子含有層を有する側の面の表面粗さＲａが、０．０２μｍ～０．２０μｍであるフィルム。
＜１６＞　第一延伸方向に延伸された一軸延伸フィルム上に、粒子を含有する層を形成する工程、及び、上記一軸延伸フィルム及び上記一軸延伸フィルム上に形成された上記粒子を含有する層を、上記一軸延伸フィルムにおけるフィルム面に沿って上記第一延伸方向と直交する第二延伸方向に延伸する工程を含む＜１５＞に記載のフィルムの製造方法。 The present disclosure includes the following aspects.
<1> a temporary support and a photosensitive resin layer provided on the temporary support, wherein the temporary support has a particle-containing layer containing particles, and the temporary support has a photosensitivity. The surface roughness Ra of the surface opposite to the surface having the resin layer is 0.02 μm to 0.20 μm, and the photosensitive resin layer has an acid group protected by an acid-decomposable group. A photosensitive transfer material containing a polymer containing units and a photoacid generator.
<2> The photosensitive transfer material according to <1>, wherein the temporary support has a haze value of 0.2% or less.
<3> The photosensitive transfer material according to <1> or <2>, wherein the particle-containing layer has a thickness of 10 nm to 100 nm.
<4> The photosensitive transfer material according to any one of <1> to <3>, wherein the particle-containing layer is provided on only one surface of the temporary support.
<5> The photosensitive transfer material according to any one of <1> to <4>, wherein the arithmetic average particle diameter of the particles is less than 100 nm.
<6> Any one of <1> to <5>, wherein the surface roughness Ra of the surface of the temporary support opposite to the surface having the photosensitive resin layer is 0.05 μm to 0.10 μm. The photosensitive transfer material described in 1.
<7> The photosensitive transfer material according to any one of <1> to <6>, wherein the temporary support has a thickness of more than 18 μm and 30 μm or less.
<8> The photosensitive transfer material according to any one of <1> to <7>, in which the temporary support contains a polyester resin.
<9> The photosensitive transfer material according to any one of <1> to <8>, wherein the acid group protected by the acid-decomposable group is a carboxy group protected by an acetal-type acid-decomposable group.
<10> The photosensitive transfer material according to any one of <1> to <9>, wherein the polymer has an acid value of 10 mgKOH/g or less.
<11> The photosensitive transfer material according to any one of <1> to <10>, in which the photo-acid generator includes a photo-acid generator that generates an alkylsulfonic acid having 1 to 4 carbon atoms.
<12> A step of bringing the outermost layer of the photosensitive transfer material of the photosensitive transfer material according to any one of <1> to <11> on the side having a photosensitive resin layer into contact with a substrate and bonding the substrate. And a step of pattern-exposing the photosensitive resin layer, and a step of developing the exposed photosensitive resin layer to form a resin pattern in this order.
<13> The outermost layer on the side having the photosensitive resin layer with respect to the temporary support in the photosensitive transfer material according to any one of <1> to <11> is brought into contact with a substrate having a conductive layer. And the step of adhering, the step of pattern-exposing the photosensitive resin layer, the step of developing the exposed photosensitive resin layer to form a resin pattern, and the step in the region where the resin pattern is not arranged. A method of manufacturing circuit wiring, which includes a step of etching a conductive layer in this order.
<14> The outermost layer on the side having the photosensitive resin layer with respect to the temporary support in the photosensitive transfer material according to any one of <1> to <11> is brought into contact with a substrate having a conductive layer. And the step of adhering, the step of pattern-exposing the photosensitive resin layer, the step of developing the exposed photosensitive resin layer to form a resin pattern, and the step in the region where the resin pattern is not arranged. A method of manufacturing a touch panel, comprising: a step of etching a conductive layer;
<15> A particle-containing layer containing particles is provided on at least one surface, a haze value is 0.2% or less, and a surface roughness Ra of the surface having the particle-containing layer is 0.02 μm to 0. A film that is 20 μm.
<16> A step of forming a layer containing particles on a uniaxially stretched film stretched in a first stretching direction, and a layer containing the particles formed on the uniaxially stretched film and the uniaxially stretched film. The method for producing a film according to <15>, including a step of stretching in a second stretching direction orthogonal to the first stretching direction along a film surface of the uniaxially stretched film.
　本開示に係る一実施形態によれば、搬送時のシワの発生の抑制と、露光後の経時安定性とを両立した感光性転写材料を提供することができる。
　また、本開示に係る他の一実施形態によれば、上記感光性転写材料を用いた樹脂パターンの製造方法、回路配線の製造方法、及び、タッチパネルの製造方法を提供することができる。
　本開示に係る更に他の一実施形態によれば、透明性、及び、搬送時のシワ発生抑制性に優れるフィルム及びその製造方法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 photosensitive transfer material that achieves both suppression of wrinkling during transport and stability over time after exposure.
Further, according to another embodiment of the present disclosure, it is possible to provide a method for manufacturing a resin pattern using the photosensitive transfer material, a method for manufacturing circuit wiring, and a method for manufacturing a touch panel.
According to still another embodiment of the present disclosure, it is possible to provide a film having excellent transparency and a property of suppressing the generation of wrinkles during transportation, and a manufacturing method thereof.
本開示に係る感光性転写材料の層構成の一例を示す概略図である。It is a schematic diagram showing an example of layer composition of a photosensitive transfer material concerning this indication. パターンＡを示す概略図である。It is a schematic diagram showing pattern A. パターンＢを示す概略図である。It is a schematic diagram showing pattern B. 本開示に好適に用いられるラミネート装置の一例を示す模式断面図である。It is a schematic cross section which shows an example of the laminating apparatus suitably used for this indication.
　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、溶媒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。 The contents of the present disclosure will be described below. The description will be made with reference to the accompanying drawings, but the reference numerals may be omitted.
Further, in the present specification, the numerical range represented by “to” means a range including the numerical values before and after “to” as the lower limit value and the upper limit value.
Moreover, in this specification, "(meth)acryl" represents both acryl and methacryl, or either, and "(meth)acrylate" represents both an acrylate and a methacrylate.
Further, in the present specification, the amount of each component in the composition is the sum of the corresponding plurality of substances present in the composition, unless a plurality of substances corresponding to each component are present in the composition. Means quantity.
In the present specification, the term “step” is included in the term as long as the intended purpose of the step is achieved, not only when it is an independent step but also when it cannot be clearly distinguished from other steps.
In the description of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not included includes not only those having no substituent but also 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).
In the present specification, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. In addition, as the light used for the exposure, generally, the bright line spectrum of a mercury lamp, far-ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays (active energy rays) such as electron rays are used. Can be mentioned.
In addition, the chemical structural formulas in the present specification may be described as simplified structural formulas in which hydrogen atoms are omitted.
In the present disclosure, “mass %” and “weight %” have the same meaning, and “mass part” and “weight part” have the same meaning.
Further, in the present disclosure, a combination of two or more preferable aspects is a more preferable aspect.
In addition, the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure are columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (both manufactured by Tosoh Corporation) unless otherwise specified. The gel permeation chromatography (GPC) analyzer was used to detect the solvent THF (tetrahydrofuran) with a differential refractometer, and the molecular weight was calculated using polystyrene as a standard substance.
（感光性転写材料）
　本開示に係る感光性転写材料は、仮支持体と、上記仮支持体に支持された感光性樹脂層とを有し、上記仮支持体が、粒子を含有する粒子含有層を有し、上記仮支持体の感光性樹脂層を有する側の面とは反対側の面の表面粗さＲａが、０．０２μｍ～０．２０μｍであり、上記感光性樹脂層が、酸分解性基で保護された酸基を有する構成単位を含有する重合体、及び、光酸発生剤を含有する。
　また、本開示に係る感光性転写材料は、上記のように、ポジ型感光性樹脂層を有するポジ型感光性転写材料である。また、上記感光性樹脂層は、化学増幅ポジ型感光性樹脂層であることが好ましい。 (Photosensitive transfer material)
The photosensitive transfer material according to the present disclosure has a temporary support and a photosensitive resin layer supported by the temporary support, and the temporary support has a particle-containing layer containing particles, The surface roughness Ra of the surface of the temporary support opposite to the surface having the photosensitive resin layer is 0.02 μm to 0.20 μm, and the photosensitive resin layer is protected with an acid-decomposable group. And a polymer containing a structural unit having an acid group, and a photoacid generator.
Further, the photosensitive transfer material according to the present disclosure is a positive type photosensitive transfer material having a positive type photosensitive resin layer as described above. The photosensitive resin layer is preferably a chemically amplified positive photosensitive resin layer.
　従来の感光性転写材料では、搬送時に掛かる応力により、シワが発生する場合があり、特にロールトゥロールにより搬送及び転写する場合にシワの発生が顕著に見られることを、本発明者らは見出した。
　また、酸分解性基で保護された酸基を有する構成単位を含有する重合体、及び、光酸発生剤を含有する、いわゆる化学増幅ポジ型感光性樹脂層は、露光して現像し、非露光部が残ることでパターンを形成するが、上記粒子に由来する露光時の光の拡散により、非露光部においても少量の酸が発生し、その酸が拡散されるため、露光後に時間が経過した後に現像した際に得られるパターンのサイズが変化してしまうという問題があることを、本発明者らは見出した。
　本開示において、露光後に時間が経過した後に現像しても、得られるパターンのサイズが変化しにくいという性質を、「露光後の経時安定性（ＰＥＤ：Ｐｏｓｔ　Ｅｘｐｏｓｕｒｅ　Ｄｅｌａｙ　ｓｔａｂｉｌｉｔｙ））に優れる」ともいう。
　一方、特開２０００－２２１６８８号公報等に記載されているネガ型感光性樹脂層の場合、露光部が硬化することによりパターンを形成するが、重合開始種の拡散距離は短く、かつ発生量も少ないため、露光後に時間が経過した後に現像した際に得られるパターンのサイズが変化してしまうという課題は発生しない。
　よって、露光後に時間が経過した後に現像した際に得られるパターンのサイズが変化してしまうという課題は、化学増幅ポジ型感光性樹脂層に特有の課題である。 The present inventors have found that in conventional photosensitive transfer materials, wrinkles may occur due to stress applied during transportation, and wrinkles are particularly noticeable when transported and transferred by roll-to-roll. It was
Further, a polymer containing a constitutional unit having an acid group protected by an acid-decomposable group, and a so-called chemically amplified positive photosensitive resin layer containing a photo-acid generator are exposed to light and developed, A pattern is formed by leaving the exposed part, but due to the diffusion of light at the time of exposure derived from the particles, a small amount of acid is generated even in the non-exposed part, and the acid is diffused, so that the time elapsed after the exposure. The present inventors have found that there is a problem in that the size of the pattern obtained when developed after that is changed.
In the present disclosure, the property that the size of the obtained pattern does not easily change even after development after a lapse of time after exposure is also referred to as “excellent in stability over time after exposure (PED: Post Exposure Delay stability)”. ..
On the other hand, in the case of the negative type photosensitive resin layer described in JP-A-2000-221688 and the like, a pattern is formed by curing the exposed portion, but the diffusion distance of the polymerization initiation species is short and the amount of generation is also small. Since the number is small, the problem that the size of the pattern obtained when developing is changed after a lapse of time after exposure does not occur.
Therefore, the problem that the size of the pattern obtained when developing is changed after a lapse of time after exposure is a problem peculiar to the chemically amplified positive photosensitive resin layer.
　本発明者らは鋭意検討を重ねた結果、上記構成の感光性転写材料とすることにより、搬送時のシワの発生の抑制（「搬送時のシワ発生抑制性」ともいう。）と、露光後の経時安定性とを両立した感光性転写材料が得られることを見出した。
　詳細な上記効果の発現機構は不明であるが、上記仮支持体が、粒子を含有する粒子含有層を有し、上記仮支持体の感光性樹脂層を有する側の面とは反対側の面の表面粗さＲａが、０．０２μｍ～０．２０μｍであることにより、仮支持体の表面及び内部の少なくとも一方に存在する上記粒子の形状の影響により形成された凹凸部分が、搬送時の仮支持体と搬送部材との接触面積を小さくし、搬送による不要な応力等が感光性転写材料に掛かることを抑制し、シワの発生が抑制され、搬送時のシワ発生抑制性に優れると推定される。
　また、酸分解性基で保護された酸基を有する構成単位を含有する重合体、及び、光酸発生剤を含有する感光性樹脂層を有する感光性転写材料において、上記仮支持体が、粒子を含有する粒子含有層を有し、上記仮支持体の感光性樹脂層を有する側の面とは反対側の面の表面粗さＲａが、０．０２μｍ～０．２０μｍであることにより、上記粒子に由来する露光時の光の拡散が抑制され、得られるパターンの直線性に優れるとともに、非露光部における酸の発生及び拡散を抑制し、露光後の経時安定性に優れると推定される。 As a result of intensive studies by the present inventors, the use of the photosensitive transfer material having the above-described configuration suppresses the generation of wrinkles during transportation (also referred to as “wrinkle generation inhibition during transportation”) and after exposure. It was found that a photosensitive transfer material having both stability with time can be obtained.
Although the detailed mechanism of manifestation of the effect is unknown, the temporary support has a particle-containing layer containing particles, and the surface opposite to the surface having the photosensitive resin layer of the temporary support. Has a surface roughness Ra of 0.02 μm to 0.20 μm, the uneven portion formed by the shape of the particles present on at least one of the surface and the inside of the temporary support has a temporary roughness during transportation. It is presumed that the contact area between the support and the transport member is reduced, unnecessary stress due to transport is suppressed from being applied to the photosensitive transfer material, wrinkles are suppressed, and wrinkle generation during transfer is excellent. It
Further, in the photosensitive transfer material having a polymer containing a structural unit having an acid group protected by an acid-decomposable group, and a photosensitive resin layer containing a photo-acid generator, the temporary support is particles. The surface roughness Ra of the surface of the temporary support opposite to the surface having the photosensitive resin layer is 0.02 μm to 0.20 μm. It is presumed that the diffusion of light derived from particles during exposure is suppressed, the linearity of the obtained pattern is excellent, the generation and diffusion of acid in the non-exposed portion is suppressed, and the temporal stability after exposure is excellent.
　以下、本開示に係る感光性転写材料について、詳細に説明する。 Hereinafter, the photosensitive transfer material according to the present disclosure will be described in detail.
＜仮支持体＞
　本開示に係る感光性転写材料は、仮支持体を有し、上記仮支持体が、粒子を含有する粒子含有層を有し、上記仮支持体の感光性樹脂層を有する側の面とは反対側の面の表面粗さＲａが、０．０２μｍ～０．２０μｍである。 <Temporary support>
The photosensitive transfer material according to the present disclosure has a temporary support, the temporary support has a particle-containing layer containing particles, and the surface of the temporary support on the side having the photosensitive resin layer is The surface roughness Ra of the opposite surface is 0.02 μm to 0.20 μm.
　上記仮支持体は、上記粒子含有層を１層のみ有していても、２層以上有していてもよい。上記粒子含有層は、搬送時のシワ発生抑制性、露光後の経時安定性、及び、得られるパターンの直線性の観点から、上記仮支持体の片面のみに設けられているか、又は、上記仮支持体の両面にそれぞれ設けられていることが好ましく、上記仮支持体の片面のみに設けられていることがより好ましく、上記仮支持体の感光性樹脂層を有する側の面とは反対側の面のみに設けられていることが特に好ましい。 The above temporary support may have only one layer containing the above-mentioned particle-containing layer or may have two or more layers. The particle-containing layer is provided on only one side of the temporary support, from the viewpoint of wrinkle generation suppression during transport, stability over time after exposure, and linearity of the obtained pattern, or the above temporary support. It is preferably provided on both sides of the support, and more preferably provided on only one side of the temporary support, on the side opposite to the side having the photosensitive resin layer of the temporary support. It is particularly preferable that it is provided only on the surface.
　上記粒子含有層に含有される粒子としては、例えば、無機粒子、有機粒子等が挙げられる。
　無機粒子としては、例えば、酸化ケイ素（シリカ）粒子、酸化チタン（チタニア）粒子、酸化ジルコニウム（ジルコニア）粒子、酸化マグネシウム（マグネシア）粒子、酸化アルミニウム（アルミナ）粒子等が挙げられる。
　有機粒子としては、例えば、アクリル樹脂粒子、ポリエステル粒子、ポリウレタン粒子、ポリカーボネート粒子、ポリオレフィン粒子、ポリスチレン粒子等の有機樹脂粒子などが挙げられる。
　上記粒子含有層に含有される粒子は、上記の中でも、露光後の経時安定性、及び、得られるパターンの直線性の観点から、無機粒子であることが好ましく、シリカ粒子であることがより好ましい。 Examples of the particles contained in the particle-containing layer include inorganic particles and organic particles.
Examples of the inorganic particles include silicon oxide (silica) particles, titanium oxide (titania) particles, zirconium oxide (zirconia) particles, magnesium oxide (magnesia) particles, aluminum oxide (alumina) particles, and the like.
Examples of the organic particles include organic resin particles such as acrylic resin particles, polyester particles, polyurethane particles, polycarbonate particles, polyolefin particles, and polystyrene particles.
Among the above, the particles contained in the particle-containing layer are preferably inorganic particles, and more preferably silica particles, from the viewpoint of temporal stability after exposure, and linearity of the obtained pattern. ..
　上記粒子含有層は、粒子を１種単独で含有していても、２種以上の粒子を含有していてもよい。
　上記粒子含有層における粒子の含有量は、上記表面粗さＲａの範囲を満たすことができれば特に制限はないが、表面粗さの制御容易性、及び、搬送時のシワ発生抑制性の観点から、上記粒子含有層の全質量に対して０．０１質量％～２０質量％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、０．５質量％～５質量％であることが特に好ましい。
　また、上記粒子含有層における粒子は、上記粒子含有層の内部に存在しても、一部が上記粒子含有層の表面に露出していてもよい。
　例えば、上記仮支持体の感光性樹脂層を有する側の面とは反対側の面に、上記粒子含有層を有する場合、仮支持体における上記反対側の面に粒子が露出していてもよい。 The particle-containing layer may contain one kind of particle alone, or may contain two or more kinds of particles.
The content of particles in the particle-containing layer is not particularly limited as long as it can satisfy the range of the surface roughness Ra, but from the viewpoint of controllability of the surface roughness, and wrinkle generation suppressing property during transport, It is preferably 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass, and 0.5% by mass to 5% by mass with respect to the total mass of the particle-containing layer. Is particularly preferable.
The particles in the particle-containing layer may be present inside the particle-containing layer or may be partially exposed on the surface of the particle-containing layer.
For example, when the particle-containing layer is provided on the surface of the temporary support opposite to the surface having the photosensitive resin layer, the particles may be exposed on the opposite surface of the temporary support. ..
　上記粒子含有層に含有される粒子以外の材質としては、特に制限はなく、例えば、後述する仮支持体の材質として例示される材質と同様のものを挙げることができる。
　上記粒子含有層は、表面粗さの制御容易性、及び、搬送時のシワ発生抑制性の観点から、樹脂を含むことが好ましく、バインダーポリマーとして、樹脂を含むことがより好ましく、アクリル樹脂を含むことが特に好ましい。
　また、上記粒子含有層は、表面粗さの制御容易性、及び、搬送時のシワ発生抑制性の観点から、上記粒子含有層以外の部分の仮支持体に含まれる樹脂と異なる樹脂を含むことが好ましく、上記粒子含有層はアクリル樹脂を含み、かつ上記粒子含有層以外の部分の仮支持体はポリエステル樹脂を含むことが特に好ましい。 The material other than the particles contained in the particle-containing layer is not particularly limited, and examples thereof include the same materials as the materials of the temporary support described later.
The particle-containing layer preferably contains a resin, more preferably contains a resin as the binder polymer, and contains an acrylic resin, from the viewpoints of the controllability of the surface roughness and the property of suppressing the generation of wrinkles during transportation. Is particularly preferable.
Further, the particle-containing layer contains a resin different from the resin contained in the temporary support in the part other than the particle-containing layer, from the viewpoint of controllability of surface roughness and wrinkle generation suppressing property during transportation. It is particularly preferable that the particle-containing layer contains an acrylic resin, and the temporary support other than the particle-containing layer contains a polyester resin.
　上記粒子含有層は、樹脂を１種単独で含有していても、２種以上の樹脂を含有していてもよい。
　上記粒子含有層における樹脂の含有量としては、特に制限はないが、表面粗さの制御容易性、及び、搬送時のシワ発生抑制性の観点から、上記粒子含有層の全質量に対し、１０質量％～９９．９質量％であることが好ましく、２０質量％～９９．５質量％であることがより好ましく、５０質量％～９９質量％であることが更に好ましく、８０質量％～９８質量％であることが特に好ましい。 The particle-containing layer may contain one type of resin or two or more types of resin.
The content of the resin in the particle-containing layer is not particularly limited, but is 10 with respect to the total mass of the particle-containing layer from the viewpoint of controllability of surface roughness and wrinkle suppression during transport. The content is preferably from 9 to 99.9% by mass, more preferably from 20 to 99.5% by mass, further preferably from 50 to 99% by mass, and from 80 to 98% by mass. % Is particularly preferable.
　また、上記粒子含有層は、粒子及び樹脂以外のその他の化合物を含有してもよい。
　その他の化合物としては、界面活性剤、ワックス等が挙げられる。 Further, the particle-containing layer may contain other compounds than the particles and the resin.
Examples of other compounds include surfactants and waxes.
－界面活性剤－
　上記粒子含有層は、層厚均一性の観点から、界面活性剤を含有することが好ましい。
　界面活性剤としては、アニオン系、カチオン系、ノニオン系（非イオン系）、又は、両性のいずれでも使用することができるが、好ましい界面活性剤はアニオン系界面活性剤である。
　アニオン系界面活性剤の例としては、ラピゾール（登録商標）Ａ－９０、Ａ－８０、ＢＷ－３０、Ｂ－９０、Ｃ－７０（以上、日油（株）製）、ＮＩＫＫＯＬ（登録商標）ＯＴＰ－１００（以上、日光ケミカル（株）製）、コハクール（登録商標）ＯＮ、Ｌ－４０、フォスファノール（登録商標）７０２（以上、東邦化学工業（株）製）、ビューライト（登録商標）Ａ－５０００、ＳＳＳ（以上、三洋化成工業（株）製）等が挙げられる。 -Surfactant-
The particle-containing layer preferably contains a surfactant from the viewpoint of layer thickness uniformity.
The surfactant may be anionic, cationic, nonionic (nonionic), or amphoteric, and the preferred surfactant is anionic.
Examples of anionic surfactants include Rapizole (registered trademark) A-90, A-80, BW-30, B-90, C-70 (all manufactured by NOF Corporation) and NIKKOL (registered trademark). OTP-100 (above, manufactured by Nikko Chemical Co., Ltd.), Kohakul (registered trademark) ON, L-40, Phosphanol (registered trademark) 702 (above, manufactured by Toho Chemical Industry Co., Ltd.), Beaulite (registered trademark) ) A-5000, SSS (above, Sanyo Chemical Industry Co., Ltd.) and the like.
　界面活性剤は、１種単独で用いてもよいし、２種以上の界面活性剤を併用してもよい。
　界面活性剤の含有量は、特に限定されないが、上記粒子含有層の全質量に対して、１０質量％以下であることが好ましく、０．００１質量％～１０質量％であることがより好ましく、０．０１質量％～３質量％であることが更に好ましい。 The surfactant may be used alone or in combination of two or more kinds.
The content of the surfactant is not particularly limited, but is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, based on the total mass of the particle-containing layer. It is more preferably 0.01% by mass to 3% by mass.
－ワックス－
　上記粒子含有層は、上記粒子含有層を塗布により形成する場合の塗布液の塗布性の観点から、ワックスを含有してもよい。
　ワックスの具体例としては、カルナバワックス、キャンデリラワックス、ライスワックス、木ロウ、ホホバ油、パームワックス、ロジン変性ワックス、オウリキュリーワックス、サトウキビワックス、エスパルトワックス、バークワックス等の植物系ワックス；ミツロウ、ラノリン、鯨ロウ、イボタロウ、セラックワックス等の動物系ワックス；モンタンワックス、オゾケライト、セレシンワックス等の鉱物系ワックス；パラフィンワックス、マイクロクリスタリンワックス、ペトロラクタム等の石油系ワックス；フィッシャートロプッシュワックス、ポリエチレンワックス、酸化ポリエチレンワックス、ポリプロピレンワックス、酸化ポリプロピレンワックス等の合成炭化水素系ワックス；が挙げられる。 -wax-
The particle-containing layer may contain wax from the viewpoint of the coating property of the coating liquid when the particle-containing layer is formed by coating.
Specific examples of waxes include plant waxes such as carnauba wax, candelilla wax, rice wax, wax, jojoba oil, palm wax, rosin modified wax, auri curly wax, sugar cane wax, esparto wax, and bark wax; beeswax. , Animal waxes such as lanolin, whale wax, ivowa wax, shellac wax; mineral waxes such as montan wax, ozokerite, ceresin wax; petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam; Fischer-Tropsch wax, polyethylene Examples of the wax include synthetic hydrocarbon waxes such as wax, oxidized polyethylene wax, polypropylene wax, and oxidized polypropylene wax.
　ワックスは、１種単独で用いてもよいし、２種以上のワックスを併用してもよい。
　ワックスの含有量は、特に限定されないが、上記粒子含有層の全質量に対して、１０質量％以下であることが好ましく、０．００１質量％～１０質量％であることがより好ましく、０．０１質量％～３質量％であることが更に好ましい。 The wax may be used alone or in combination of two or more.
The content of the wax is not particularly limited, but is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and more preferably 0. 0% by mass based on the total mass of the particle-containing layer. It is more preferably from 01% by mass to 3% by mass.
　上記粒子の算術平均粒径は、表面粗さの制御容易性、搬送時のシワ発生抑制性、露光後の経時安定性、及び、得られるパターンの直線性の観点から、２０ｎｍ～３００ｎｍであることが好ましく、３０ｎｍ～２００ｎｍであることがより好ましく、４０ｎｍ～１２０ｎｍであることが更に好ましく、４０ｎｍ～８０ｎｍであることが特に好ましい。
　また、上記粒子の算術平均粒径は、透明性、搬送時のシワ発生抑制性、露光後の経時安定性、及び、得られるパターンの直線性の観点から、１００ｎｍ未満であることが好ましい。上記粒子の算術平均粒径が１００ｎｍ未満であることにより、光散乱を高いレベルで抑制できるため、高い透明性を実現でき、露光後の経時安定性に優れるものと考えられる。また、上記粒子の算術平均粒径が１００ｎｍ未満の場合であっても、フィルムの最表面に多数の粒子を配置させることで、上記仮支持体の感光性樹脂層を有する側の面とは反対側の面の表面粗さＲａを０．０２μｍ～０．２μｍとすることができ、搬送時のシワがより抑制されると考えられる。
　本開示における粒子の算術平均粒径は、（株）日立ハイテクノロジーズ製ＨＴ－７７００型透過型電子顕微鏡（ＴＥＭ）を用いて、加速電圧１００ｋＶで仮支持体を観察し、任意に抽出した粒子４００個の直径の平均値（算術平均値）を求めることで得られる値である。なお、明らかに大きな凝集物（異物、ゴミ等）はカウントしない（上記の計算から除く；つまり、粒子として選択しない）ものとする。 The arithmetic average particle diameter of the above particles is 20 nm to 300 nm from the viewpoints of controllability of surface roughness, suppression of wrinkling during transport, stability over time after exposure, and linearity of the obtained pattern. Is more preferable, 30 nm to 200 nm is more preferable, 40 nm to 120 nm is still more preferable, and 40 nm to 80 nm is particularly preferable.
Further, the arithmetic average particle diameter of the above particles is preferably less than 100 nm from the viewpoint of transparency, wrinkle generation suppressing property during transportation, stability over time after exposure, and linearity of the obtained pattern. When the arithmetic average particle diameter of the particles is less than 100 nm, light scattering can be suppressed at a high level, so that high transparency can be realized and stability over time after exposure is considered to be excellent. Further, even when the arithmetic mean particle diameter of the particles is less than 100 nm, by disposing a large number of particles on the outermost surface of the film, the surface of the temporary support is opposite to the surface having the photosensitive resin layer. It is considered that the surface roughness Ra of the side surface can be set to 0.02 μm to 0.2 μm, and wrinkles during transportation can be further suppressed.
The arithmetic mean particle size of the particles in the present disclosure is 400 particles arbitrarily extracted by observing a temporary support at an acceleration voltage of 100 kV using a HT-7700 transmission electron microscope (TEM) manufactured by Hitachi High-Technologies Corporation. It is a value obtained by obtaining the average value (arithmetic average value) of the individual diameters. Note that obviously large aggregates (foreign matter, dust, etc.) are not counted (excluded from the above calculation; that is, not selected as particles).
　上記粒子含有層の厚さは、表面粗さの制御容易性、及び、搬送時のシワ発生抑制性の観点から、５ｎｍ～３００ｎｍであることが好ましく、１０ｎｍ～１００ｎｍであることがより好ましく、３０ｎｍ～７０ｎｍであることが特に好ましい。なお、上記粒子含有層を２層以上有する場合は、上記粒子含有層の好ましい厚さは、上記粒子含有層１層毎の好ましい厚さである。 The thickness of the particle-containing layer is preferably 5 nm to 300 nm, more preferably 10 nm to 100 nm, and more preferably 30 nm, from the viewpoint of easy control of the surface roughness and the property of suppressing the generation of wrinkles during transportation. Particularly preferably, it is from about 70 nm. When the particle-containing layer has two or more layers, the preferred thickness of the particle-containing layer is the preferred thickness of each particle-containing layer.
　上記粒子含有層の厚さは、以下の方法により測定することができる。
　仮支持体の厚さ方向の断面観察像において、無作為に選択した１０箇所で測定される上記粒子含有層の厚さの算術平均値を求め、得られる値を仮支持体の厚さとする。仮支持体の厚さ方向の断面観察像は、走査型電子顕微鏡（ＳＥＭ）又はレーザー顕微鏡を用いて得ることができる。 The thickness of the particle-containing layer can be measured by the following method.
In the cross-sectional observation image in the thickness direction of the temporary support, the arithmetic mean value of the thicknesses of the particle-containing layers measured at 10 randomly selected points is obtained, and the obtained value is taken as the thickness of the temporary support. The cross-sectional observation image in the thickness direction of the temporary support can be obtained using a scanning electron microscope (SEM) or a laser microscope.
　上記仮支持体の感光性樹脂層を有する側の面とは反対側の面（「バック面」ともいう。）の表面粗さＲａは、０．０２μｍ～０．２０μｍであり、搬送時のシワ発生抑制性、露光後の経時安定性、及び、得られるパターンの直線性の観点から、０．０２μｍ～０．１５μｍであることがより好ましく、０．０３μｍ～０．１２μｍであることがより好ましく、０．０５μｍ～０．１０μｍであることが特に好ましい。また、上記表面粗さＲａが０．２０μｍ以下であると、露光後の経時安定性が良好である。更に、標記表面粗さＲａが０．０２μｍ以上であると、ロールｔｏロールで搬送した際においても、シワの発生が抑制できる。
　また、上記仮支持体の感光性樹脂層を有する側の面の表面粗さＲａは、露光後の経時安定性、及び、得られるパターンの直線性の観点から、上記仮支持体の感光性樹脂層を有する側の面とは反対側の面の表面粗さＲａよりも小さいことが好ましい。 The surface of the temporary support on the side opposite to the surface having the photosensitive resin layer (also referred to as “back surface”) has a surface roughness Ra of 0.02 μm to 0.20 μm, and wrinkles during transportation are observed. From the viewpoints of generation inhibition, stability with time after exposure, and linearity of the obtained pattern, 0.02 μm to 0.15 μm is more preferable, and 0.03 μm to 0.12 μm is more preferable. , 0.05 μm to 0.10 μm is particularly preferable. Further, when the surface roughness Ra is 0.20 μm or less, the temporal stability after exposure is good. Furthermore, when the surface roughness Ra of the marking is 0.02 μm or more, it is possible to suppress the generation of wrinkles even when conveyed by roll to roll.
Further, the surface roughness Ra of the surface of the temporary support on the side having the photosensitive resin layer is, from the viewpoint of stability with time after exposure and linearity of the obtained pattern, the photosensitive resin of the temporary support. It is preferably smaller than the surface roughness Ra of the surface opposite to the surface having the layer.
　上記仮支持体の上記表面粗さＲａは、以下の方法によって測定することができる。
　仮支持体の測定面について、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、仮支持体の表面プロファイルを得る。なお、測定及び解析ソフトには、ＭｅｔｒｏＰｒｏ　ｖｅｒ８．３．２のＭｉｃｒｏｓｃｏｐｅ　Ａｐｐｌｉｃａｔｉｏｎを用いる。次に、上記解析ソフト（ＭｅｔｒｏＰｒｏ　ｖｅｒ８．３．２－Ｍｉｃｒｏｓｃｏｐｅ　Ａｐｐｌｉｃａｔｉｏｎ）にて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、算術平均粗さを算出し、得られる値を表面粗さＲａとする。 The surface roughness Ra of the temporary support can be measured by the following method.
Regarding the measurement surface of the temporary support, a three-dimensional optical profiler (New View7300, manufactured by Zygo) is used to obtain the surface profile of the temporary support under the following conditions. As the measurement and analysis software, the Microscope Application of MetroPro ver 8.3.2 is used. Next, the Surface Map screen is displayed by the above-mentioned analysis software (MetroPro ver 8.3.2-Microscope Application), and histogram data is obtained in the Surface Map screen. The arithmetic mean roughness is calculated from the obtained histogram data, and the obtained value is defined as the surface roughness Ra.
－測定条件－
　対物レンズ：５０倍
　Ｚｏｏｍ：０．５倍
　測定領域：１．００ｍｍ×１．００ｍｍ
　（解析条件）
　Ｒｅｍｏｖｅｄ：ｐｌａｎｅ
　Ｆｉｌｔｅｒ：ｏｆｆ
　ＦｉｌｔｅｒＴｙｐｅ：ａｖｅｒａｇｅ
　Ｒｅｍｏｖｅ　ｓｐｉｋｅｓ：ｏｎ
　Ｓｐｉｋｅ　Ｈｅｉｇｈｔ（ｘＲＭＳ）：７．５ -Measurement condition-
Objective lens: 50 times Zoom: 0.5 times Measurement area: 1.00 mm x 1.00 mm
(Analysis conditions)
Removed: plane
Filter: off
FilterType: average
Remove spikes: on
Spike Height (xRMS): 7.5
　上記仮支持体は、上記粒子含有層以外の材質として、基材を有することが好ましい。
　上記仮支持体としては、露光後の経時安定性、及び、得られるパターンの直線性の観点から、基材の一方の面のみに上記粒子含有層を有するものや、基材の両面にそれぞれ上記粒子含有層を有するものが好ましく挙げられ、基材の一方の面のみに上記粒子含有層を有するものがより好ましく挙げられる。
　上記基材としては、例えば、ガラス基材、樹脂フィルム等が挙げられる。上記の中でも、強度、可撓性等の観点から、樹脂フィルムが好ましい。また、仮支持体が複層構造を有する場合、上記したガラス基材、樹脂フィルム等を基材として用いてもよい。
　樹脂フィルムに含有される樹脂としては、例えば、シクロオレフィンポリマー、ポリエステル樹脂、トリ酢酸セルロース、ポリスチレン樹脂、ポリカーボネート樹脂等が挙げられる。 The temporary support preferably has a base material as a material other than the particle-containing layer.
As the temporary support, from the viewpoint of the temporal stability after exposure, and the linearity of the obtained pattern, the temporary support having the particle-containing layer on only one surface of the base material, or the both surfaces of the base material described above, respectively. Preferred are those having a particle-containing layer, and more preferred are those having the above-mentioned particle-containing layer only on one surface of the substrate.
Examples of the base material include a glass base material and a resin film. Among the above, the resin film is preferable from the viewpoint of strength, flexibility and the like. When the temporary support has a multi-layer structure, the above-mentioned glass base material, resin film or the like may be used as the base material.
Examples of the resin contained in the resin film include cycloolefin polymer, polyester resin, cellulose triacetate, polystyrene resin, and polycarbonate resin.
　中でも、上記仮支持体は、光学特性、耐溶剤性及び耐熱性の観点から、ポリエステル樹脂を含むことが好ましく、ポリエチレンテレフタレートを含むことがより好ましい。
　また、上記仮支持体は、上記基材として、光学特性、耐溶剤性及び耐熱性の観点から、ポリエステル樹脂基材を有することが好ましく、ポリエチレンテレフタレート基材を有することがより好ましい。 Among them, the temporary support preferably contains a polyester resin, more preferably polyethylene terephthalate, from the viewpoints of optical properties, solvent resistance and heat resistance.
Further, the temporary support preferably has a polyester resin substrate as the substrate, and more preferably a polyethylene terephthalate substrate, from the viewpoint of optical characteristics, solvent resistance, and heat resistance.
　樹脂フィルムとしては、シクロオレフィンポリマーフィルム、ポリエステル樹脂フィルム、トリ酢酸セルロースフィルム、ポリスチレン樹脂フィルム、ポリカーボネート樹脂フィルム等が挙げられる。上記の中でも、樹脂フィルムは、光学特性、耐溶剤性、及び耐熱性の観点から、ポリエステル樹脂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 resin film include cycloolefin polymer film, polyester resin film, cellulose triacetate film, polystyrene resin film, polycarbonate resin film and the like. Among the above, the resin film is preferably a polyester resin film, and more preferably a polyethylene terephthalate film, from the viewpoint of optical characteristics, solvent resistance, and heat resistance.
　仮支持体の厚さは、特に制限はないが、露光後の経時安定性、及び、得られるパターンの直線性の観点から、５μｍ以上５０μｍ以下であることが好ましく、１８μｍを超え３０μｍ以下であることがより好ましく、１９μｍ以上２８μｍ以下であることが特に好ましい。 The thickness of the temporary support is not particularly limited, but is preferably 5 μm or more and 50 μm or less, and more than 18 μm and 30 μm or less, from the viewpoint of temporal stability after exposure and linearity of the obtained pattern. It is more preferable that the thickness is 19 μm or more and 28 μm or less.
　仮支持体の厚さは、以下の方法により測定することができる。
　仮支持体の厚さ方向の断面観察像において、無作為に選択した１０箇所で測定される仮支持体の厚さの算術平均値を求め、得られる値を仮支持体の厚さとする。仮支持体の厚さ方向の断面観察像は、走査型電子顕微鏡（ＳＥＭ）又はレーザー顕微鏡を用いて得ることができる。 The thickness of the temporary support can be measured by the following method.
In the cross-sectional observation image in the thickness direction of the temporary support, the arithmetic mean value of the thickness of the temporary support measured at 10 randomly selected places is calculated, and the obtained value is defined as the thickness of the temporary support. The cross-sectional observation image in the thickness direction of the temporary support can be obtained using a scanning electron microscope (SEM) or a laser microscope.
　上記粒子含有層を有する仮支持体の市販品としては、例えば、ルミラー（登録商標。以下同じ。）１６ＫＳ４０（東レ（株）製）、コスモシャイン（登録商標）Ａ－１５１７（東洋紡（株）製）等が挙げられる。 Examples of commercial products of the temporary support having the particle-containing layer include Lumirror (registered trademark; the same applies hereinafter) 16KS40 (manufactured by Toray Co., Ltd.) and Cosmoshine (registered trademark) A-1517 (manufactured by Toyobo Co., Ltd.). ) And the like.
　上記仮支持体のヘーズ値は、露光後の経時安定性、及び、得られるパターンの直線性の観点から、０．８％以下であることが好ましく、０．５％以下であることがより好ましく、０．３％以下であることが更に好ましく、０．２％以下であることが特に好ましい。特にヘーズ値が、０．２％以下であると、露光後の経時安定性により優れる。
　上記仮支持体のヘーズ値は、ヘーズメーターＮＤＨ４００（日本電色工業（株）製）を用いて、仮支持体の面方向の１０箇所においてヘーズ値を測定し、その平均値として得られる値である。 The haze value of the temporary support is preferably 0.8% or less, and more preferably 0.5% or less, from the viewpoint of the temporal stability after exposure and the linearity of the obtained pattern. , 0.3% or less is more preferable, and 0.2% or less is particularly preferable. In particular, when the haze value is 0.2% or less, the temporal stability after exposure is more excellent.
The haze value of the temporary support is a value obtained as an average value by measuring the haze value at 10 positions in the surface direction of the temporary support using a haze meter NDH400 (manufactured by Nippon Denshoku Industries Co., Ltd.). is there.
　仮支持体の製造方法は、制限されず、公知の製造方法を適宜適用することができる。仮支持体が樹脂フィルムである場合、例えば、押出成形等の公知の製造方法によって樹脂フィルムを製造することができる。また、必要に応じて、延伸（例えば、２軸延伸）等によって仮支持体の厚さを調節してもよい。
　また、上記粒子含有層は、例えば、粒子含有層に含まれる成分を水等の公知の溶剤に分散又は溶解した組成物を、仮支持体の感光性樹脂層を設ける側とは反対側の面に塗布することにより形成される。
　仮支持体が延伸により製造される場合、上記組成物を塗布した後に延伸を行ってもよい。
　上記仮支持体は、基材として二軸延伸フィルムを含むことが好ましく、基材として直交する２つの延伸方向にそれぞれ延伸された二軸延伸フィルムを含むことがより好ましく、基材として直交する２つの延伸方向にそれぞれ延伸された二軸延伸フィルムを含み、かつ上記２つの延伸方向のうちの１つの延伸方向に延伸された粒子含有層を含む仮支持体であることが特に好ましい。
　また、仮支持体の製造方法は、第一延伸方向に延伸された一軸延伸フィルム上に、粒子を含有する層を形成する工程、並びに、上記一軸延伸フィルム及び上記一軸延伸フィルム上に形成された上記粒子を含有する層を、上記一軸延伸フィルムにおけるフィルム面に沿って上記第一延伸方向と直交する第二延伸方向に延伸する工程を含むことが好ましい。 The method for producing the temporary support is not limited, and known production methods can be applied as appropriate. When the temporary support is a resin film, the resin film can be manufactured by a known manufacturing method such as extrusion molding. Further, if necessary, the thickness of the temporary support may be adjusted by stretching (for example, biaxial stretching) or the like.
Further, the particle-containing layer, for example, a composition obtained by dispersing or dissolving the components contained in the particle-containing layer in a known solvent such as water, the surface of the temporary support opposite to the side on which the photosensitive resin layer is provided. It is formed by applying to.
When the temporary support is produced by stretching, stretching may be performed after applying the composition.
The temporary support preferably contains a biaxially stretched film as a base material, more preferably a biaxially stretched film stretched in two orthogonal drawing directions as a base material, and more preferably as a base material. It is particularly preferable that the temporary support includes a biaxially stretched film stretched in each of the two stretching directions and includes a particle-containing layer stretched in one of the two stretching directions.
In addition, the method for producing the temporary support is a step of forming a layer containing particles on a uniaxially stretched film stretched in the first stretching direction, and the uniaxially stretched film and the uniaxially stretched film. It is preferable to include a step of stretching the layer containing the particles in a second stretching direction orthogonal to the first stretching direction along the film surface of the uniaxially stretched film.
＜感光性樹脂層＞
　本開示に係る感光性転写材料は、感光性樹脂層を有し、上記感光性樹脂層が、酸分解性基で保護された酸基を有する構成単位を含有する重合体、及び、光酸発生剤を含有する。
　本開示における感光性樹脂層は、ポジ型感光性樹脂層であり、公知のポジ型感光性樹脂層を用いることができる。また、本開示において用いられる感光性樹脂層は、感度及び解像度の観点から、酸分解性樹脂、すなわち、酸分解性基で保護された酸基を有する構成単位を有する重合体と、光酸発生剤とを含む化学増幅ポジ型感光性樹脂層であることが好ましい。
　後述するオニウム塩、オキシムスルホネート化合物等の光酸発生剤は、活性放射線（活性光線）に感応して生成される酸が、上記重合体中の保護された酸基の脱保護に対して触媒として作用するので、１個の光量子の作用で生成した酸が、多数の脱保護反応に寄与し、量子収率は１を超え、例えば、１０の数乗のような大きい値となる。このようないわゆる化学増幅の結果として、高感度が得られる。
　一方、活性光線に感応する光酸発生剤としてキノンジアジド化合物を用いた場合、逐次型光化学反応によりカルボキシ基を生成するが、その量子収率は必ず１以下であり、化学増幅型には該当しない。 <Photosensitive resin layer>
A photosensitive transfer material according to the present disclosure has a photosensitive resin layer, the photosensitive resin layer is a polymer containing a structural unit having an acid group protected by an acid-decomposable group, and photoacid generation Contains an agent.
The photosensitive resin layer in the present disclosure is a positive photosensitive resin layer, and a known positive photosensitive resin layer can be used. Further, the photosensitive resin layer used in the present disclosure is, from the viewpoint of sensitivity and resolution, an acid-decomposable resin, that is, a polymer having a structural unit having an acid group protected by an acid-decomposable group, and a photoacid generator. It is preferably a chemically amplified positive photosensitive resin layer containing an agent.
The photo-acid generators such as onium salts and oxime sulfonate compounds described below have an acid generated in response to actinic radiation (actinic rays) as a catalyst for deprotection of the protected acid group in the polymer. Since it acts, the acid generated by the action of one photon contributes to many deprotection reactions, and the quantum yield exceeds 1, which is a large value such as 10 to the power of several. High sensitivity is obtained as a result of such so-called chemical amplification.
On the other hand, when a quinonediazide compound is used as a photoacid generator sensitive to actinic rays, a carboxy group is produced by a sequential photochemical reaction, but its quantum yield is always 1 or less, which is not a chemical amplification type.
〔酸分解性基で保護された酸基を有する構成単位Ａを有する重合体Ｘ〕
　上記感光性樹脂層は、酸分解性基で保護された酸基を有する構成単位（「酸分解性基で保護された酸基を有する構成単位Ａ」、又は、単に「構成単位Ａ」ともいう。）を有する重合体（「酸分解性基で保護された酸基を有する構成単位を有する重合体Ｘ」、又は、単に「重合体Ｘ」ともいう。）を含む。
　また、上記感光性樹脂層は、構成単位Ａを有する重合体Ｘに加え、他の重合体を含んでいてもよい。本開示においては、構成単位Ａを有する重合体Ｘ及び他の重合体をあわせて、「重合体成分」ともいう。
　重合体Ｘは、露光により生じる触媒量の酸等の酸性物質の作用により、重合体Ｘ中の酸分解性基で保護された酸基が脱保護反応を受け酸基となる。この酸基により、感光性樹脂層の現像液への溶解が可能となる。 [Polymer X having a structural unit A having an acid group protected by an acid-decomposable group]
The photosensitive resin layer is also referred to as a constitutional unit having an acid group protected by an acid-decomposable group (“a constitutional unit A having an acid group protected by an acid-decomposable group”, or simply “constitutional unit A”). .) (“polymer X having a structural unit having an acid group protected by an acid-decomposable group” or simply “polymer X”).
In addition to the polymer X having the structural unit A, the photosensitive resin layer may contain another polymer. In the present disclosure, the polymer X having the structural unit A and other polymers are collectively referred to as “polymer component”.
In the polymer X, the acid group protected by the acid-decomposable group in the polymer X undergoes a deprotection reaction due to the action of a catalytic amount of an acid substance such as an acid generated by exposure to be an acid group. This acid group enables the photosensitive resin layer to be dissolved in the developing solution.
　重合体Ｘは、付加重合型の樹脂であることが好ましく、（メタ）アクリル酸又はそのエステルに由来する構成単位を有する重合体であることがより好ましい。なお、（メタ）アクリル酸又はそのエステルに由来する構成単位以外の構成単位、例えば、スチレン化合物に由来する構成単位、ビニル化合物に由来する構成単位等を有していてもよい。
　以下に構成単位Ａの好ましい態様について説明する。 The polymer X is preferably an addition polymerization type resin, and more preferably a polymer having a structural unit derived from (meth)acrylic acid or its ester. In addition, you may have a structural unit other than the structural unit derived from (meth)acrylic acid or its ester, for example, the structural unit derived from a styrene compound, the structural unit derived from a vinyl compound, etc.
Hereinafter, preferred embodiments of the structural unit A will be described.
－構成単位Ａ－
　上記重合体成分は、酸分解性基で保護された酸基を有する構成単位Ａを有する重合体Ｘを含むことが好ましい。感光性樹脂層が構成単位Ａを有する重合体Ｘを含むことにより、極めて高感度な化学増幅ポジ型の感光性樹脂層とすることができる。
　本開示における酸基及び酸分解性基は、公知のものを使用でき、特に限定されない。具体的な酸基としては、カルボキシ基、及び、フェノール性水酸基が好ましく挙げられる。また、酸分解性基としては、酸により比較的分解し易い基（例えば、１－アルコキシアルキル基、テトラヒドロピラニル基、又は、テトラヒドロフラニル基等のアセタール型保護基）又は酸により分解するものの酸分解容易性が比較的低い基（例えば、ｔｅｒｔ－ブチル基等の第三級アルキル基、ｔｅｒｔ－ブチルオキシカルボニル基等の第三級アルキルオキシカルボニル基（炭酸エステル型保護基））が挙げられる。
　これらの中でも、酸分解性基としては、感度、及び、解像度の観点から、アセタールの形で保護された構造を有する基（アセタール型酸分解性基）であることが好ましい。
　更に、上記酸分解性基で保護された酸基は、感度、及び、解像度の観点から、アセタール型酸分解性基で保護されたカルボキシ基であることがより好ましい。
　また、酸分解性基としては、導電パターンの形成に適用した場合における導電配線の線幅のバラツキが抑制される観点から、分子量が３００以下（例えば３０～３００）の酸分解性基であることが好ましい。
　上記感光性樹脂層に含まれる重合体Ｘは、１種のみであっても、２種以上であってもよい。 -Structural unit A-
The polymer component preferably contains a polymer X having a structural unit A having an acid group protected by an acid-decomposable group. By containing the polymer X having the structural unit A in the photosensitive resin layer, a chemically amplified positive photosensitive resin layer having extremely high sensitivity can be obtained.
As the acid group and the acid-decomposable group in the present disclosure, known groups can be used and are not particularly limited. Preferred specific acid groups include a carboxy group and a phenolic hydroxyl group. The acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal-type protecting group such as a 1-alkoxyalkyl group, a tetrahydropyranyl group, or a tetrahydrofuranyl group) or an acid that is decomposed by an acid. Examples thereof include groups having relatively low decomposability (for example, tertiary alkyl groups such as tert-butyl group, tertiary alkyloxycarbonyl groups such as tert-butyloxycarbonyl group (carbonic acid ester type protecting group)).
Among these, the acid-decomposable group is preferably a group having a structure protected in the form of acetal (acetal-type acid-decomposable group) from the viewpoint of sensitivity and resolution.
Further, the acid group protected by the acid-decomposable group is more preferably a carboxy group protected by an acetal-type acid-decomposable group from the viewpoint of sensitivity and resolution.
Further, the acid-decomposable group is an acid-decomposable group having a molecular weight of 300 or less (for example, 30 to 300) from the viewpoint of suppressing variation in the line width of the conductive wiring when applied to the formation of a conductive pattern. Is preferred.
The polymer X contained in the photosensitive resin layer may be only one kind or two or more kinds.
　酸分解性基で保護された酸基を有する構成単位Ａは、感度及び解像度の観点から、下記式Ａ１、式Ａ２、又は式Ａ３により表される構成単位であることが好ましい。 The structural unit A having an acid group protected by an acid-decomposable group is preferably a structural unit represented by the following formula A1, formula A2, or formula A3 from the viewpoint of sensitivity and resolution.
Figure JPOXMLDOC01-appb-C000001
 
Figure JPOXMLDOC01-appb-C000001
 
　式Ａ１中、Ｒ１１及びＲ１２はそれぞれ独立に、水素原子、アルキル基又はアリール基を表し、Ｒ１１及びＲ１２の少なくとも一方がアルキル基又はアリール基であり、Ｒ１３はアルキル基又はアリール基を表し、Ｒ１１又はＲ１２と、Ｒ１３とが連結して環状エーテルを形成してもよく、Ｒ１４は水素原子又はメチル基を表し、Ｘ１は単結合又は二価の連結基を表し、Ｒ１５は置換基を表し、ｎは０～４の整数を表す。
　式Ａ２中、Ｒ２１及びＲ２２はそれぞれ独立に、水素原子、アルキル基又はアリール基を表し、Ｒ２１及びＲ２２の少なくとも一方がアルキル基又はアリール基であり、Ｒ２３はアルキル基又はアリール基を表し、Ｒ２１又はＲ２２と、Ｒ２３とが連結して環状エーテルを形成してもよく、Ｒ２４はそれぞれ独立に、ヒドロキシ基、ハロゲン原子、アルキル基、アルコキシ基、アルケニル基、アリール基、アラルキル基、アルコキシカルボニル基、ヒドロキシアルキル基、アリールカルボニル基、アリールオキシカルボニル基又はシクロアルキル基を表し、ｍは０～３の整数を表す。
　式Ａ３中、Ｒ３１及びＲ３２はそれぞれ独立に、水素原子、アルキル基又はアリール基を表し、Ｒ３１及びＲ３２の少なくとも一方がアルキル基又はアリール基であり、Ｒ３３はアルキル基又はアリール基を表し、Ｒ３１又はＲ３２と、Ｒ３３とが連結して環状エーテルを形成してもよく、Ｒ３４は水素原子又はメチル基を表し、Ｘ０は単結合又は二価の連結基を表す。 In formula A1, R 11 and R 12 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 11 and R 12 is an alkyl group or an aryl group, and R 13 is an alkyl group or an aryl group. R 11 or R 12 and R 13 may combine to form a cyclic ether, R 14 represents a hydrogen atom or a methyl group, and X 1 represents a single bond or a divalent linking group. , R 15 represents a substituent, and n represents an integer of 0 to 4.
In formula A2, R 21 and R 22 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 21 and R 22 is an alkyl group or an aryl group, and R 23 is an alkyl group or an aryl group. R 21 or R 22 and R 23 may be linked to form a cyclic ether, and R 24 is independently a hydroxy group, a halogen atom, an alkyl group, an alkoxy group, an alkenyl group or an aryl group. Represents an aralkyl group, an alkoxycarbonyl group, a hydroxyalkyl group, an arylcarbonyl group, an aryloxycarbonyl group or a cycloalkyl group, and m represents an integer of 0 to 3.
In formula A3, R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group or an aryl group. R 31 or R 32 and R 33 may combine to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or a divalent linking group. ..
　式Ａ３中、Ｒ３１又はＲ３２がアルキル基の場合、炭素数１～１０のアルキル基であることが好ましい。Ｒ３１又はＲ３２がアリール基の場合、フェニル基であることが好ましい。Ｒ３１及びＲ３２は、それぞれ、水素原子又は炭素数１～４のアルキル基であることが好ましい。
　式Ａ３中、Ｒ３３は、アルキル基又はアリール基を表し、炭素数１～１０のアルキル基であることが好ましく、炭素数１～６のアルキル基であることがより好ましい。
　また、Ｒ３１～Ｒ３３におけるアルキル基及びアリール基は、置換基を有していてもよい。
　式Ａ３中、Ｒ３１又はＲ３２と、Ｒ３３とが連結して環状エーテルを形成してもよく、Ｒ３１又はＲ３２と、Ｒ３３とが連結して環状エーテルを形成することが好ましい。環状エーテルの環員数は特に制限はないが、５又は６であることが好ましく、５であることがより好ましい。
　式Ａ３中、Ｘ０は単結合又はアリーレン基を表し、単結合であることが好ましい。アリーレン基は、置換基を有していてもよい。
　上記式Ａ３で表される構成単位Ａは、アセタール型酸分解性基で保護されたカルボキシ基を有する構成単位である。重合体Ｘが式Ａ３で表される構成単位Ａを含むことで、パターン形成時の感度に優れ、また、解像度がより優れる。 In formula A3, when R 31 or R 32 is an alkyl group, it is preferably an alkyl group having 1 to 10 carbon atoms. When R 31 or R 32 is an aryl group, it is preferably a phenyl group. R 31 and R 32 are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In formula A3, R 33 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
Moreover, the alkyl group and the aryl group in R 31 to R 33 may have a substituent.
In formula A3, R 31 or R 32 and R 33 may be linked to each other to form a cyclic ether, and R 31 or R 32 and R 33 are preferably linked to each other to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In formula A3, X 0 represents a single bond or an arylene group, and is preferably a single bond. The arylene group may have a substituent.
The structural unit A represented by the above formula A3 is a structural unit having a carboxy group protected by an acetal-type acid-decomposable group. When the polymer X contains the structural unit A represented by the formula A3, the sensitivity during pattern formation is excellent and the resolution is further excellent.
　式Ａ３中、Ｒ３４は水素原子又はメチル基を表し、重合体Ｘのガラス転移温度（Ｔｇ）をより低くし得るという観点から、水素原子であることが好ましい。
　より具体的には、重合体Ｘに含まれる構成単位Ａの全量に対し、式Ａ３におけるＲ３４が水素原子である構成単位は２０質量％以上であることが好ましい。
　なお、構成単位Ａ中の、式Ａ３におけるＲ３４が水素原子である構成単位の含有量（含有割合：質量比）は、１３Ｃ－核磁気共鳴スペクトル（ＮＭＲ）測定から常法により算出されるピーク強度の強度比により確認することができる。 In formula A3, R 34 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the glass transition temperature (Tg) of the polymer X can be further lowered.
More specifically, with respect to the total amount of the structural unit A contained in the polymer X, the structural unit in which R 34 in the formula A3 is a hydrogen atom is preferably 20% by mass or more.
The content (content ratio: mass ratio) of the structural unit in which R 34 in the formula A3 is a hydrogen atom in the structural unit A is calculated by a conventional method from 13 C-nuclear magnetic resonance spectrum (NMR) measurement. It can be confirmed by the intensity ratio of peak intensity.
　また、式Ａ１～式Ａ３の好ましい態様としては、国際公開第２０１８／１７９６４０号の段落００４４～段落００５８を参照することができる。 Further, as preferred embodiments of the formulas A1 to A3, reference can be made to paragraphs 0044 to 0058 of WO2018/179640.
　式Ａ１～式Ａ３において、酸分解性基は、感度の観点から、環状構造を有する基であることが好ましく、テトラヒドロフラン環又はテトラヒドロピラン環構造を有する基であるがより好ましく、テトラヒドロフラン環構造を有する基であることが更に好ましく、テトラヒドロフラニル基であることが特に好ましい。 In formulas A1 to A3, the acid-decomposable group is preferably a group having a cyclic structure, more preferably a group having a tetrahydrofuran ring or a tetrahydropyran ring structure, and more preferably a tetrahydrofuran ring structure, from the viewpoint of sensitivity. A group is more preferable, and a tetrahydrofuranyl group is particularly preferable.
　重合体Ｘに含まれる構成単位Ａは、１種であっても、２種以上であってもよい。
　重合体Ｘにおける構成単位Ａの含有量は、重合体成分の全質量に対して、１０質量％～７０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％～４０質量％であることが更に好ましい。上記範囲であると、解像度がより向上する。
　重合体Ｘが２種以上の構成単位Ａを含む場合、上記構成単位Ａの含有量は、２種以上の構成単位Ａの総含有量を表すものとする。
　重合体成分における構成単位Ａの含有量（含有割合：質量比）は、１３Ｃ－ＮＭＲ測定から常法により算出されるピーク強度の強度比により確認することができる。 The structural unit A contained in the polymer X may be one type or two or more types.
The content of the structural unit A in the polymer X is preferably 10% by mass to 70% by mass, more preferably 15% by mass to 50% by mass, and more preferably 20% by mass to the total mass of the polymer component. It is more preferably from 40% by mass to 40% by mass. Within the above range, the resolution is further improved.
When the polymer X contains two or more structural units A, the content of the structural units A represents the total content of the two or more structural units A.
The content (content ratio: mass ratio) of the structural unit A in the polymer component can be confirmed by the intensity ratio of peak intensities calculated by a conventional method from 13 C-NMR measurement.
－酸基を有する構成単位Ｂ－
　重合体Ｘは、酸基を有する構成単位Ｂ（単に「構成単位Ｂ」ともいう。）を含んでいてもよい。
　構成単位Ｂは、酸分解性基で保護されていない酸基、すなわち、保護基を有さない酸基を有する構成単位である。重合体Ｘが構成単位Ｂを含むことで、パターン形成時の感度が良好となり、パターン露光後の現像工程においてアルカリ性の現像液に溶けやすくなり、現像時間の短縮化を図ることができる。
　本明細書における酸基とは、ｐＫａが１２以下のプロトン解離性基を意味する。
　酸基のｐＫａは、感度向上の観点から、１０以下が好ましく、６以下がより好ましい。また、酸基のｐＫａは、－５以上であることが好ましい。
　上記酸基としては、カルボキシ基、スルホンアミド基、ホスホン酸基、スルホ基、フェノール性水酸基、及び、スルホニルイミド基等が例示される。中でも、カルボキシ基又はフェノール性水酸基が好ましく、カルボキシ基がより好ましい。 -Structural unit B having an acid group-
The polymer X may include a structural unit B having an acid group (also simply referred to as “structural unit B”).
The structural unit B is a structural unit having an acid group not protected by an acid-decomposable group, that is, an acid group having no protective group. When the polymer X contains the structural unit B, the sensitivity at the time of pattern formation becomes good, the polymer X easily dissolves in an alkaline developing solution in the developing step after pattern exposure, and the developing time can be shortened.
The acid group in the present specification means a proton dissociative group having a pKa of 12 or less.
From the viewpoint of improving the sensitivity, the pKa of the acid group is preferably 10 or less, more preferably 6 or less. The pKa of the acid group is preferably −5 or more.
Examples of the acid group include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfo group, a phenolic hydroxyl group, and a sulfonylimide group. Among them, a carboxy group or a phenolic hydroxyl group is preferable, and a carboxy group is more preferable.
　重合体Ｘに含まれる構成単位Ｂは、１種のみであっても、２種以上であってもよい。
　重合体Ｘにおける構成単位Ｂの含有量は、重合体成分の全質量に対して、０．０１質量％～２０質量％であることが好ましく、０．０１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い。上記範囲であると、解像性がより良好となる。
　重合体Ｘが２種以上の構成単位Ｂを含む場合、上記構成単位Ｂの含有量は、２種以上の構成単位Ｂの総含有量を表すものとする。
　重合体Ｘにおける構成単位Ｂの含有量（含有割合：質量比）は、１３Ｃ－ＮＭＲ測定から常法により算出されるピーク強度の強度比により確認することができる。 The structural unit B contained in the polymer X may be only one type or two or more types.
The content of the structural unit B in the polymer X is preferably 0.01% by mass to 20% by mass, and more preferably 0.01% by mass to 10% by mass, based on the total mass of the polymer component. It is more preferably 0.1% by mass to 5% by mass. Within the above range, the resolution becomes better.
When the polymer X contains two or more structural units B, the content of the structural unit B represents the total content of the two or more structural units B.
The content (content ratio: mass ratio) of the structural unit B in the polymer X can be confirmed by an intensity ratio of peak intensities calculated by a conventional method from 13 C-NMR measurement.
－その他の構成単位Ｃ－
　重合体Ｘは、既述の構成単位Ａ及び構成単位Ｂ以外の、その他の構成単位Ｃ（単に「構成単位Ｃ」ともいう。）を、本開示に係る感光性転写材料の効果を損なわない範囲で含むことが好ましい。
　構成単位Ｃを形成するモノマーとしては、特に制限はなく、例えば、スチレン類、（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸環状アルキルエステル、（メタ）アクリル酸アリールエステル、不飽和ジカルボン酸ジエステル、ビシクロ不飽和化合物、マレイミド化合物、不飽和芳香族化合物、共役ジエン系化合物、不飽和モノカルボン酸、不飽和ジカルボン酸、不飽和ジカルボン酸無水物、脂肪族環式骨格を有する基、その他の不飽和化合物を挙げることができる。
　構成単位Ｃを用い、その種類及び含有量の少なくともいずれかを調整することで、重合体Ｘの諸特性を調整することができる。特に、構成単位Ｃを含むことで、重合体ＸのＴｇ、酸価及び親疎水性を容易に調整することができる。
　重合体Ｘは、構成単位Ｃを１種のみ含んでもよく、２種以上含んでいてもよい。 -Other building blocks C-
The polymer X is a range that does not impair the effects of the photosensitive transfer material according to the present disclosure, other than the above-described structural unit A and structural unit B, other structural unit C (also simply referred to as “structural unit C”). It is preferable to include.
The monomer forming the structural unit C is not particularly limited, and examples thereof include styrenes, (meth)acrylic acid alkyl ester, (meth)acrylic acid cyclic alkyl ester, (meth)acrylic acid aryl ester, and unsaturated dicarboxylic acid diester. , Bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, groups having an aliphatic cyclic skeleton, other Mention may be made of saturated compounds.
By using the structural unit C and adjusting at least one of the type and content thereof, various properties of the polymer X can be adjusted. In particular, by including the structural unit C, the Tg, acid value and hydrophilicity/hydrophobicity of the polymer X can be easily adjusted.
The polymer X may include only one type of the structural unit C or may include two or more types.
　構成単位Ｃは、具体的には、スチレン、α－メチルスチレン、アセトキシスチレン、メトキシスチレン、エトキシスチレン、クロロスチレン、ビニル安息香酸メチル、ビニル安息香酸エチル、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸２－エチルヘキシル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸シクロペンチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸イソボルニル、アクリロニトリル、又は、エチレングリコールモノアセトアセテートモノ（メタ）アクリレートなどを重合して形成される構成単位を挙げることができる。その他、特開２００４－２６４６２３号公報の段落００２１～段落００２４に記載の化合物を挙げることができる。 The structural unit C is specifically styrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, methyl (meth)acrylate, (meth)acrylic. Ethyl acid, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth) 2-Hydroxypropyl acrylate, benzyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth)acrylate, etc. A structural unit formed by polymerizing In addition, compounds described in paragraphs 0021 to 0024 of JP-A-2004-264623 can be mentioned.
　構成単位Ｃは、解像性の観点から、塩基性基を有する構成単位を含むことが好ましい。
　上記塩基性基としては、具体的には、脂肪族アミノ基、芳香族アミノ基、又は、含窒素複素芳香環基などの窒素原子を有する基が挙げられ、脂肪族アミノ基が好ましい。
　脂肪族アミノ基は、第一級アミノ基、第二級アミノ基、又は、第三級アミノ基のいずれであってもよいが、解像性の観点から、第二級アミノ基、又は、第三級アミノ基であることが好ましい。 From the viewpoint of resolution, the structural unit C preferably contains a structural unit having a basic group.
Specific examples of the basic group include groups having a nitrogen atom such as an aliphatic amino group, an aromatic amino group, and a nitrogen-containing heteroaromatic ring group, and an aliphatic amino group is preferable.
The aliphatic amino group may be any of a primary amino group, a secondary amino group, or a tertiary amino group, but from the viewpoint of resolution, a secondary amino group or a secondary amino group, or It is preferably a tertiary amino group.
　塩基性基を有する構成単位を形成するモノマーとしては、具体的には、メタクリル酸１，２，２，６，６－ペンタメチル－４－ピペリジル、メタクリル酸２－（ジメチルアミノ）エチル、アクリル酸２，２，６，６－テトラメチル－４－ピペリジル、メタクリル酸２，２，６，６－テトラメチル－４－ピペリジル、アクリル酸２，２，６，６－テトラメチル－４－ピペリジル、メタクリル酸２－（ジエチルアミノ）エチル、アクリル酸２－（ジメチルアミノ）エチル、アクリル酸２－（ジエチルアミノ）エチル、メタクリル酸Ｎ－（３－ジメチルアミノ）プロピル、アクリル酸Ｎ－（３－ジメチルアミノ）プロピル、メタクリル酸Ｎ－（３－ジエチルアミノ）プロピル、アクリル酸Ｎ－（３－ジエチルアミノ）プロピル、メタクリル酸２－（ジイソプロピルアミノ）エチル、メタクリル酸２－モルホリノエチル、アクリル酸２－モルホリノエチル、Ｎ－［３－（ジメチルアミノ）プロピル］アクリルアミド、４－アミノスチレン、４－ビニルピリジン、２－ビニルピリジン、３－ビニルピリジン、１－ビニルイミダゾール、２－メチル－１－ビニルイミダゾール、１－アリルイミダゾール、１－ビニル－１，２，４－トリアゾール等が挙げられる。中でもメタクリル酸１，２，２，６，６－ペンタメチル－４－ピペリジルが好ましい。 Specific examples of the monomer forming the structural unit having a basic group include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2-(dimethylamino)ethyl methacrylate, and acrylic acid 2 ,2,6,6-Tetramethyl-4-piperidyl, 2,2,6,6-Tetramethyl-4-piperidyl methacrylate, 2,2,6,6-Tetramethyl-4-piperidyl acrylate, Methacrylic acid 2-(diethylamino)ethyl, 2-(dimethylamino)ethyl acrylate, 2-(diethylamino)ethyl acrylate, N-(3-dimethylamino)propyl methacrylate, N-(3-dimethylamino)propyl acrylate, N-(3-diethylamino)propyl methacrylate, N-(3-diethylamino)propyl acrylate, 2-(diisopropylamino)ethyl methacrylate, 2-morpholinoethyl methacrylate, 2-morpholinoethyl acrylate, N-[3 -(Dimethylamino)propyl]acrylamide, 4-aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazole, 2-methyl-1-vinylimidazole, 1-allylimidazole, 1- Examples thereof include vinyl-1,2,4-triazole. Of these, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate is preferred.
　また、構成単位Ｃとしては、芳香環を有する構成単位、又は、脂肪族環式骨格を有する構成単位が、得られる転写材料の電気特性を向上させる観点で好ましい。これら構成単位を形成するモノマーとして、具体的には、スチレン、α－メチルスチレン、ジシクロペンタニル（メタ）アクリレート、シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、及び、ベンジル（メタ）アクリレート等が挙げられ、シクロヘキシル（メタ）アクリレートが好ましく用いられる。 Further, as the structural unit C, a structural unit having an aromatic ring or a structural unit having an aliphatic cyclic skeleton is preferable from the viewpoint of improving the electrical characteristics of the resulting transfer material. Specific examples of the monomer that forms these structural units include styrene, α-methylstyrene, dicyclopentanyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and Examples thereof include benzyl (meth)acrylate, and cyclohexyl (meth)acrylate is preferably used.
　また、構成単位Ｃを形成するモノマーとしては、例えば、（メタ）アクリル酸アルキルエステルが、密着性の観点で好ましい。中でも、炭素数４～１２のアルキル基を有する（メタ）アクリル酸アルキルエステルが密着性の観点でより好ましい。具体的には、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ｎ－ブチル、及び、（メタ）アクリル酸２－エチルヘキシルが挙げられる。 Further, as the monomer forming the structural unit C, for example, (meth)acrylic acid alkyl ester is preferable from the viewpoint of adhesion. Among them, alkyl (meth)acrylate having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of adhesion. Specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate.
　構成単位Ｃの含有量は、重合体成分の全質量に対し、９０質量％以下が好ましく、８５質量％以下がより好ましく、８０質量％以下が更に好ましい。下限値としては、１０質量％以上が好ましく、２０質量％以上がより好ましい。上記範囲であると、解像度及び密着性がより向上する。
　重合体成分が２種以上の構成単位Ｃを含む場合、上記構成単位Ｃの含有量は、２種以上の構成単位Ｃの総含有量を表すものとする。 The content of the structural unit C is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less, based on the total mass of the polymer component. The lower limit is preferably 10% by mass or more, and more preferably 20% by mass or more. Within the above range, the resolution and adhesiveness are further improved.
When the polymer component contains two or more structural units C, the content of the structural unit C represents the total content of the two or more structural units C.
　以下、本開示における重合体Ｘの好ましい例を挙げるが、本開示は以下の例示に限定されない。なお、下記例示化合物における構成単位の比率、重量平均分子量は、好ましい物性を得るために適宜選択される。 Hereinafter, preferred examples of the polymer X in the present disclosure will be given, but the present disclosure is not limited to the following examples. In addition, the ratio of the structural units and the weight average molecular weight in the following exemplified compounds are appropriately selected to obtain preferable physical properties.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
－重合体Ｘのガラス転移温度：Ｔｇ－
　本開示における重合体Ｘのガラス転移温度（Ｔｇ）は、転写性の観点から、９０℃以下であることが好ましく、２０℃以上６０℃以下であることがより好ましく、３０℃以上５０℃以下であることが更に好ましい。 -Glass transition temperature of polymer X: Tg-
From the viewpoint of transferability, the glass transition temperature (Tg) of the polymer X in the present disclosure is preferably 90° C. or lower, more preferably 20° C. or higher and 60° C. or lower, and 30° C. or higher and 50° C. or lower. More preferably,
　本開示における重合体のＴｇを、既述の好ましい範囲に調整する方法としては、例えば、目的とする重合体の各構成単位の単独重合体のＴｇと各構成単位の質量比より、ＦＯＸ式を指針にして、目的とする重合体のＴｇを制御することが可能である。
　ＦＯＸ式について、以下に説明する。
　重合体に含まれる第１の構成単位の単独重合体のＴｇをＴｇ１、第１の構成単位の共重合体における質量分率をＷ１とし、第２の構成単位の単独重合体のＴｇをＴｇ２とし、第２の構成単位の共重合体における質量分率をＷ２としたときに、第１の構成単位と第２の構成単位とを含む共重合体のＴｇ０（Ｋ）は、以下の式にしたがって推定することが可能である。
　ＦＯＸ式：１／Ｔｇ０＝（Ｗ１／Ｔｇ１）＋（Ｗ２／Ｔｇ２）
　既述のＦＯＸ式を用いて、共重合体に含まれる各構成単位の種類と質量分率を調整して、所望のＴｇを有する共重合体を得ることができる。
　また、重合体の重量平均分子量を調整することにより、重合体のＴｇを調整することも可能である。 As a method of adjusting the Tg of the polymer in the present disclosure to the preferable range described above, for example, from the Tg of the homopolymer of each structural unit of the target polymer and the mass ratio of each structural unit, the FOX formula is It is possible to control the Tg of the desired polymer using the guidelines.
The FOX formula will be described below.
Tg of the homopolymer of the first structural unit contained in the polymer is Tg1, the mass fraction of the copolymer of the first structural unit is W1, and Tg of the homopolymer of the second structural unit is Tg2. When the mass fraction of the copolymer of the second constitutional unit is W2, Tg0(K) of the copolymer containing the first constitutional unit and the second constitutional unit is calculated according to the following formula. It is possible to estimate.
FOX formula: 1/Tg0=(W1/Tg1)+(W2/Tg2)
A copolymer having a desired Tg can be obtained by adjusting the type and mass fraction of each structural unit contained in the copolymer using the above-mentioned FOX formula.
It is also possible to adjust the Tg of the polymer by adjusting the weight average molecular weight of the polymer.
－重合体Ｘの酸価－
　重合体Ｘの酸価は、解像性の観点から、０ｍｇＫＯＨ／ｇ以上５０ｍｇＫＯＨ／ｇ以下であることが好ましく、０ｍｇＫＯＨ／ｇ以上２０ｍｇＫＯＨ／ｇ以下であることがより好ましく、０ｍｇＫＯＨ／ｇ以上１０ｍｇＫＯＨ／ｇ以下であることが更に好ましい。
　また、重合体Ｘの酸価は、露光後の経時安定性、及び、得られるパターンの直線性の観点から、１０ｍｇＫＯＨ／ｇ以下であることが好ましい。 -Acid Value of Polymer X-
From the viewpoint of resolution, the acid value of the polymer X is preferably 0 mgKOH/g or more and 50 mgKOH/g or less, more preferably 0 mgKOH/g or more and 20 mgKOH/g or less, and 0 mgKOH/g or more and 10 mgKOH/g. It is even more preferably g or less.
Further, the acid value of the polymer X is preferably 10 mgKOH/g or less from the viewpoint of the temporal stability after exposure and the linearity of the obtained pattern.
　本開示における重合体の酸価は、重合体１ｇあたりの酸性成分を中和するのに要する水酸化カリウムの質量を表したものである。具体的には、測定サンプルをテトラヒドロフラン／水＝９／１（体積比）混合溶媒に溶解し、電位差滴定装置（商品名：ＡＴ－５１０、京都電子工業（株）製）を用いて、得られた溶液を２５℃において、０．１ｍｏｌ／Ｌ水酸化ナトリウム水溶液で中和滴定する。滴定ｐＨ曲線の変曲点を滴定終点として、次式により酸価を算出する。
　　　Ａ＝５６．１１×Ｖｓ×０．１×ｆ／ｗ
　Ａ：酸価（ｍｇＫＯＨ／ｇ）
　Ｖｓ：滴定に要した０．１ｍｏｌ／Ｌ水酸化ナトリウム水溶液の使用量（ｍＬ）
　ｆ：０．１ｍｏｌ／Ｌ水酸化ナトリウム水溶液の力価
　ｗ：測定サンプルの質量（ｇ）（固形分換算） The acid value of the polymer in the present disclosure represents the mass of potassium hydroxide required to neutralize the acidic component per 1 g of the polymer. Specifically, the measurement sample was dissolved in a mixed solvent of tetrahydrofuran/water=9/1 (volume ratio) and obtained using a potentiometric titrator (trade name: AT-510, manufactured by Kyoto Electronics Manufacturing Co., Ltd.). The solution is neutralized and titrated with a 0.1 mol/L sodium hydroxide aqueous solution at 25°C. Using the inflection point of the titration pH curve as the end point of titration, the acid value is calculated by the following formula.
A=56.11×Vs×0.1×f/w
A: Acid value (mgKOH/g)
Vs: amount of 0.1 mol/L sodium hydroxide aqueous solution used for titration (mL)
f: titer of 0.1 mol/L sodium hydroxide aqueous solution w: mass of measurement sample (g) (solid content conversion)
－重合体Ｘの分子量：Ｍｗ－
　重合体Ｘの分子量は、ポリスチレン換算重量平均分子量で、６０，０００以下であることが好ましい。重合体Ｘの重量平均分子量が６０，０００以下であると、転写材料を転写する際において低温（例えば１３０℃以下）での転写を実現することができる。
　また、重合体Ｘの重量平均分子量は、現像残渣抑制の観点から、２，０００～６０，０００であることが好ましく、３，０００～５０，０００であることがより好ましく、１０，０００～２０，０００であることが特に好ましい。
　重合体Ｘの数平均分子量と重量平均分子量との比（分散度）は、１．０～５．０が好ましく、１．０５～３．５がより好ましい。 -Molecular weight of polymer X: Mw-
The molecular weight of the polymer X is preferably 60,000 or less in terms of polystyrene equivalent weight average molecular weight. When the weight average molecular weight of the polymer X is 60,000 or less, it is possible to realize the transfer at a low temperature (for example, 130° C. or less) when transferring the transfer material.
The weight average molecular weight of the polymer X is preferably 2,000 to 60,000, more preferably 3,000 to 50,000, and more preferably 10,000 to 20 from the viewpoint of suppressing development residues. It is particularly preferable that it is 1,000.
The ratio (dispersion degree) of the number average molecular weight and the weight average molecular weight of the polymer X is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.
　なお、本開示における重合体の重量平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によって測定することができ、測定装置としては、様々な市販の装置を用いることができ、装置の内容、及び、測定技術は、公知のものを用いることができる。
　ゲルパーミエーションクロマトグラフィ（ＧＰＣ）による重量平均分子量の測定は、測定装置として、ＨＬＣ（登録商標）－８２２０ＧＰＣ（東ソー（株）製）を用い、カラムとして、ＴＳＫｇｅｌ（登録商標）Ｓｕｐｅｒ　ＨＺＭ－Ｍ（４．６ｍｍＩＤ×１５ｃｍ、東ソー（株）製）、Ｓｕｐｅｒ　ＨＺ４０００（４．６ｍｍＩＤ×１５ｃｍ、東ソー（株）製）、Ｓｕｐｅｒ　ＨＺ３０００（４．６ｍｍＩＤ×１５ｃｍ、東ソー（株）製）、Ｓｕｐｅｒ　ＨＺ２０００（４．６ｍｍＩＤ×１５ｃｍ、東ソー（株）製）をそれぞれ１本、直列に連結したものを用い、溶離液として、ＴＨＦ（テトラヒドロフラン）を用いることができる。
　また、測定条件としては、試料濃度を０．２質量％、流速を０．３５ｍｌ／ｍｉｎ、サンプル注入量を１０μＬ、及び測定温度を４０℃とし、示差屈折率（ＲＩ）検出器を用いて行うことができる。
　検量線は、東ソー（株）製の「標準試料ＴＳＫ　ｓｔａｎｄａｒｄ，ｐｏｌｙｓｔｙｒｅｎｅ」：「Ｆ－４０」、「Ｆ－２０」、「Ｆ－４」、「Ｆ－１」、「Ａ－５０００」、「Ａ－２５００」及び「Ａ－１０００」の７サンプルのいずれかを用いて作製できる。 The weight average molecular weight of the polymer in the present disclosure can be measured by GPC (gel permeation chromatography), and various commercially available devices can be used as the measuring device. A known measurement technique can be used.
The weight average molecular weight is measured by gel permeation chromatography (GPC) using HLC (registered trademark)-8220 GPC (manufactured by Tosoh Corporation) as a measuring device and TSKgel (registered trademark) Super HZM-M (4) as a column. .6 mmID×15 cm, Tosoh Corporation, Super HZ4000 (4.6 mmID×15 cm, Tosoh Corporation), Super HZ3000 (4.6 mmID×15 cm, Tosoh Corporation), Super HZ2000 (4.6 mmID). It is possible to use THF (tetrahydrofuran) as an eluent by using one having a size of 15 cm each, manufactured by Tosoh Corporation and connected in series.
The measurement conditions are as follows: the sample concentration is 0.2 mass %, the flow rate is 0.35 ml/min, the sample injection amount is 10 μL, and the measurement temperature is 40° C., using a differential refractive index (RI) detector. be able to.
The calibration curve is “standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “A-5000”, It can be manufactured using any of the seven samples of “A-2500” and “A-1000”.
－重合体Ｘの製造方法－
　重合体Ｘの製造方法（合成法）は特に限定されないが、一例を挙げると、構成単位Ａを形成するためのモノマー、更に必要に応じて、構成単位Ｂを形成するためのモノマー及び構成単位Ｃを形成するためのモノマーを含む有機溶剤中、重合開始剤を用いて重合することにより合成することができる。また、いわゆる高分子反応で合成することもできる。 -Method for producing polymer X-
The production method (synthesis method) of the polymer X is not particularly limited, but, for example, a monomer for forming the structural unit A, and, if necessary, a monomer for forming the structural unit B and a structural unit C are given. It can be synthesized by polymerizing with a polymerization initiator in an organic solvent containing a monomer for forming a. It can also be synthesized by a so-called polymer reaction.
－重合体成分又は重合体Ｘの含有量－
　本開示における上記感光性樹脂層は、密着性の観点から、上記感光性樹脂層の全質量に対し、上記重合体成分を５０質量％～９９．９質量％の割合で含むことが好ましく、７０質量％～９８質量％の割合で含むことがより好ましい。
　また、上記感光性樹脂層は、密着性の観点から、上記感光性樹脂層の全質量に対し、重合体Ｘを５０質量％～９９．９質量％の割合で含むことが好ましく、７０質量％～９８質量％の割合で含むことがより好ましい。 -Content of Polymer Component or Polymer X-
From the viewpoint of adhesion, the photosensitive resin layer in the present disclosure preferably contains the polymer component in a ratio of 50% by mass to 99.9% by mass with respect to the total mass of the photosensitive resin layer, 70 It is more preferable that the content is in the range of mass% to 98 mass %.
From the viewpoint of adhesion, the photosensitive resin layer preferably contains the polymer X in a proportion of 50% by mass to 99.9% by mass, and 70% by mass with respect to the total mass of the photosensitive resin layer. More preferably, it is contained in a proportion of about 98% by mass.
〔他の重合体〕
　上記感光性樹脂層は、重合体成分として、重合体Ｘに加え、本開示に係る感光性転写材料の効果を損なわない範囲において、酸分解性基で保護された酸基を有する構成単位を含まない重合体（「他の重合体」ともいう。）を更に含んでいてもよい。
　本開示における重合体成分は、特に述べない限り、重合体Ｘに加え、必要に応じて添加される他の重合体を含めたものを意味するものとする。なお、後述する架橋剤、分散剤及び界面活性剤に該当する化合物は、高分子化合物であっても、重合体成分に含まないものとする。
　上記感光性樹脂層が他の重合体を含む場合、他の重合体の含有量は、全重合体成分中、５０質量％以下であることが好ましく、３０質量％以下であることがより好ましく、２０質量％以下であることが更に好ましい。 [Other polymers]
The photosensitive resin layer contains, as a polymer component, a structural unit having an acid group protected by an acid-decomposable group, in addition to the polymer X, as long as the effect of the photosensitive transfer material according to the present disclosure is not impaired. The polymer may be further included (also referred to as "other polymer").
Unless otherwise stated, the polymer component in the present disclosure means the polymer including the polymer X and other polymers added as necessary. In addition, even if it is a high molecular compound, the compound applicable to the below-mentioned crosslinking agent, dispersant, and surfactant shall not be included in the polymer component.
When the photosensitive resin layer contains another polymer, the content of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less, based on all polymer components. It is more preferably 20% by mass or less.
　上記感光性樹脂層は、重合体Ｘに加え、他の重合体を１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。
　他の重合体として、例えばポリヒドロキシスチレンを用いることができ、市販されている、ＳＭＡ　１０００Ｐ、ＳＭＡ　２０００Ｐ、ＳＭＡ　３０００Ｐ、ＳＭＡ　１４４０Ｆ、ＳＭＡ　１７３５２Ｐ、ＳＭＡ　２６２５Ｐ、及び、ＳＭＡ　３８４０Ｆ（以上、サートマー社製）、ＡＲＵＦＯＮ　ＵＣ－３０００、ＡＲＵＦＯＮ　ＵＣ－３５１０、ＡＲＵＦＯＮ　ＵＣ－３９００、ＡＲＵＦＯＮ　ＵＣ－３９１０、ＡＲＵＦＯＮ　ＵＣ－３９２０、及び、ＡＲＵＦＯＮ　ＵＣ－３０８０（以上、東亞合成（株）製）、並びに、Ｊｏｎｃｒｙｌ　６９０、Ｊｏｎｃｒｙｌ　６７８、Ｊｏｎｃｒｙｌ　６７、及び、Ｊｏｎｃｒｙｌ　５８６（以上、ＢＡＳＦ社製）等を用いることもできる。 In addition to the polymer X, the photosensitive resin layer may include only one type of other polymer, or may include two or more types thereof.
As another polymer, for example, polyhydroxystyrene can be used, and commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, manufactured by Sartomer). , ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 (all manufactured by Toagosei Co., Ltd.), and Joncryl 690, Joncr. , Joncryl 67, and Joncryl 586 (above, manufactured by BASF) can also be used.
〔光酸発生剤〕
　上記感光性樹脂層は、光酸発生剤を含む。
　本開示で使用される光酸発生剤は、紫外線、遠紫外線、Ｘ線、電子線等の活性光線を照射することにより酸を発生することができる化合物である。
　本開示で使用される光酸発生剤としては、波長３００ｎｍ以上、好ましくは波長３００ｎｍ～４５０ｎｍの活性光線に感応し、酸を発生する化合物が好ましいが、そ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酸発生剤についても、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。
　本開示で使用される光酸発生剤としては、ｐＫａが４以下の酸を発生する光酸発生剤が好ましく、ｐＫａが３以下の酸を発生する光酸発生剤がより好ましく、ｐＫａが２以下の酸を発生する光酸発生剤が特に好ましい。ｐＫａの下限値は特に定めないが、例えば、－１０．０以上であることが好ましい。
　また、光酸発生剤は、露光後の経時安定性、得られるパターンの直線性、及び、現像残渣抑制の観点から、炭素数１～４のアルキルスルホン酸を発生する光酸発生剤を含むことが好ましく、炭素数１～４のアルキルスルホン酸を発生する光酸発生剤とアリールスルホン酸を発生する光酸発生剤とを含むことがより好ましい。
　上記アルキルスルホン酸を発生する光酸発生剤は、露光後の経時安定性、得られるパターンの直線性、及び、現像残渣抑制の観点から、メタンスルホン酸（メシル酸）を発生する光酸発生剤であることが好ましい。
　また、上記アリールスルホン酸を発生する光酸発生剤は、露光後の経時安定性、得られるパターンの直線性、及び、現像残渣抑制の観点から、ｐ－トルエンスルホン酸（トシル酸）を発生する光酸発生剤であることが好ましい。
　ｐＫａが４．０以下の酸を発生する光酸発生剤、ｐＫａが３．０以下の酸を発生する光酸発生剤、ｐＫａが２．０以下の酸を発生する光酸発生剤等を用いた場合には、比較的強い酸が発生することになる。 [Photo acid generator]
The photosensitive resin layer contains a photo-acid generator.
The photo-acid generator used in the present disclosure is a compound capable of generating an acid when irradiated with an actinic ray such as an ultraviolet ray, a deep ultraviolet ray, an X-ray or an electron beam.
The photo-acid generator used in the present disclosure is preferably a compound that reacts with an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm to generate an acid, but its chemical structure is not limited. Further, regarding a photo-acid generator which is not directly sensitive to actinic rays having a wavelength of 300 nm or more, when used in combination with a sensitizer, it is a compound which is sensitive to actinic rays having a wavelength of 300 nm or more and generates an acid. It can be preferably used in combination.
The photoacid generator used in the present disclosure is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and a pKa of 2 or less. Particularly preferred are photoacid generators that generate the above acid. The lower limit of pKa is not particularly limited, but is preferably -10.0 or more, for example.
Further, the photo-acid generator contains a photo-acid generator capable of generating an alkylsulfonic acid having 1 to 4 carbon atoms from the viewpoints of stability over time after exposure, linearity of the obtained pattern, and suppression of development residue. Is preferable, and it is more preferable to include a photoacid generator that generates an alkylsulfonic acid having 1 to 4 carbon atoms and a photoacid generator that generates an arylsulfonic acid.
The photoacid generator that generates the alkylsulfonic acid is a photoacid generator that generates methanesulfonic acid (mesyl acid) from the viewpoints of temporal stability after exposure, linearity of the obtained pattern, and development residue suppression. Is preferred.
Further, the photoacid generator that generates the arylsulfonic acid generates p-toluenesulfonic acid (tosylic acid) from the viewpoints of stability with time after exposure, linearity of the obtained pattern, and suppression of development residue. It is preferably a photoacid generator.
Uses a photoacid generator that generates an acid with a pKa of 4.0 or less, a photoacid generator that generates an acid with a pKa of 3.0 or less, or a photoacid generator that generates an acid with a pKa of 2.0 or less. If so, a relatively strong acid will be generated.
　光酸発生剤としては、イオン性光酸発生剤及び非イオン性光酸発生剤を挙げることができる。
　イオン性光酸発生剤の例として、ジアリールヨードニウム塩類及びトリアリールスルホニウム塩類等のオニウム塩化合物、第四級アンモニウム塩類等を挙げることができる。これらのうち、オニウム塩化合物が好ましく、トリアリールスルホニウム塩類及びジアリールヨードニウム塩類が特に好ましい。
　イオン性光酸発生剤としては、特開２０１４－８５６４３号公報の段落０１１４～段落０１３３に記載のイオン性光酸発生剤も好ましく用いることができる。
　非イオン性光酸発生剤の例としては、トリクロロメチル－ｓ－トリアジン類、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などを挙げることができる。これらの中でも、感度、解像度、及び、密着性の観点から、光酸発生剤がオキシムスルホネート化合物であることが好ましい。トリクロロメチル－ｓ－トリアジン類、ジアゾメタン化合物及びイミドスルホネート化合物の具体例としては、特開２０１１－２２１４９４号公報の段落００８３～段落００８８に記載の化合物が例示できる。 Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.
Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. Of these, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.
As the ionic photoacid generator, the ionic photoacid generator described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.
Examples of the nonionic photoacid generator include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, the photo-acid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion. Specific examples of the trichloromethyl-s-triazines, diazomethane compounds and imidosulfonate compounds include the compounds described in paragraphs 0083 to 0088 of JP 2011-221494A.
　オキシムスルホネート化合物としては、国際公開第２０１８／１７９６４０号の段落００８４～段落００８８に記載されたものを好適に用いることができる。 As the oxime sulfonate compound, those described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 can be preferably used.
　光酸発生剤としては、感度及び解像度の観点から、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ばれた少なくとも１種の化合物を含むことが好ましく、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。
　また、好ましい光酸発生剤として、例えば、以下の構造の光酸発生剤が挙げられる。 From the viewpoint of sensitivity and resolution, the photo-acid generator preferably contains at least one compound selected from the group consisting of onium salt compounds and oxime sulfonate compounds, and more preferably contains oxime sulfonate compounds. ..
In addition, examples of preferable photoacid generators include photoacid generators having the following structures.
Figure JPOXMLDOC01-appb-C000004
 
Figure JPOXMLDOC01-appb-C000004
 
　上記感光性樹脂層は、光酸発生剤を、１種単独で含んでいてもよいし、２種以上の光酸発生剤を含んでいてもよい。
　上記感光性樹脂層における光酸発生剤の含有量は、感度及び解像度の観点から、上記感光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 photosensitive resin layer may contain one photoacid generator alone, or may contain two or more photoacid generators.
From the viewpoint of sensitivity and resolution, the content of the photo-acid generator in the photosensitive resin layer is preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer, and 0 It is more preferably from 0.5% by mass to 5% by mass.
〔その他の添加剤〕
　本開示における上記感光性樹脂層は、重合体Ｘ、光酸発生剤及び溶剤に加え、必要に応じて、その他の添加剤を含むことができる。
　その他の添加剤としては、公知のものを用いることができ、例えば、可塑剤、増感剤、ヘテロ環状化合物、アルコキシシラン化合物、塩基性化合物、防錆剤、界面活性剤等が挙げられる。
　可塑剤、増感剤、ヘテロ環状化合物及びアルコキシシラン化合物としては、国際公開第２０１８／１７９６４０号の段落００９７～段落０１１９に記載されたものが挙げられる。
　更に、本開示に係る感光性転写材料における感光性樹脂層は、溶剤を含んでいてもよい。溶剤を含む感光性樹脂組成物により感光性樹脂層を形成した場合、溶剤が残留することもある。
　感光性樹脂層における溶剤の含有量は、感光性樹脂層の全質量に対し、５質量％以下であることが好ましく、２質量％以下であることがより好ましく、１質量％以下であることが更に好ましい。 [Other additives]
The above-mentioned photosensitive resin layer in the present disclosure can contain other additives in addition to the polymer X, the photo-acid generator and the solvent, if necessary.
As other additives, known ones can be used, and examples thereof include a plasticizer, a sensitizer, a heterocyclic compound, an alkoxysilane compound, a basic compound, a rust preventive, and a surfactant.
Examples of the plasticizer, sensitizer, heterocyclic compound and alkoxysilane compound include those described in paragraphs 0097 to 0119 of International Publication No. 2018/179640.
Further, the photosensitive resin layer in the photosensitive transfer material according to the present disclosure may contain a solvent. When the photosensitive resin layer is formed from the photosensitive resin composition containing a solvent, the solvent may remain.
The content of the solvent in the photosensitive resin layer is preferably 5% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less, based on the total mass of the photosensitive resin layer. More preferable.
－塩基性化合物－
　上記感光性樹脂層は、塩基性化合物を更に含むことが好ましい。
　塩基性化合物は、化学増幅レジストで用いられる塩基性化合物の中から任意に選択して使用することができる。例えば、脂肪族アミン、芳香族アミン、複素環式アミン、第四級アンモニウムヒドロキシド、及び、カルボン酸の第四級アンモニウム塩等が挙げられる。これらの具体例としては、特開２０１１－２２１４９４号公報の段落０２０４～段落０２０７に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。
　また、塩基性化合物としては、Ｎ－シクロヘキシル－Ｎ’－［２－（４－モルホリニル）エチル］チオ尿素（ＣＭＴＵ）を好適に用いることができる。また、ＣＭＴＵの市販品としては、東洋化成工業（株）製のものが挙げられる。 -Basic compound-
The photosensitive resin layer preferably further contains a basic compound.
The basic compound can be arbitrarily selected and used from the basic compounds used in the chemically amplified resist. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include the compounds described in paragraphs 0204 to 0207 of JP 2011-221494 A, the contents of which are incorporated herein.
As the basic compound, N-cyclohexyl-N'-[2-(4-morpholinyl)ethyl]thiourea (CMTU) can be preferably used. Further, examples of commercially available CMTU include those manufactured by Toyo Kasei Co., Ltd.
　塩基性化合物としては、露光後の経時安定性、得られるパターンの直線性、及び、現像残渣抑制の観点から、ベンゾトリアゾール化合物が好ましい。
　ベンゾトリアゾール化合物としては、ベンゾトリアゾール骨格を有する化合物であれば制限されず、公知のベンゾトリアゾール化合物を用いることができる。
　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－［Ｎ，Ｎ－ビス（２－エチルヘキシル）アミノメチル］ベンゾトリアゾール、５－カルボキシベンゾトリアゾール、１－（ヒドロキシメチル）－１Ｈ－ベンゾトリアゾール、１－アセチル－１Ｈ－ベンゾトリアゾール、１－アミノベンゾトリアゾール、９－（１Ｈ－ベンゾトリアゾール－１－イルメチル）－９Ｈ－カルバゾール、１－クロロ－１Ｈ－ベンゾトリアゾール、１－（２－ピリジニル）ベンゾトリアゾール、１－ヒドロキシベンゾトリアゾール、１－メチルベンゾトリアゾール、１－エチルベンゾトリアゾール、１－（１’－ヒドロキシエチル）ベンゾトリアゾール、１－（２’－ヒドロキシエチル）ベンゾトリアゾール、１－プロピルベンゾトリアゾール、１－（１’－ヒドロキシプロピル）ベンゾトリアゾール、１－（２’－ヒドロキシプロピル）ベンゾトリアゾール、１－（３’－ヒドロキシプロピル）ベンゾトリアゾール、４－ヒドロキシ－１Ｈ－ベンゾトリアゾール、５－メチル－１Ｈ－ベンゾトリアゾール、メチルベンゾトリアゾール－５－カルボキシレート、エチルベンゾトリアゾール－５－カルボキシレート、ｔ－ブチル－ベンゾトリアゾール－５－カルボキシレート、シクロペンチルエチル－ベンゾトリアゾール－５－カルボキシレート、１Ｈ－ベンゾトリアゾール－１－アセトニトリル、１Ｈ－ベンゾトリアゾール－１－カルボキシアルデヒド、２－メチル－２Ｈ－ベンゾトリアゾール、２－エチル－２Ｈ－ベンゾトリアゾールなどが挙げられる。 As the basic compound, a benzotriazole compound is preferable from the viewpoints of stability over time after exposure, linearity of the obtained pattern, and suppression of development residue.
The benzotriazole compound is not limited as long as it has a benzotriazole skeleton, and a known benzotriazole compound can be used.
Examples of the benzotriazole compound include 1,2,3-benzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole, 5-carboxybenzotriazole, 1-(hydroxymethyl)-1H -Benzotriazole, 1-acetyl-1H-benzotriazole, 1-aminobenzotriazole, 9-(1H-benzotriazol-1-ylmethyl)-9H-carbazole, 1-chloro-1H-benzotriazole, 1-(2- Pyridinyl)benzotriazole, 1-hydroxybenzotriazole, 1-methylbenzotriazole, 1-ethylbenzotriazole, 1-(1'-hydroxyethyl)benzotriazole, 1-(2'-hydroxyethyl)benzotriazole, 1-propyl Benzotriazole, 1-(1'-hydroxypropyl)benzotriazole, 1-(2'-hydroxypropyl)benzotriazole, 1-(3'-hydroxypropyl)benzotriazole, 4-hydroxy-1H-benzotriazole, 5- Methyl-1H-benzotriazole, methylbenzotriazole-5-carboxylate, ethylbenzotriazole-5-carboxylate, t-butyl-benzotriazole-5-carboxylate, cyclopentylethyl-benzotriazole-5-carboxylate, 1H- Examples thereof include benzotriazole-1-acetonitrile, 1H-benzotriazole-1-carboxaldehyde, 2-methyl-2H-benzotriazole and 2-ethyl-2H-benzotriazole.
　上記感光性樹脂層は、塩基性化合物を、１種単独で含んでいてもよいし、２種以上の塩基性化合物を含んでいてもよい。
　塩基性化合物の含有量は、上記感光性樹脂層の全質量に対して、０．００１質量％～５質量％であることが好ましく、０．００５質量％～３質量％であることがより好ましい。 The photosensitive resin layer may contain one basic compound alone, or may contain two or more basic compounds.
The content of the basic compound is preferably 0.001% by mass to 5% by mass, and more preferably 0.005% by mass to 3% by mass, based on the total mass of the photosensitive resin layer. ..
－界面活性剤－
　上記感光性樹脂層は、厚さ均一性の観点から界面活性剤を含有することが好ましい。
　界面活性剤としては、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る。好ましい界面活性剤はノニオン性界面活性剤である。
　ノニオン性界面活性剤の例としては、ポリオキシエチレン高級アルキルエーテル類、ポリオキシエチレン高級アルキルフェニルエーテル類、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類、シリコーン系、フッ素系界面活性剤を挙げることができる。 -Surfactant-
The photosensitive resin layer 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. A preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. ..
　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を用いることができる。
　また、界面活性剤の市販品としては、例えば、メガファックＦ－５５２又はＦ－５５４（以上、ＤＩＣ（株）製）を用いることができる。
　その他、特許第４５０２７８４号公報の段落００１７、特開２００９－２３７３６２号公報の段落００６０～段落００７１に記載の界面活性剤も用いることができる。 As the surfactant, for example, the surfactants described in paragraphs 0120 to 0125 of International Publication No. 2018/179640 can be used.
As a commercially available product of the surfactant, for example, Megafac F-552 or F-554 (above, manufactured by DIC Corporation) can be used.
In addition, the surfactants described in Paragraph 0017 of Japanese Patent No. 4502784 and Paragraph 0060 to Paragraph 0071 of Japanese Patent Laid-Open No. 2009-237362 can be used.
　上記感光性樹脂層は、界面活性剤を、１種単独で含んでいてもよいし、２種以上の界面活性剤を含んでいてもよい。
　界面活性剤の含有量は、上記感光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 photosensitive resin layer may contain one type of surfactant alone, or may contain two or more types of surfactants.
The content of the surfactant is preferably 0.001% by mass to 10% by mass, and more preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive resin layer. ..
　また、本開示における上記感光性樹脂層には、その他の添加剤として、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、着色剤、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、及び、有機又は無機の沈殿防止剤などの公知の添加剤を更に加えることができる。
　これらの成分の好ましい態様については特開２０１４－８５６４３号公報の段落０１６５～段落０１８４にそれぞれ記載があり、この公報の内容は本明細書に組み込まれる。 In addition, the photosensitive resin layer in the present disclosure, as other additives, metal oxide particles, antioxidants, dispersants, acid multiplying agents, development accelerators, conductive fibers, colorants, thermal radical polymerization initiation Known additives such as agents, thermal acid generators, UV absorbers, thickeners, cross-linking agents, and organic or inorganic suspending agents can be further added.
Preferred embodiments of these components are described in paragraphs 0165 to 0184 of JP-A-2014-85643, and the contents of this publication are incorporated herein.
＜＜感光性樹脂層の平均厚さ＞＞
　感光性樹脂層の平均厚さは、０．５μｍ～２０μｍであることが好ましい。感光性樹脂層の厚みが２０μｍ以下であるとパターンの解像度がより優れ、０．５μｍ以上であるとパターン直線性の観点から好ましい。
　また、感光性樹脂層の平均厚さは、０．８μｍ～１５μｍであることがより好ましく、１．０μｍ～１０μｍであることが特に好ましい。
　本開示における各層の平均厚さの測定方法は、転写材料の面方向に対し垂直な方向の断面を走査型電子顕微鏡（ＳＥＭ）により観察し、層の厚さを１０点以上測定し、その平均値を平均厚さとすることを含む。 <<Average Thickness of Photosensitive Resin Layer>>
The average thickness of the photosensitive resin layer is preferably 0.5 μm to 20 μm. When the thickness of the photosensitive resin layer is 20 μm or less, the resolution of the pattern is better, and when it is 0.5 μm or more, it is preferable from the viewpoint of pattern linearity.
Further, the average thickness of the photosensitive resin layer is more preferably 0.8 μm to 15 μm, and particularly preferably 1.0 μm to 10 μm.
The method for measuring the average thickness of each layer in the present disclosure is performed by observing a cross section in a direction perpendicular to the surface direction of the transfer material with a scanning electron microscope (SEM), measuring the layer thickness at 10 points or more, and averaging the measured values. Including the value as the average thickness.
＜＜感光性樹脂層の形成方法＞＞
　本開示における感光性樹脂層は、感光性樹脂層の形成に用いる成分と、溶剤とを含有する感光性樹脂組成物を調製し、塗布及び乾燥して形成することができる。各成分を、それぞれ予め溶剤に溶解させた溶液とした後、得られた溶液を所定の割合で混合して組成物を調製することもできる。以上の如くして調製した組成物は、例えば、孔径０．２μｍ～３０μｍのフィルター等を用いてろ過を行ってもよい。
　感光性樹脂組成物を仮支持体又はカバーフィルム上に塗布し、乾燥させることで、本開示における感光性樹脂層を形成することができる。
　塗布方法は特に限定されず、スリット塗布、スピン塗布、カーテン塗布、インクジェット塗布などの公知の方法で塗布することができる。
　また、仮支持体又はカバーフィルム上に後述の中間層又はその他の層を形成した上に、感光性樹脂層を形成することもできる。 <<Method of forming photosensitive resin layer>>
The photosensitive resin layer in the present disclosure can be formed by preparing, coating and drying a photosensitive resin composition containing a component used for forming the photosensitive resin layer and a solvent. It is also possible to prepare a composition by dissolving each component in advance in a solvent and then mixing the obtained solutions at a predetermined ratio. The composition prepared as described above may be filtered using, for example, a filter having a pore size of 0.2 μm to 30 μm.
The photosensitive resin composition according to the present disclosure can be formed by applying the photosensitive resin composition onto a temporary support or a cover film and drying it.
The coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, inkjet coating and the like.
Further, the photosensitive resin layer may be formed on the intermediate layer or other layers described below on the temporary support or the cover film.
〔感光性樹脂組成物〕
　感光性樹脂組成物は、感光性樹脂層の形成に用いる成分と、溶剤とを含むことが好ましい。各成分に溶剤を含有させて粘度を調節し、塗布及び乾燥することで、感光性樹脂層を好適に形成することができる。  [Photosensitive resin composition]
The photosensitive resin composition preferably contains a component used for forming the photosensitive resin layer and a solvent. A photosensitive resin layer can be preferably formed by adding a solvent to each component to adjust the viscosity, and applying and drying.
－溶剤－
　溶剤としては、公知の溶媒を使用でき、例えば、国際公開第２０１８／１７９６４０号の段落００９２～段落００９４に記載された溶剤を用いることができる。 -solvent-
As the solvent, known solvents can be used, and for example, the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 can be used.
　また、特開２０１８－１７７８８９公報の段落００１４に記載された２０℃における蒸気圧が１ｋＰａ以上１６ｋＰａ以下の溶剤を好ましく用いることができる。
　本開示に用いることができる溶剤は、１種単独で用いてもよく、２種を併用してもよい。 Further, the solvent having a vapor pressure at 20° C. of 1 kPa or more and 16 kPa or less described in paragraph 0014 of JP-A-2018-177889 can be preferably used.
The solvent that can be used in the present disclosure may be used alone or in combination of two kinds.
　感光性樹脂組成物を塗布する際における溶剤の含有量は、感光性樹脂組成物中の全固形分１００質量部に対し、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 of the solvent when applying the photosensitive resin composition is preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. It is more preferably from about 900 parts by mass.
＜中間層＞
　本開示に係る感光性転写材料は、中間層を有することが好ましい。
　中間層は、後述する重合体を含むことが好ましい。 <Middle layer>
The photosensitive transfer material according to the present disclosure preferably has an intermediate layer.
The intermediate layer preferably contains the polymer described below.
〔重合体〕
　中間層は、重合体を含むことができる。
　中間層に用いられる重合体としては、水溶性樹脂又はアルカリ可溶性樹脂が好ましい。本開示において、「水溶性」とは、２２℃においてｐＨ７．０の水１００ｇへの溶解度が０．１ｇ以上であることを意味し、「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。
　また、上記「水溶性又はアルカリ可溶性」とは、水溶性か、アルカリ可溶性のいずれかであっても、水溶性かつアルカリ可溶性であってもよい。
　また、重合体は、２２℃におけるｐＨ７．０の水１００ｇへの溶解度が、１ｇ以上であることが好ましく、５ｇ以上であることがより好ましい。
　水溶性樹脂としては、例えばセルロース樹脂、ポリビニルアルコール樹脂、ポリビニルピロリドン樹脂、アクリルアミド樹脂、（メタ）アクリレート樹脂、ポリエチレンオキサイド樹脂、ゼラチン、ビニルエーテル樹脂、ポリアミド樹脂、及びこれらの共重合体などの樹脂が挙げられる。中でも、露光後の経時安定性の観点から、セルロース樹脂であることが好ましく、ヒドロキシプロピルセルロース及びヒドロキシプロピルメチルセルロースよりなる群から選ばれた少なくとも１種の樹脂であることがより好ましい。
　アルカリ可溶性樹脂としては、アルカリ可溶性アクリル樹脂が好ましく、塩を形成してもよい酸基を有するアクリル樹脂がより好ましい。 [Polymer]
The intermediate layer can include a polymer.
The polymer used for the intermediate layer is preferably a water-soluble resin or an alkali-soluble resin. In the present disclosure, “water-soluble” means that the solubility in 100 g of water having a pH of 7.0 at 22° C. is 0.1 g or more, and “alkali-soluble” means 1 mass of sodium carbonate at 22° C. %, the solubility in 100 g of the aqueous solution is 0.1 g or more.
The term "water-soluble or alkali-soluble" may be either water-soluble or alkali-soluble, or water-soluble and alkali-soluble.
The solubility of the polymer in 100 g of water having a pH of 7.0 at 22° C. is preferably 1 g or more, more preferably 5 g or more.
Examples of the water-soluble resin include cellulose resins, polyvinyl alcohol resins, polyvinylpyrrolidone resins, acrylamide resins, (meth)acrylate resins, polyethylene oxide resins, gelatin, vinyl ether resins, polyamide resins, and resins such as copolymers thereof. To be Among them, from the viewpoint of stability with time after exposure, a cellulose resin is preferable, and at least one resin selected from the group consisting of hydroxypropyl cellulose and hydroxypropylmethyl cellulose is more preferable.
As the alkali-soluble resin, an alkali-soluble acrylic resin is preferable, and an acrylic resin having an acid group which may form a salt is more preferable.
　中間層は、重合体を、１種単独で含んでいてもよいし、２種以上の重合体を含んでいてもよい。
　重合体の含有量は、密着性の観点から、中間層の全質量に対して、２０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。 The intermediate layer may contain one kind of polymer alone, or may contain two or more kinds of polymers.
From the viewpoint of adhesiveness, the content of the polymer is preferably 20% by mass to 100% by mass, more preferably 50% by mass to 100% by mass, based on the total mass of the intermediate layer.
〔ｐＨ感受性色素〕
　上記中間層は、露光パターンの確認容易性の観点から、発色時における波長範囲４００ｎｍ～７８０ｎｍの極大吸収波長が４５０ｎｍ以上であり、ｐＨにより極大吸収波長が変化するｐＨ感受性色素を含むことが好ましい。
「極大吸収波長が変化する」とは、発色状態にある色素が消色する態様、消色状態にある色素が発色する態様、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指すものであってもよい。
　ｐＨ感受性色素は、視認性の観点から、光酸発生剤から発生する酸により消色する潜在性色素であることがより好ましい。 [PH-sensitive dye]
From the viewpoint of easy confirmation of the exposure pattern, it is preferable that the intermediate 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 contains a pH-sensitive dye whose maximum absorption wavelength changes with pH.
"The maximum absorption wavelength changes" means that a dye in a colored state is decolored, a dye in a decolored state is colored, and a dye in a colored state is changed to a coloring state of another hue. It may refer to any of the aspects.
From the viewpoint of visibility, the pH-sensitive dye is more preferably a latent dye that is decolorized by the acid generated from the photo-acid generator.
　ｐＨ感受性色素であることの確認は、以下の方法により行うことができる。
　色素０．１ｇを、エタノール及び水の混合溶液（エタノール／水＝１／２［質量比］）１００ｍＬに溶かし、０．１ｍｏｌ／Ｌ（１Ｎ）の塩酸水溶液を加えてｐＨ＝１に調整する。０．０１ｍｏｌ／Ｌ（０．０１Ｎ）の水酸化ナトリウム水溶液で滴定し、発色変化と発色変化が現れた際のｐＨとを確認する。なお、ｐＨは、ｐＨメーター（型番：ＨＭ－３１、東亜ディーケーケー（株）製）を用いて２５℃で測定される値である。 It can be confirmed that it is a pH-sensitive dye by the following method.
0.1 g of the dye is dissolved in 100 mL of a mixed solution of ethanol and water (ethanol/water=1/2 [mass ratio]), and 0.1 mol/L (1N) aqueous hydrochloric acid solution is added to adjust pH=1. Titrate with 0.01 mol/L (0.01 N) sodium hydroxide aqueous solution to confirm the color change and the pH at which the color change appears. The pH is a value measured at 25° C. using a pH meter (model number: HM-31, manufactured by Toa DKK Co., Ltd.).
　本開示における極大吸収波長の測定方法は、大気の雰囲気下で、２５℃にて分光光度計：ＵＶ３１００（（株）島津製作所製）を用いて、４００ｎｍ～７８０ｎｍの範囲で透過スペクトルを測定し、光の強度が極小となる波長（極大吸収波長）を測定するものとする。 The method for measuring the maximum absorption wavelength in the present disclosure is to measure a transmission spectrum in the range of 400 nm to 780 nm using a spectrophotometer: UV3100 (manufactured by Shimadzu Corporation) at 25° C. in an atmosphere of air. The wavelength at which the light intensity becomes a minimum (maximum absorption wavelength) shall be measured.
　露光により消色する色素としては、例えば、ロイコ化合物、ジフェニルメタン系色素、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、アントラキノン系色素等が挙げられる。
　中でも、色素としては、視認性の観点から、ロイコ化合物が好ましい。
　ロイコ化合物としては、トリアリールメタン系（例えばトリフェニルメタン系）、スピロピラン系、フルオラン系、ジフェニルメタン系、ローダミンラクタム系、インドリルフタリド系、ロイコオーラミン系等のロイコ化合物が挙げられる。中でも、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）が好ましく、トリフェニルメタン系色素がより好ましい。
　また、ロイコ化合物としては、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し、ラクトン環、スルチン環、又は、スルトン環が開環又は閉環するものが好ましく、スルトン環を有し、スルトン環が閉環して消色するロイコ化合物であることがより好ましい。 Examples of dyes that are decolorized by exposure include leuco compounds, diphenylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.
Among them, leuco compounds are preferable as the dye from the viewpoint of visibility.
Examples of the leuco compound include triarylmethane-based (eg, triphenylmethane-based), spiropyran-based, fluorane-based, diphenylmethane-based, rhodamine lactam-based, indolylphthalide-based, leucoauramine-based leuco compounds. Of these, leuco compounds having a triarylmethane skeleton (triarylmethane dyes) are preferable, and triphenylmethane dyes are more preferable.
From the viewpoint of visibility, the leuco compound preferably has a lactone ring, a sultin ring, or a sultone ring, and a lactone ring, a sultin ring, or a compound in which the sultone ring is opened or closed, and has a sultone ring. However, it is more preferable to use a leuco compound in which the sultone ring is closed and decolorized.
　色素は、色素の析出による欠陥を防止する観点からは、水溶性の化合物であることが好ましい。
　また、色素は、２２℃におけるｐＨ７．０の水１００ｇへの溶解度が、１ｇ以上であることが好ましく、５ｇ以上であることがより好ましい。 The dye is preferably a water-soluble compound from the viewpoint of preventing defects due to precipitation of the dye.
The solubility of the dye in 100 g of water having a pH of 7.0 at 22° C. is preferably 1 g or more, more preferably 5 g or more.
　中間層は、色素を、１種単独で含んでいてもよいし、２種以上の色素を含んでいてもよい。
　上記中間層における色素の含有量は、視認性の観点から、中間層の全質量に対し、０．０１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く、１．０質量％～３．０質量％であることが更に好ましい。 The intermediate layer may include one type of dye alone, or may include two or more types of dye.
From the viewpoint of visibility, the content of the dye in the intermediate layer is preferably 0.01% by mass to 10% by mass, and is 0.5% by mass to 5% by mass, based on the total mass of the intermediate layer. It is more preferable that the content is 1.0% by mass to 3.0% by mass.
〔界面活性剤〕
　中間層は、厚さ均一性の観点から界面活性剤を含有することが好ましい。界面活性剤としては、フッ素原子を有する界面活性剤、ケイ素原子を有する界面活性剤、フッ素原子もケイ素原子も有さない界面活性剤のいずれも使用することができる。中でも、界面活性剤としては、感光性樹脂層及び中間層におけるスジの発生抑制、及び、密着性の観点から、フッ素原子を有する界面活性剤であることが好ましく、パーフルオロアルキル基とポリアルキレンオキシ基とを有する界面活性剤であることがより好ましい。
　また、界面活性剤としては、アニオン性、カチオン性、ノニオン性（非イオン性）、又は、両性のいずれでも使用することができるが、好ましい界面活性剤はノニオン性界面活性剤である。
　界面活性剤は、界面活性剤の析出抑制の観点から、２５℃の水１００ｇに対する溶解度が１ｇ以上であるものが好ましい。 [Surfactant]
The intermediate layer preferably contains a surfactant from the viewpoint of thickness uniformity. As the surfactant, any of a surfactant having a fluorine atom, a surfactant having a silicon atom, and a surfactant having neither a fluorine atom nor a silicon atom can be used. Among them, the surfactant is preferably a surfactant having a fluorine atom from the viewpoint of suppressing the generation of streaks in the photosensitive resin layer and the intermediate layer, and the adhesiveness, and a perfluoroalkyl group and a polyalkyleneoxy group. It is more preferable that the surfactant has a group.
As the surfactant, any of anionic, cationic, nonionic (nonionic) or amphoteric can be used, but the preferred surfactant is a nonionic surfactant.
The surfactant preferably has a solubility of 1 g or more in 100 g of water at 25° C. from the viewpoint of suppressing the precipitation of the surfactant.
　中間層は、界面活性剤を、１種単独で含んでいてもよいし、２種以上の界面活性剤を含んでいてもよい。
　上記中間層における界面活性剤の含有量は、感光性樹脂層及び中間層におけるスジの発生抑制、及び、密着性の観点から、中間層の全質量に対して、０．０５質量％～２．０質量％であることが好ましく、０．１質量％～１．０質量％であることがより好ましく、０．２質量％～０．５質量％であることが特に好ましい。 The intermediate layer may include one type of surfactant alone, or may include two or more types of surfactant.
The content of the surfactant in the intermediate layer is 0.05% by mass to 2.% with respect to the total mass of the intermediate layer from the viewpoints of suppressing the generation of streaks in the photosensitive resin layer and the intermediate layer and adhering. It is preferably 0% by mass, more preferably 0.1% by mass to 1.0% by mass, and particularly preferably 0.2% by mass to 0.5% by mass.
〔無機フィラー〕
　中間層は無機フィラーを含んでいてもよい。本開示における無機フィラーは特に制限はない。シリカ粒子、酸化アルミニウム粒子、酸化ジルコニウム粒子等が挙げられ、シリカ粒子がより好ましい。透明性の観点から粒径の小さい粒子が好ましく、１００ｎｍ以下の平均粒径のものが更に好ましい。例えば市販品であればスノーテックス（登録商標）が好適に用いられる。 (Inorganic filler)
The intermediate layer may include an inorganic filler. The inorganic filler in the present disclosure is not particularly limited. Examples thereof include silica particles, aluminum oxide particles and zirconium oxide particles, and silica particles are more preferable. From the viewpoint of transparency, particles having a small particle size are preferable, and particles having an average particle size of 100 nm or less are more preferable. For example, if it is a commercially available product, Snowtex (registered trademark) is preferably used.
　上記中間層における上記粒子の体積分率（中間層における粒子が占める体積割合）は、中間層と感光層との密着性の観点から、中間層の全体積に対し、５％～９０％であることが好ましく、１０％～８０％であることがより好ましく、２０％～６０％であることが更に好ましい。 The volume fraction of the particles in the intermediate layer (volume ratio of the particles in the intermediate layer) is 5% to 90% with respect to the total volume of the intermediate layer from the viewpoint of adhesion between the intermediate layer and the photosensitive layer. It is preferably 10% to 80%, more preferably 20% to 60%.
〔ｐＨ調整剤〕
　中間層はｐＨ調整剤を含んでいてもよい。ｐＨ調整剤を含むことで、中間層中の色素の発色状態又は消色状態をより安定的に維持することができ、感光性樹脂層と中間層との密着性がより向上する。
　本開示におけるｐＨ調整剤は特に制限はない。例えば水酸化ナトリウム、水酸化カリウム、水酸化リチウム、有機アミン、有機アンモニウム塩等が挙げられる。水溶性の観点から水酸化ナトリウムが好ましい。感光性樹脂層と中間層との密着性の観点からは、有機アンモニウム塩が好ましい。 [PH adjuster]
The intermediate layer may contain a pH adjuster. By including the pH adjusting agent, the coloring state or the decoloring state of the dye in the intermediate layer can be maintained more stably, and the adhesiveness between the photosensitive resin layer and the intermediate layer is further improved.
The pH adjusting agent in the present disclosure is not particularly limited. Examples thereof include sodium hydroxide, potassium hydroxide, lithium hydroxide, organic amines, organic ammonium salts and the like. Sodium hydroxide is preferred from the viewpoint of water solubility. From the viewpoint of adhesiveness between the photosensitive resin layer and the intermediate layer, organic ammonium salts are preferable.
＜＜中間層の平均厚さ＞＞
　中間層の平均厚さは、感光性樹脂層と中間層との密着性、及び、パターン形成性の観点から、０．３μｍ～１０μｍであることが好ましく、０．３μｍ～５μｍであることがより好ましく、０．３μｍ～２μｍであることが特に好ましい。
　また、中間層の平均厚さは、感光性樹脂層の平均厚さよりも薄いことが好ましい。 <<Average thickness of the intermediate layer>>
The average thickness of the intermediate layer is preferably 0.3 μm to 10 μm, and more preferably 0.3 μm to 5 μm, from the viewpoint of adhesion between the photosensitive resin layer and the intermediate layer and pattern formability. It is particularly preferably 0.3 μm to 2 μm.
Further, the average thickness of the intermediate layer is preferably thinner than the average thickness of the photosensitive resin layer.
　中間層は、２層以上の層を有することができる。
　中間層が２層以上の層を有する場合、各層の平均厚さは上記範囲内であれば特に限定されないが、中間層における２層以上の層のうち、感光性樹脂層に最も近い層の平均厚さは、中間層と感光性樹脂層との密着性、及び、パターン形成性の観点から、０．３μｍ～１０μｍが好ましく、０．３μｍ～５μｍがより好ましく、０．３μｍ～２μｍが特に好ましい。 The intermediate layer can have two or more layers.
When the intermediate layer has two or more layers, the average thickness of each layer is not particularly limited as long as it is within the above range, but of the two or more layers in the intermediate layer, the average of the layers closest to the photosensitive resin layer. The thickness is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and particularly preferably 0.3 μm to 2 μm, from the viewpoints of the adhesiveness between the intermediate layer and the photosensitive resin layer and the pattern formability. ..
＜＜中間層の形成方法＞＞
　本開示における中間層は、中間層の形成に用いる成分と、水溶性溶剤とを含有する中間層形成用組成物を調製し、塗布及び乾燥して形成することができる。各成分を、それぞれ予め溶剤に溶解させた溶液とした後、得られた溶液をあらかじめ定めた割合で混合して組成物を調製することもできる。以上の如くして調製した組成物は、孔径３．０μｍのフィルター等を用いてろ過を行ってもよい。
　中間層形成用組成物を仮支持体に塗布し、乾燥させることで、仮支持体上に中間層を形成することができる。塗布方法は特に限定されず、スリット塗布、スピン塗布、カーテン塗布、インクジェット塗布などの公知の方法で塗布することができる。 <<Method of forming intermediate layer>>
The intermediate layer in the present disclosure can be formed by preparing a composition for forming an intermediate layer containing a component used for forming the intermediate layer and a water-soluble solvent, coating and drying the composition. It is also possible to prepare a composition by dissolving each component in advance in a solvent and then mixing the obtained solutions in a predetermined ratio. The composition prepared as described above may be filtered using a filter having a pore size of 3.0 μm.
The intermediate layer can be formed on the temporary support by applying the intermediate layer-forming composition to the temporary support and drying the composition. The coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, inkjet coating and the like.
〔中間層形成組成物〕
　中間層形成組成物は、中間層の形成に用いる成分と、水溶性溶剤とを含むことが好ましい。各成分に水溶性溶剤を含有させて粘度を調節し、塗布及び乾燥することで、中間層を好適に形成することができる。 [Intermediate layer forming composition]
The intermediate layer forming composition preferably contains a component used for forming the intermediate layer and a water-soluble solvent. A water-soluble solvent is contained in each component to adjust the viscosity, and the intermediate layer can be suitably formed by coating and drying.
－水溶性溶剤－
　水溶性溶剤としては、公知の水溶性溶剤を用いることができ、例えば、水、炭素数１～６のアルコール等が挙げられ、水を含むことが好ましい。炭素数１～６のアルコールとしては、具体的には、メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、ｎ－ペンタノール、及び、ｎ－ヘキサノールが挙げられる。中でも、メタノール、エタノール、ｎ－プロパノール、及び、イソプロパノールよりなる群から選ばれた少なくとも１種を用いることが好ましい。 -Water-soluble solvent-
As the water-soluble solvent, a known water-soluble solvent can be used, and examples thereof include water and alcohols having 1 to 6 carbon atoms, and water is preferable. Specific examples of the alcohol having 1 to 6 carbon atoms include methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, and n-hexanol. Among them, it is preferable to use at least one selected from the group consisting of methanol, ethanol, n-propanol, and isopropanol.
＜カバーフィルム＞
　本開示に係る感光性転写材料は、感光性転写材料における仮支持体が設けられた側の面とは反対側の面に、カバーフィルムを有することが好ましい。
　カバーフィルムとしては、樹脂フィルム、紙等が挙げられ、強度及び可撓性等の観点から、樹脂フィルムが特に好ましい。樹脂フィルムとしては、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、ポリカーボネートフィルム等が挙げられる。中でも、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が好ましい。 <Cover film>
The photosensitive transfer material according to the present disclosure preferably has a cover film on the surface of the photosensitive transfer material opposite to the surface on which the temporary support is provided.
Examples of the cover film include a resin film and paper, and a resin film is particularly preferable from the viewpoint of strength and flexibility. Examples of the resin film include polyethylene film, polypropylene film, polyethylene terephthalate film, cellulose triacetate film, polystyrene film and polycarbonate film. Among them, polyethylene film, polypropylene film and polyethylene terephthalate film are preferable.
　カバーフィルムの平均厚さは特に限定されず、例えば、１μｍ～２ｍｍのものが好ましく挙げられる。 The average thickness of the cover film is not particularly limited, and one having a thickness of 1 μm to 2 mm is preferable.
＜その他の層＞
　本開示に係る感光性転写材料は、上述した以外の層（以下、「その他の層」ともいう。）を有していてもよい。その他の層としては、コントラストエンハンスメント層、熱可塑性樹脂層等を挙げることができる。
　コントラストエンハンスメント層の好ましい態様については国際公開第２０１８／１７９６４０号の段落０１３４、熱可塑性樹脂層の好ましい態様については特開２０１４－８５６４３号公報の段落０１８９～段落０１９３、及び、更に他の層の好ましい態様については特開２０１４－８５６４３号公報の段落０１９４～段落０１９６にそれぞれ記載があり、この公報の内容は本明細書に組み込まれる。 <Other layers>
The photosensitive transfer material according to the present disclosure may have a layer other than those described above (hereinafter, also referred to as “other layer”). Examples of the other layer include a contrast enhancement layer and a thermoplastic resin layer.
Regarding a preferred embodiment of the contrast enhancement layer, paragraph 0134 of International Publication No. 2018/179640, regarding a preferred embodiment of the thermoplastic resin layer, paragraphs 0189 to 0193 of JP-A-2014-85643, and further other layers are preferred. Aspects are described in paragraphs 0194 to 0196 of JP-A-2014-85643, respectively, and the contents of this publication are incorporated herein.
　ここで図１を参照して、本開示に係る感光性転写材料の層構成の一例を概略的に示す。
　図１に示す感光性転写材料１００は、仮支持体１２と、感光性樹脂層１４－１及び中間層１４－２を積層してなる転写層１４と、カバーフィルム１６とがこの順に積層されている。以下、本開示において「転写層」と記載した場合は、積層された感光性樹脂層及び中間層の両方を表すものとする。 Here, referring to FIG. 1, an example of a layer configuration of a photosensitive transfer material according to the present disclosure is schematically illustrated.
The photosensitive transfer material 100 shown in FIG. 1 comprises a temporary support 12, a transfer layer 14 formed by stacking a photosensitive resin layer 14-1 and an intermediate layer 14-2, and a cover film 16 stacked in this order. There is. Hereinafter, in the present disclosure, the term “transfer layer” refers to both the laminated photosensitive resin layer and the intermediate layer.
（感光性転写材料の製造方法）
　本開示に係る感光性転写材料の製造方法は、特に制限はなく、公知の製造方法、例えば、公知の各層の形成方法等を用いることができる。
　中でも、本開示に係る感光性転写材料の製造方法としては、中間層形成用組成物を仮支持体上に塗布及び乾燥し中間層を形成する工程、並びに、感光性樹脂組成物を中間層上に塗布及び乾燥し感光性樹脂層を形成する工程を含む方法が好ましく挙げられる。
　また、本開示に係る感光性転写材料の製造方法は、上記感光性樹脂層を形成する工程の後に、上記感光性樹脂層上にカバーフィルムを設ける工程を更に含むことが好ましい。 (Method for manufacturing photosensitive transfer material)
The method for manufacturing the photosensitive transfer material according to the present disclosure is not particularly limited, and a known manufacturing method such as a known method for forming each layer can be used.
Among them, the method for producing the photosensitive transfer material according to the present disclosure includes a step of applying an intermediate layer-forming composition on a temporary support and drying the intermediate layer to form an intermediate layer, and a photosensitive resin composition on the intermediate layer. A preferable method is a method including a step of applying and drying to form a photosensitive resin layer.
The method for producing a photosensitive transfer material according to the present disclosure preferably further includes a step of providing a cover film on the photosensitive resin layer after the step of forming the photosensitive resin layer.
（樹脂パターンの製造方法、及び、回路配線の製造方法）
　本開示に係る樹脂パターンの製造方法は、本開示に係る感光性転写材料を用いた樹脂パターンの製造方法であれば、特に制限はないが、本開示に係る感光性転写材料における上記仮支持体に対して感光性樹脂層を有する側の最外層を基板に接触させて貼り合わせる工程（以下、「貼り合わせ工程」ということがある。）と、上記感光性樹脂層をパターン露光する工程（以下、「露光工程」ということがある。）と、露光された上記感光性樹脂層を現像してパターンを形成する工程（以下、「現像工程」ということがある。）と、をこの順に含むことが好ましい。
　また、本開示に係る樹脂パターンの製造方法における上記基板は、導電層を有する基板であることが好ましく、表面に導電層を有する基板であることがより好ましい。
　本開示に係る回路配線の製造方法は、本開示に係る感光性転写材料を用いる方法であればよいが、本開示に係る感光性転写材料の、上記仮支持体に対して感光性樹脂層を有する側の最外層を、導電層を有する基板に貼り合わせる工程（以下、「貼り合わせ工程」ということがある。）と、貼り合わせた上記感光性転写材料における上記感光性樹脂層をパターン露光する工程と、パターン露光された上記感光性樹脂層を少なくとも現像して樹脂パターンを形成する工程と、上記樹脂パターンが配置されていない領域における上記基板をエッチング処理する工程（以下、「エッチング工程」ということがある。）と、をこの順に含むことが好ましい。
　本開示に係る回路配線の製造方法における上記基板は、表面に上記導電層を有する基板であることが好ましい。 (Resin pattern manufacturing method and circuit wiring manufacturing method)
The method for producing a resin pattern according to the present disclosure is not particularly limited as long as it is a method for producing a resin pattern using the photosensitive transfer material according to the present disclosure, but the temporary support in the photosensitive transfer material according to the present disclosure is not particularly limited. A step of bringing the outermost layer on the side having the photosensitive resin layer into contact with the substrate and attaching them (hereinafter, sometimes referred to as “attaching step”); and a step of pattern-exposing the photosensitive resin layer (hereinafter, “exposing”). , And “exposure step”) and a step of developing the exposed photosensitive resin layer to form a pattern (hereinafter, sometimes referred to as “developing step”). Is preferred.
Further, the substrate in the method for producing a resin pattern according to the present disclosure is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on its surface.
The method for manufacturing the circuit wiring according to the present disclosure may be a method using the photosensitive transfer material according to the present disclosure, but a photosensitive resin layer is formed on the temporary support of the photosensitive transfer material according to the present disclosure. A step of bonding the outermost layer on the side having the conductive layer to a substrate having a conductive layer (hereinafter, also referred to as “bonding step”), and pattern-exposing the photosensitive resin layer in the bonded photosensitive transfer material. A step of forming a resin pattern by developing at least the pattern-exposed photosensitive resin layer, and a step of etching the substrate in a region where the resin pattern is not arranged (hereinafter referred to as "etching step"). In some cases.) and
The substrate in the circuit wiring manufacturing method according to the present disclosure is preferably a substrate having the conductive layer on its surface.
　また、本開示に係る回路配線の製造方法は、上記貼り合わせ工程、上記露光工程、上記現像工程、及び、上記エッチング工程の４工程を１セットとして、複数回繰り返す態様も好ましく挙げられる。
　更に、後述するように基板を再利用（リワーク）できるため、本開示に係る回路配線の製造方法は、上記貼り合わせ工程、上記露光工程、上記現像工程、及び、上記エッチング工程の４工程を行った後、上記樹脂パターンに対して上記露光工程を行い、上記現像工程、及び、上記エッチング工程を更に行う態様も好ましく挙げられる。 The circuit wiring manufacturing method according to the present disclosure preferably includes a mode in which four steps of the bonding step, the exposure step, the development step, and the etching step are set as one set and repeated a plurality of times.
Furthermore, since the substrate can be reused (reworked) as described below, the method for manufacturing circuit wiring according to the present disclosure includes four steps of the bonding step, the exposure step, the development step, and the etching step. After that, a preferable mode is one in which the exposure step is performed on the resin pattern, and the developing step and the etching step are further performed.
　以下、リワークについて説明する。
　上記感光性樹脂層は、活性光線を照射していない部分を像として残すポジ型である。上記感光性樹脂層では、活性光線を照射することにより、例えば活性光線を照射されて酸を発生する感光剤などを用いて露光部の溶解性を高めるため、パターン露光時点では露光部及び未露光部がいずれも硬化せず、得られたパターン形状が不良であった場合には全面露光などによって基板を再利用（リワーク）できる。
　上記回路配線の製造方法の実施形態としては、国際公開第２００６／１９０４０５号を参考にすることができ、この内容は本明細書に組み込まれる。 The rework will be described below.
The above-mentioned photosensitive resin layer is of a positive type, which leaves an area not irradiated with actinic rays as an image. In the above-mentioned photosensitive resin layer, by irradiating with actinic rays, for example, in order to increase the solubility of the exposed parts by using a photosensitizer which is irradiated with the actinic rays to generate an acid, the exposed parts and unexposed parts are exposed at the time of pattern exposure. If none of the parts are cured and the obtained pattern shape is defective, the substrate can be reused (reworked) by exposing the entire surface.
As an embodiment of the method for manufacturing the circuit wiring, reference can be made to WO 2006/190405, the contents of which are incorporated herein.
＜貼り合わせ工程＞
　本開示に係る樹脂パターンの製造方法、又は、本開示に係る回路配線の製造方法は、本開示に係る感光性転写材料における上記仮支持体に対して感光性樹脂層を有する側の最外層を、基板、好ましくは導電層を有する基板に接触させて貼り合わせる工程（貼り合わせ工程）を含むことが好ましい。
　上記貼り合わせ工程においては、上記導電層と、本開示に係る感光性転写材料における上記仮支持体に対して感光性樹脂層を有する側の最外層と、が接触するように圧着させることが好ましい。上記態様であると、露光及び現像後のパターン形成された感光性樹脂層を、導電層をエッチングする際のエッチングレジストとして好適に用いることができる。
　上記基板と上記感光性転写材料とを圧着する方法としては、特に制限はなく、公知の転写方法、及び、ラミネート方法を用いることができる。
　感光性転写材料の基板への貼り合わせは、感光性転写材料の、感光性樹脂層を有する側の最外層を基板上に重ね、ロール等による加圧及び加熱することに行われることが好ましい。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等の公知のラミネーターを使用することができる。本開示に係る回路配線の製造方法は、ロールツーロール方式により行われることが好ましい。そのため、基板を構成する基材は、樹脂フィルムであることが好ましい。
　以下、ロールツーロール方式について説明する。
　ロールツーロール方式とは、基板として、巻き取り及び巻き出しが可能な基板を用い、回路配線の製造方法に含まれるいずれかの工程の前に、基板又は基板を含む構造体を巻き出す工程（「巻き出し工程」ともいう。）と、いずれかの工程の後に、基材又は基板を含む構造体を巻き取る工程（「巻き取り工程」ともいう。）と、を含み、少なくともいずれかの工程（好ましくは、全ての工程、又は加熱工程以外の全ての工程）を、基材又は基板を含む構造体を搬送しながら行う方式をいう。
　巻き出し工程における巻き出し方法、及び巻き取り工程における巻取り方法としては、特に制限されず、ロールツーロール方式を適用する製造方法において、公知の方法を用いればよい。 <Laminating process>
The method for producing a resin pattern according to the present disclosure, or the method for producing a circuit wiring according to the present disclosure, provides the outermost layer on the side having a photosensitive resin layer with respect to the temporary support in the photosensitive transfer material according to the present disclosure. It is preferable to include a step (bonding step) of bringing the substrate, preferably a substrate having a conductive layer, into contact with each other for bonding.
In the laminating step, it is preferable to perform pressure bonding so that the conductive layer and the outermost layer on the side having the photosensitive resin layer with respect to the temporary support in the photosensitive transfer material according to the present disclosure come into contact with each other. .. According to the above aspect, the patterned photosensitive resin layer after exposure and development can be preferably used as an etching resist when etching the conductive layer.
The method for pressure-bonding the substrate and the photosensitive transfer material is not particularly limited, and known transfer methods and laminating methods can be used.
The sticking of the photosensitive transfer material to the substrate is preferably performed by stacking the outermost layer of the photosensitive transfer material on the side having the photosensitive resin layer on the substrate and applying pressure and heating with a roll or the like. For laminating, a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator capable of improving productivity can be used. The method of manufacturing circuit wiring according to the present disclosure is preferably performed by a roll-to-roll method. Therefore, the base material forming the substrate is preferably a resin film.
The roll-to-roll method will be described below.
The roll-to-roll method uses a substrate that can be wound and unwound as a substrate, and unwinds the substrate or a structure including the substrate before any step included in the method for manufacturing circuit wiring ( Also referred to as "winding step") and a step of winding a structure including a base material or a substrate after any step (also referred to as "winding step"). (Preferably, all steps or all steps other than the heating step) are performed while a structure including a base material or a substrate is being conveyed.
The unwinding method in the unwinding step and the winding method in the winding step are not particularly limited, and known methods may be used in the manufacturing method to which the roll-to-roll method is applied.
　本開示に用いられる基板は、導電層を有する基板であることが好ましく、基材の表面に導電層を有する基板であることがより好ましい。
　導電層を有する基板は、例えば、ガラス、シリコン、フィルムなどの基材上に、導電層を有し、必要により任意の層が形成されてもよい。
　基材は透明であることが好ましい。
　基材の屈折率は、１．５０～１．５２であることが好ましい。
　基材は、ガラス基材等の透光性基材で構成されていてもよく、コーニング社のゴリラガラスに代表される強化ガラスなどを用いることができる。また、上述の透明基材としては、特開２０１０－８６６８４号公報、特開２０１０－１５２８０９号公報及び特開２０１０－２５７４９２号公報に用いられている材料を好ましく用いることができる。
　基材として樹脂フィルム基材を用いる場合は、光学的に歪みが小さい基材、及び、透明度が高い基材を用いることがより好ましい。具体的な素材としては、ポリエチレンテレフタレート（ｐｏｌｙｅｔｈｙｌｅｎｅ　ｔｅｒｅｐｈｔｈａｌａｔｅ；ＰＥＴ）、ポリエチレンナフタレート、ポリカーボネート、トリアセチルセルロース、シクロオレフィンポリマーを挙げることができる。 The substrate used in the present disclosure is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface of the base material.
The substrate having a conductive layer may have a conductive layer on a base material such as glass, silicon, or a film, and any layer may be formed if necessary.
The substrate is preferably transparent.
The refractive index of the base material is preferably 1.50 to 1.52.
The base material may be composed of a translucent base material such as a glass base material, and a tempered glass typified by Corning's gorilla glass can be used. Further, as the above-mentioned transparent base material, the materials used in JP 2010-86684 A, JP 2010-152809 A and JP 2010-257492 A can be preferably used.
When a resin film base material is used as the base material, it is more preferable to use a base material having small optical distortion and a base material having high transparency. Specific examples of the material include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.
　基材上に導電層を有する基板は、ロールツーロール方式で製造する観点から、フィルム基材であることが好ましい。本開示に係る回路配線の製造方法においては、回路配線がタッチパネル用の回路配線である場合、基材はシート状樹脂組成物であることが特に好ましい。 The substrate having the conductive layer on the base material is preferably a film base material from the viewpoint of manufacturing by a roll-to-roll method. In the circuit wiring manufacturing method according to the present disclosure, when the circuit wiring is a circuit wiring for a touch panel, the base material is particularly preferably a sheet-shaped resin composition.
　基材上に形成されている導電層としては、一般的な回路配線又はタッチパネル配線に用いられる任意の導電層を挙げることができる。
　導電層としては、導電性及び細線形成性の観点から、金属層、導電性金属酸化物層、グラフェン層、カーボンナノチューブ層、及び、導電ポリマー層よりなる群から選ばれた少なくとも１種の層が好ましく挙げられる。導電層は金属層であることがより好ましく、銅層、又は、銀層であることが特に好ましい。
　また、基材上に導電層を１層有していても、２層以上有していてもよい。２層以上の場合は、異なる材質の導電層を有することが好ましい。
　導電層の材料としては、金属及び導電性金属酸化物などを挙げることができる。
　金属としては、Ａｌ、Ｚｎ、Ｃｕ、Ｆｅ、Ｎｉ、Ｃｒ、Ｍｏ、Ａｇ、Ａｕ等を挙げることができる。
　導電性金属酸化物としては、ＩＴＯ（Ｉｎｄｉｕｍ　Ｔｉｎ　Ｏｘｉｄｅ）、ＩＺＯ（Ｉｎｄｉｕｍ　Ｚｉｎｃ　Ｏｘｉｄｅ）、ＳｉＯ２等を挙げることができる。なお、本開示における「導電性」とは、体積抵抗率が１×１０６Ωｃｍ未満であることをいう。体積抵抗率は１×１０４Ωｃｍ未満であることが好ましい。 Examples of the conductive layer formed on the base material include any conductive layer used for general circuit wiring or touch panel wiring.
As the conductive layer, at least one layer selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer is selected from the viewpoints of conductivity and thin wire forming property. Preferred examples include: The conductive layer is more preferably a metal layer, and particularly preferably a copper layer or a silver layer.
Further, the substrate may have one conductive layer or two or more conductive layers. In the case of two or more layers, it is preferable to have conductive layers of different materials.
Examples of the material of the conductive layer include metals and conductive metal oxides.
Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag and Au.
Examples of the conductive metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO 2 . It should be noted that “conductivity” in the present disclosure means that the volume resistivity is less than 1×10 6 Ωcm. The volume resistivity is preferably less than 1×10 4 Ωcm.
　本開示に係る回路配線の製造方法において、基材上に複数の導電層を有する基板を用いる場合、複数の導電層のうち少なくとも一つの導電層は導電性金属酸化物を含むことが好ましい。
　導電層は、静電容量型タッチパネルに用いられる視認部のセンサーに相当する電極パターン又は周辺取り出し部の配線であることが好ましい。 In the method for manufacturing circuit wiring according to the present disclosure, when using a substrate having a plurality of conductive layers on a base material, at least one conductive layer of the plurality of conductive layers preferably contains a conductive metal oxide.
The conductive layer is preferably an electrode pattern corresponding to the sensor of the visual recognition part used in the capacitive touch panel or a wiring of the peripheral extraction part.
＜露光工程＞
　本開示に係る樹脂パターンの製造方法、又は、本開示に係る回路配線の製造方法は、上記貼り合わせる工程後、上記感光性樹脂層をパターン露光する工程（露光工程）を含むことが好ましい。 <Exposure process>
The method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure preferably includes a step (exposure step) of pattern-exposing the photosensitive resin layer after the bonding step.
　本開示においてパターンの詳細な配置及び具体的サイズは特に制限されない。本開示に係る回路配線の製造方法により製造される回路配線を有する入力装置を備えた表示装置（例えばタッチパネル）の表示品質を高め、また、取り出し配線の占める面積をできるだけ小さくしたいことから、パターンの少なくとも一部（特にタッチパネルの電極パターン及び取り出し配線の部分）は１００μｍ以下の細線であることが好ましく、７０μｍ以下の細線であることが更に好ましい。 In the present disclosure, the detailed arrangement and specific size of the pattern are not particularly limited. In order to improve the display quality of a display device (for example, a touch panel) including an input device having circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure, and to make the area occupied by the extraction wiring as small as possible, At least a part (particularly the electrode pattern of the touch panel and the part of the extraction wiring) is preferably a fine wire of 100 μm or less, and more preferably a fine wire of 70 μm or less.
　露光に使用する光源としては、感光性樹脂層を露光可能な波長域の光（例えば、３６５ｎｍ、４０５ｎｍ等）を照射するものであれば、適宜選定して用いることができる。具体的には、超高圧水銀灯、高圧水銀灯、メタルハライドランプ、ＬＥＤ（Light Emitting Diode）等が挙げられる。 The light source used for exposure may be appropriately selected and used as long as it irradiates light in a wavelength range capable of exposing the photosensitive resin layer (for example, 365 nm, 405 nm, etc.). Specific examples include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).
　露光量としては、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 dose 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、感光性樹脂層から仮支持体を剥離した後にパターン露光してもよく、仮支持体を剥離する前に、仮支持体を介してパターン露光し、その後、仮支持体を剥離してもよい。感光性樹脂層とマスクとの接触によるマスク汚染の防止、及びマスクに付着した異物による露光への影響を避けるためには、仮支持体を剥離せずにパターン露光することが好ましい。なお、パターン露光は、マスクを介した露光でもよいし、レーザー等を用いたダイレクト露光でもよい。 In the exposure step, pattern exposure may be performed after peeling the temporary support from the photosensitive resin layer, pattern exposure is performed via the temporary support before peeling the temporary support, and then the temporary support is peeled. You may. In order to prevent the contamination of the mask due to the contact between the photosensitive resin layer and the mask and to avoid the influence of foreign matter attached to the mask on the exposure, it is preferable to perform the pattern exposure without peeling the temporary support. The pattern exposure may be exposure through a mask or direct exposure using a laser or the like.
＜現像工程＞
　本開示に係る樹脂パターンの製造方法、又は、本開示に係る回路配線の製造方法は、上記露光する工程後、露光された上記感光性樹脂層を現像して樹脂パターンを形成する工程（現像工程）を含むことが好ましい。
　また、上記感光性転写材料が中間層を有する場合、現像工程においては、露光された部分の中間層も、露光された感光性樹脂層とともに除去される。更に、現像工程においては、未露光部の中間層も現像液に溶解あるいは分散する形で除去されてもよい。 <Developing process>
A method of manufacturing a resin pattern according to the present disclosure, or a method of manufacturing a circuit wiring according to the present disclosure includes a step of developing the exposed photosensitive resin layer after the exposing step to form a resin pattern (developing step). ) Is preferably included.
When the photosensitive transfer material has an intermediate layer, the exposed intermediate layer is removed together with the exposed photosensitive resin layer in the developing step. Further, in the developing step, the intermediate layer in the unexposed area may also be removed in the form of being dissolved or dispersed in the developing solution.
　上記現像工程における露光された上記感光性樹脂層の現像は、現像液を用いて行うことができる。
　現像液としては、感光性樹脂層の非画像部を除去することができれば特に制限はなく、例えば、特開平５－７２７２４号公報に記載の現像液など、公知の現像液を使用することができる。なお、現像液は感光性樹脂層の露光部（ポジ型）が溶解型の現像挙動をする現像液が好ましい。例えば、ｐＫａ＝７～１３の化合物を０．０５ｍｏｌ／Ｌ（リットル）～５ｍｏｌ／Ｌの濃度で含むアルカリ水溶液系の現像液が好ましい。現像液は、更に、水溶性の有機溶剤、界面活性剤等を含有してもよい。本開示において好適に用いられる現像液としては、例えば、国際公開第２０１５／０９３２７１号の段落０１９４に記載の現像液が挙げられる。 Development of the exposed photosensitive resin layer in the developing step can be performed using a developer.
The developer is not particularly limited as long as it can remove the non-image part of the photosensitive resin layer, and known developers such as the developer described in JP-A-5-72724 can be used. .. The developing solution is preferably a developing solution in which the exposed portion (positive type) of the photosensitive resin layer has a dissolution type developing behavior. For example, an alkaline aqueous solution-based developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol/L (liter) to 5 mol/L is preferable. The developer may further contain a water-soluble organic solvent, a surfactant and the like. Examples of the developer preferably used in the present disclosure include the developers described in paragraph 0194 of WO 2015/093271.
　現像方式としては、特に制限はなくパドル現像、シャワー現像、シャワー及びスピン現像、ディップ現像等のいずれでもよい。ここで、シャワー現像について説明すると、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、露光部分を除去することができる。また、現像の後に、洗浄剤などをシャワーにより吹き付け、ブラシなどで擦りながら、現像残渣を除去することが好ましい。現像液の液温度は２０℃～４０℃であることが好ましい。 The development method is not particularly limited, and may be paddle development, shower development, shower and spin development, dip development, or the like. Explaining shower development here, the exposed portion can be removed by spraying a developing solution onto the photosensitive resin layer after exposure with a shower. Further, after the development, it is preferable to remove a development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like. The liquid temperature of the developer is preferably 20°C to 40°C.
　本開示に係る樹脂パターンの製造方法、又は、本開示に係る回路配線の製造方法は、更に、現像して得られた感光性樹脂層を含むパターンを加熱処理するポストベーク工程を有していてもよい。
　ポストベークの加熱は８．１ｋＰａ～１２１．６ｋＰａの環境下で行うことが好ましく、５０．６６ｋＰａ以上の環境下で行うことがより好ましい。一方、１１１．４６ｋＰａ以下の環境下で行うことがより好ましく、１０１．３ｋＰａ以下の環境下で行うことが特に好ましい。
　ポストベークの温度は、８０℃～２５０℃であることが好ましく、１１０℃～１７０℃であることがより好ましく、１３０℃～１５０℃であることが特に好ましい。
　ポストベークの時間は、１分～３０分であることが好ましく、２分～１０分であることがより好ましく、２分～４分であることが特に好ましい。
　ポストベークは、空気環境下で行っても、窒素置換環境下で行ってもよい。 The method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure further includes a post-baking step of heat-treating a pattern including a photosensitive resin layer obtained by development. Good.
The post-baking heating is preferably performed in an environment of 8.1 kPa to 121.6 kPa, more preferably 50.66 kPa or more. On the other hand, it is more preferably performed in an environment of 111.46 kPa or less, and particularly preferably in an environment of 101.3 kPa or less.
The post-baking temperature is preferably 80°C to 250°C, more preferably 110°C to 170°C, and particularly preferably 130°C to 150°C.
The post-baking time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.
Post-baking may be performed in an air environment or a nitrogen substitution environment.
　また、本開示に係る樹脂パターンの製造方法は、さらに、ポスト露光工程等、その他の工程を有していてもよい。本開示に係る回路配線の製造方法は、後述のエッチング工程の前に、ポスト露光工程等、その他の工程を有していてもよい。 Further, the resin pattern manufacturing method according to the present disclosure may further include other steps such as a post exposure step. The circuit wiring manufacturing method according to the present disclosure may include other steps such as a post-exposure step before the etching step described below.
＜エッチング工程＞
　本開示に係る回路配線の製造方法は、上記樹脂パターンが配置されていない領域における基板をエッチング処理する工程（エッチング工程）を含むことが好ましい。 <Etching process>
The circuit wiring manufacturing method according to the present disclosure preferably includes a step (etching step) of etching the substrate in a region where the resin pattern is not arranged.
　上記エッチング工程では、上記現像工程により上記感光性樹脂層から形成されたパターンを、エッチングレジストとして使用し、上記導電層のエッチング処理を行う。
　エッチング処理の方法としては、特開２０１０－１５２１５５号公報の段落００４８～段落００５４等に記載の方法、公知のプラズマエッチング等のドライエッチングによる方法など、公知の方法を適用することができる。 In the etching step, the pattern formed from the photosensitive resin layer in the developing step is used as an etching resist to etch the conductive layer.
As a method for the etching treatment, known methods such as the method described in paragraphs 0048 to 0054 of JP 2010-152155 A, a method by dry etching such as a known plasma etching and the like can be applied.
　例えば、エッチング処理の方法としては、一般的に行われている、エッチングの対象をエッチング液に浸漬するウェットエッチング法が挙げられる。ウェットエッチングに用いられるエッチング液は、エッチングの対象に合わせて酸性タイプ又はアルカリ性タイプのエッチング液を適宜選択すればよい。
　酸性タイプのエッチング液としては、塩酸、硫酸、フッ酸、リン酸等の酸性成分単独の水溶液、酸性成分と塩化第二鉄、フッ化アンモニウム、過マンガン酸カリウム等の塩の混合水溶液等が例示される。酸性成分は、複数の酸性成分を組み合わせた成分を使用してもよい。
　アルカリ性タイプのエッチング液としては、水酸化ナトリウム、水酸化カリウム、アンモニア、有機アミン、テトラメチルアンモニウムハイドロオキサイドのような有機アミンの塩等のアルカリ成分単独の水溶液、アルカリ成分と過マンガン酸カリウム等の塩の混合水溶液等が例示される。アルカリ成分は、複数のアルカリ成分を組み合わせた成分を使用してもよい。 For example, as an etching method, a generally used wet etching method in which an object to be etched is immersed in an etching solution can be used. As the etching solution used for wet etching, an acidic type or alkaline type etching solution may be appropriately selected according to the object of etching.
Examples of the acidic type etching solution include an aqueous solution of an acidic component such as hydrochloric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid alone, a mixed aqueous solution of an acidic component and a salt of ferric chloride, ammonium fluoride, potassium permanganate, or the like. To be done. As the acidic component, a component obtained by combining a plurality of acidic components may be used.
As the alkaline type etching solution, an aqueous solution of an alkali component alone such as sodium hydroxide, potassium hydroxide, ammonia, an organic amine, a salt of an organic amine such as tetramethylammonium hydroxide, an alkali component and potassium permanganate, etc. Examples include mixed aqueous solutions of salts. As the alkaline component, a component obtained by combining a plurality of alkaline components may be used.
　エッチング液の温度は特に制限されないが、４５℃以下であることが好ましい。本開示においてエッチングマスク（エッチングパターン）として使用される樹脂パターンは、４５℃以下の温度域における酸性及びアルカリ性のエッチング液に対して特に優れた耐性を発揮することが好ましい。樹脂パターンがこのような耐性を有すると、エッチング工程中に感光性樹脂層が剥離することが防止され、感光性樹脂層の存在しない部分が選択的にエッチングされることになる。
　エッチング工程後、工程ラインの汚染を防ぐために、必要に応じて、エッチング処理された基板を洗浄する洗浄工程、及び、洗浄された基板を乾燥する乾燥工程を行ってもよい。 The temperature of the etching solution is not particularly limited, but it is preferably 45° C. or lower. The resin pattern used as an etching mask (etching pattern) in the present disclosure preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45° C. or lower. When the resin pattern has such resistance, the photosensitive resin layer is prevented from peeling off during the etching process, and the portion where the photosensitive resin layer does not exist is selectively etched.
After the etching process, in order to prevent contamination of the process line, a cleaning process for cleaning the etched substrate and a drying process for drying the cleaned substrate may be performed, if necessary.
＜除去工程＞
　本開示に係る回路配線の製造方法は、樹脂パターンを除去する工程（除去工程）を行うことが好ましい。
　除去工程は、特に制限はなく、必要に応じて行うことができるが、エッチング工程の後に行うことが好ましい。
　残存する感光性樹脂層を除去する方法としては特に制限はないが、薬品処理により除去する方法を挙げることができ、除去液を用いることが特に好ましく挙げることができる。
　感光性樹脂層の除去方法としては、好ましくは３０℃～８０℃、より好ましくは５０℃～８０℃にて撹拌中の除去液に感光性樹脂層などを有する基板を１分～３０分間浸漬する方法が挙げられる。 <Removal process>
In the circuit wiring manufacturing method according to the present disclosure, it is preferable to perform a step of removing the resin pattern (removal step).
The removing step is not particularly limited and may be performed as necessary, but is preferably performed after the etching step.
The method of removing the remaining photosensitive resin layer is not particularly limited, but a method of removing it by a chemical treatment can be mentioned, and it is particularly preferable to use a removing liquid.
The method for removing the photosensitive resin layer is preferably at 30° C. to 80° C., more preferably at 50° C. to 80° C., and the substrate having the photosensitive resin layer or the like is immersed in the removing solution for 1 minute to 30 minutes while stirring. There is a method.
　除去液としては、例えば、水酸化ナトリウム、水酸化カリウム等の無機アルカリ成分、又は、第１級アミン化合物、第２級アミン化合物、第３級アミン化合物、第４級アンモニウム塩化合物等の有機アルカリ成分を水、ジメチルスルホキシド、Ｎ－メチルピロリドン又はこれらの混合溶液に溶解させた除去液が挙げられる。
　また、除去液を使用し、スプレー法、シャワー法、パドル法等により除去してもよい。 Examples of the removing liquid include inorganic alkali components such as sodium hydroxide and potassium hydroxide, or organic alkalis such as primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds. A removing solution obtained by dissolving the components in water, dimethyl sulfoxide, N-methylpyrrolidone or a mixed solution thereof can be used.
Alternatively, a removing solution may be used to remove by a spray method, a shower method, a paddle method, or the like.
＜＜感光性樹脂層の全面露光＞＞
　本開示に係る回路配線の製造方法は、上記除去工程の前に、上記感光性樹脂層を全面露光する工程（「全面露光工程」ともいう。）を含むことが好ましい。更に必要に応じて、全面露光した上記感光性樹脂層を加熱する工程（「加熱工程」ともいう）を含んでもよい。全面露光工程及び加熱工程は、エッチング工程後かつ除去工程前に行われることが好ましい。
　エッチング工程の後に、エッチングマスクとして使用した上記感光性樹脂層を全面露光することにより、除去液への溶解性及び除去液の浸透性が向上し、除去液を長時間使用した場合（つまり、除去液が多少疲労した場合）においても除去性に優れる。また、更に、加熱工程を含む場合、加熱工程により、光酸発生剤の反応速度、及び、発生した酸とポジ型感光性樹脂との反応速度をより向上することができ、その結果、除去性能が向上する。 <<Overall exposure of photosensitive resin layer>>
The circuit wiring manufacturing method according to the present disclosure preferably includes a step of exposing the entire surface of the photosensitive resin layer (also referred to as “entire surface exposure step”) before the removing step. Further, if necessary, a step of heating the above-mentioned photosensitive resin layer which is entirely exposed (also referred to as “heating step”) may be included. The whole surface exposure step and the heating step are preferably performed after the etching step and before the removal step.
After the etching process, by exposing the entire surface of the photosensitive resin layer used as the etching mask, the solubility in the removing liquid and the permeability of the removing liquid are improved, and the removing liquid is used for a long time (that is, the removal is performed). Even when the liquid is slightly fatigued), it is excellent in removability. Further, when a heating step is further included, the heating step can further improve the reaction rate of the photoacid generator and the reaction rate of the generated acid with the positive photosensitive resin, and as a result, the removal performance. Is improved.
　全面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、上記露光工程と同じ波長の光を発する光源を用いることが好ましい。 The light source used for the exposure in the whole surface exposure process 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 that emits light having the same wavelength as that in the exposure step.
　全面露光工程における露光量は、除去性の観点から、５ｍＪ／ｃｍ２～１，０００ｍＪ／ｃｍ２であることが好ましく、１０ｍＪ／ｃｍ２～８００ｍＪ／ｃｍ２であることがより好ましく、１００ｍＪ／ｃｍ２～５００ｍＪ／ｃｍ２であることが特に好ましい。 Exposure amount in the overall exposure step, from the viewpoint of removability is preferably 5mJ / cm 2 ~ 1,000mJ / cm 2, more preferably 10mJ / cm 2 ~ 800mJ / cm 2, 100mJ / cm Particularly preferably, it is 2 to 500 mJ/cm 2 .
　全面露光工程における露光量は、除去性の観点から、上記露光工程における露光量以上であることが好ましく、上記露光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 whole surface exposure process is preferably equal to or more than the exposure amount in the above exposure process, and more preferably more than the exposure amount in the above exposure process.
＜その他の工程＞
　本開示に係る回路配線の製造方法は、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。例えば、以下のような工程が挙げられるが、これらの工程に制限されない。
　また、本開示における露光工程、現像工程、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。 <Other processes>
The circuit wiring manufacturing method according to the present disclosure may include any step (other steps) other than the above. For example, the following steps may be mentioned, but the present invention is not limited to these steps.
Further, as an example of the exposure step, the development step, and other steps in the present disclosure, the methods described in paragraphs 0035 to 0051 of JP 2006-23696 A can also be suitably used in the present disclosure.
＜＜カバーフィルム剥離工程＞＞
　本開示に係る樹脂パターンの製造方法、又は、本開示に係る回路配線の製造方法は、本開示に係る感光性転写材料がカバーフィルムを有する場合、上記感光性転写材料のカバーフィルムを剥離する工程（「カバーフィルム剥離工程」ということがある。）を含むことが好ましい。カバーフィルムを剥離する方法は、制限されず、公知の方法を適用することができる。 <<Cover film peeling process>>
A method of manufacturing a resin pattern according to the present disclosure, or a method of manufacturing a circuit wiring according to the present disclosure, in a case where the photosensitive transfer material according to the present disclosure has a cover film, a step of peeling the cover film of the photosensitive transfer material. (It may be referred to as a “cover film peeling step”). The method of peeling off the cover film is not limited, and a known method can be applied.
＜＜可視光線反射率を低下させる工程＞＞
　本開示に係る回路配線の製造方法は、基材上の複数の導電層の一部又は全ての可視光線反射率を低下させる処理をする工程を含むことが可能である。
　可視光線反射率を低下させる処理としては、酸化処理などを挙げることができる。例えば、銅を酸化処理して酸化銅とすることで、黒化することにより、可視光線反射率を低下させることができる。
　可視光線反射率を低下させる処理の好ましい態様については、特開２０１４－１５０１１８号公報の段落００１７～段落００２５、並びに、特開２０１３－２０６３１５号公報の段落００４１、段落００４２、段落００４８及び段落００５８に記載があり、この公報の内容は本明細書に組み込まれる。 <<Step of lowering visible light reflectance>>
The circuit wiring manufacturing method according to the present disclosure can include a step of performing a process of reducing the visible light reflectance of some or all of the plurality of conductive layers on the base material.
Examples of the treatment for lowering the visible light reflectance include oxidation treatment. For example, the visible light reflectance can be reduced by blackening by oxidizing copper into copper oxide.
For preferred embodiments of the treatment for reducing the visible light reflectance, see paragraphs 0017 to 0025 of JP-A-2014-150118, and paragraphs 0041, 0042, 0048 and 0058 of JP-A-2013-206315. There is a description, and the content of this publication is incorporated herein.
＜＜絶縁膜を形成する工程、絶縁膜上に新たな導電層を形成する工程＞＞
　本開示に係る回路配線の製造方法は、形成した回路配線上に絶縁膜を形成する工程と、絶縁膜上に新たな導電層を形成する工程と、を含むことも好ましい。
　このような構成により、上述の第二の電極パターンを、第一の電極パターンと絶縁しつつ、形成することができる。
　絶縁膜を形成する工程については、特に制限はなく、公知の永久膜を形成する方法を挙げることができる。また、絶縁性を有する感光性材料を用いて、フォトリソグラフィにより所望のパターンの絶縁膜を形成してもよい。
　絶縁膜上に新たな導電層を形成する工程については、特に制限はない。導電性を有する感光性材料を用いて、フォトリソグラフィにより所望のパターンの新たな導電層を形成してもよい。 <<Step of forming insulating film, step of forming new conductive layer on insulating film>>
The circuit wiring manufacturing method according to the present disclosure preferably also includes a step of forming an insulating film on the formed circuit wiring and a step of forming a new conductive layer on the insulating film.
With such a configuration, the above-mentioned second electrode pattern can be formed while being insulated from the first electrode pattern.
The step of forming the insulating film is not particularly limited, and a known method of forming a permanent film can be used. Further, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having an insulating property.
There is no particular limitation on the step of forming a new conductive layer on the insulating film. A new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.
　本開示に係る回路配線の製造方法は、基材の両方の表面にそれぞれ複数の導電層を有する基板を用い、基材の両方の表面に形成された導電層に対して逐次又は同時に回路形成することも好ましい。このような構成により、基材の一方の表面に第一の導電パターン、もう一方の表面に第二の導電パターンを形成したタッチパネル用回路配線を形成することができる。また、このような構成のタッチパネル用回路配線を、ロールツーロールで基材の両面から形成することも好ましい。 The circuit wiring manufacturing method according to the present disclosure uses a substrate having a plurality of conductive layers on both surfaces of a base material, and forms a circuit sequentially or simultaneously on the conductive layers formed on both surfaces of the base material. Is also preferable. With such a configuration, it is possible to form the touch panel circuit wiring in which the first conductive pattern is formed on one surface of the substrate and the second conductive pattern is formed on the other surface. It is also preferable that the touch panel circuit wiring having such a configuration is formed from both sides of the base material by roll-to-roll.
　本開示に係る回路配線の製造方法により製造される回路配線は、種々の装置に適用することができる。本開示に係る回路配線の製造方法により製造される回路配線を備えた装置としては、例えば入力装置等であり、タッチパネルであることが好ましく、静電容量型タッチパネルであることがより好ましい。また、上記入力装置は、有機ＥＬ表示装置、液晶表示装置等の表示装置に適用することができる。 The circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure can be applied to various devices. The device provided with the circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure is, for example, an input device or the like, preferably a touch panel, and more preferably a capacitance type touch panel. The input device can be applied to display devices such as organic EL display devices and liquid crystal display devices.
（タッチパネルの製造方法）
　本開示に係るタッチパネルの製造方法は、本開示に係る感光性転写材料を用いる方法であればよいが、本開示に係る感光性転写材料における上記仮支持体に対して感光性樹脂層を有する側の最外層を導電層を有する基板に接触させて貼り合わせる工程（貼り合わせ工程）と、上記感光性樹脂層をパターン露光する工程（露光工程）と、露光された上記感光性樹脂層を現像して樹脂パターンを形成する工程（現像工程）と、上記樹脂パターンが配置されていない領域における上記基板をエッチング処理する工程（エッチング工程）と、をこの順に含むことが好ましい。 (Method of manufacturing touch panel)
The method for manufacturing the touch panel according to the present disclosure may be a method that uses the photosensitive transfer material according to the present disclosure, but a side having a photosensitive resin layer with respect to the temporary support in the photosensitive transfer material according to the present disclosure. Of contacting the outermost layer of the substrate with a substrate having a conductive layer (bonding step), pattern exposing the photosensitive resin layer (exposure step), and developing the exposed photosensitive resin layer. It is preferable to include, in this order, a step of forming a resin pattern (development step) and a step of etching the substrate in an area where the resin pattern is not arranged (etching step).
　本開示に係るタッチパネルの製造方法における、各工程の具体的な態様、及び、各工程を行う順序等の実施態様については、上述の「回路配線の製造方法」の項において説明した通りであり、好ましい態様も同様である。
　本開示に係るタッチパネルの製造方法は、上述した以外は、公知のタッチパネルの製造方法を参照することができる。
　また、本開示に係るタッチパネルの製造方法は、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。 In the method for manufacturing a touch panel according to the present disclosure, specific aspects of each step, and embodiments such as the order of performing each step are as described in the above-mentioned “method for manufacturing circuit wiring”. The preferred embodiment is also the same.
As for the touch panel manufacturing method according to the present disclosure, a known touch panel manufacturing method can be referred to other than the above.
Further, the touch panel manufacturing method according to the present disclosure may include any step (other steps) other than the above.
　本開示に係るタッチパネルの製造方法において用いられるマスクのパターンの一例を、図２及び図３に示す。
　図２に示されるパターン（以下、パターンＡとも称する）、及び、図３に示されるパターン（以下、パターンＢとも称する）において、ＳＬ及びＧは非画像部（遮光部）であり、ＤＬはアライメント合わせの枠を仮想的に示したものである。本開示に係るタッチパネルの製造方法において、例えば、図２に示されるパターンＡを有するマスクを介して感光性樹脂層を露光することで、ＳＬ及びＧに対応するパターンＡを有する回路配線が形成されたタッチパネルを製造できる。具体的には、国際公開第２０１６／０１９０４０５号の図１に記載の方法で作製できる。製造されたタッチパネルの一例においては、Ｇは透明電極（タッチパネル用電極）が形成される部分であり、ＳＬは周辺取出し部の配線が形成される部分である。 An example of a mask pattern used in the method for manufacturing the touch panel according to the present disclosure is shown in FIGS. 2 and 3.
In the pattern shown in FIG. 2 (hereinafter also referred to as pattern A) and the pattern shown in FIG. 3 (hereinafter also referred to as pattern B), SL and G are non-image portions (light shielding portions), and DL is alignment. This is a hypothetical view of the matching frame. In the method for manufacturing a touch panel according to the present disclosure, for example, by exposing the photosensitive resin layer through the mask having the pattern A shown in FIG. 2, the circuit wiring having the pattern A corresponding to SL and G is formed. Touch panel can be manufactured. Specifically, it can be prepared by the method shown in FIG. 1 of WO 2016/0190405. In an example of the manufactured touch panel, G is a portion where a transparent electrode (touch panel electrode) is formed, and SL is a portion where the wiring of the peripheral extraction portion is formed.
　本開示に係るタッチパネルは、本開示に係る回路配線の製造方法により製造された回路配線を少なくとも有するタッチパネルである。また、本開示に係るタッチパネルは、透明基板と、電極と、絶縁層又は保護層とを少なくとも有することが好ましい。
　本開示に係るタッチパネルにおける検出方法としては、抵抗膜方式、静電容量方式、超音波方式、電磁誘導方式、及び、光学方式など公知の方式のいずれでもよい。中でも、静電容量方式が好ましい。
　タッチパネル型としては、いわゆる、インセル型（例えば、特表２０１２－５１７０５１号公報の図５、図６、図７、図８に記載のもの）、いわゆる、オンセル型（例えば、特開２０１３－１６８１２５号公報の図１９に記載のもの、特開２０１２－８９１０２号公報の図１や図５に記載のもの）、ＯＧＳ（Ｏｎｅ　Ｇｌａｓｓ　Ｓｏｌｕｔｉｏｎ）型、ＴＯＬ（Ｔｏｕｃｈ－ｏｎ－Ｌｅｎｓ）型（例えば、特開２０１３－５４７２７号公報の図２に記載のもの）、その他の構成（例えば、特開２０１３－１６４８７１号公報の図６に記載のもの）、各種アウトセル型（いわゆる、ＧＧ、Ｇ１・Ｇ２、ＧＦＦ、ＧＦ２、ＧＦ１、Ｇ１Ｆなど）等を挙げることができる。
　本開示に係るタッチパネルとしては、例えば、特開２０１７－１２０３４５号公報の段落０２２９に記載のものが挙げられる。 The touch panel according to the present disclosure is a touch panel including at least circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure. Further, the touch panel according to the present disclosure preferably has at least a transparent substrate, an electrode, and an insulating layer or a protective layer.
The detection method in the touch panel according to the present disclosure may be any known method such as a resistance film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method. Of these, the capacitance method is preferable.
As the touch panel type, a so-called in-cell type (for example, those described in FIGS. 5, 6, 7, and 8 of Japanese Patent Publication No. 2012-517051), a so-called on-cell type (for example, Japanese Unexamined Patent Publication No. 2013-168125). FIG. 19 of the publication, FIG. 1 and FIG. 5 of JP 2012-89102 A, OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, JP 2 of Japanese Patent Laid-Open No. 2013-54727), other configurations (for example, the one shown in FIG. 6 of Japanese Patent Laid-Open No. 2013-164871), various out-cell types (so-called GG, G1, G2, GFF, GF2, GF1, G1F, etc.) and the like.
Examples of the touch panel according to the present disclosure include those described in paragraph 0229 of JP-A-2017-120345.
（フィルム及びその製造方法）
　本開示に係るフィルムは、粒子を含有する粒子含有層を少なくとも片面に有し、ヘーズ値が、０．２％以下であり、上記粒子含有層を有する側の面の表面粗さＲａが、０．０２μｍ～０．２０μｍである。
　本開示に係るフィルムの用途としては、特に制限はない。本開示に係るフィルムは、保護フィルム、剥離フィルム、又は、感光性転写材料の仮支持体として好適に用いることができ、感光性転写材料の仮支持体として特に好適に用いることができる。 (Film and manufacturing method thereof)
The film according to the present disclosure has a particle-containing layer containing particles on at least one surface, has a haze value of 0.2% or less, and has a surface roughness Ra of the surface having the particle-containing layer of 0. It is from 0.02 μm to 0.20 μm.
The use of the film according to the present disclosure is not particularly limited. The film according to the present disclosure can be preferably used as a protective film, a release film, or a temporary support for a photosensitive transfer material, and can be particularly preferably used as a temporary support for a photosensitive transfer material.
　本開示に係るフィルムは、新規なフィルムであり、ヘーズ値が小さく、透明性に優れるとともに、上記本開示に係る感光性転写材料における仮支持体にて述べたように、搬送時のシワ発生抑制性を備える。
　従来のフィルムとしては、特開２０１７－７８８５２号公報又は特開２０００－２２１６８８号公報に記載されたものが知られているが、特開２０１７－７８８５２号公報に記載されたフィルムでは、搬送時のシワの発生を十分に抑制できなかった。また、特開２０００－２２１６８８号公報に記載されたフィルムでは、透明性が十分でなく、また、透明性と搬送時のシワ発生抑制性とを両立できなかった。また、特開２０００－２２１６８８号公報には、ポジ型の感光性転写材料について何ら記載されていない。 The film according to the present disclosure is a novel film, has a small haze value, is excellent in transparency, and, as described in the temporary support in the photosensitive transfer material according to the present disclosure, suppresses wrinkling during transport. Have sex.
As the conventional film, those described in JP-A-2017-78852 or JP-A-2000-221688 are known, but the film described in JP-A-2017-78852 is not suitable for transporting. The generation of wrinkles could not be suppressed sufficiently. Further, the film described in JP-A-2000-221688 has insufficient transparency, and it is not possible to achieve both transparency and wrinkle suppression during transport. Further, Japanese Patent Laid-Open No. 2000-221688 does not describe any positive photosensitive transfer material.
　本開示に係るフィルムの好ましい態様等の構成の詳細は、後述する態様以外、上記本開示に係る感光性転写材料における仮支持体の好ましい態様等の構成の詳細と同様である。
　本開示に係るフィルムは、光学特性、耐溶剤性及び耐熱性の観点から、ポリエステル樹脂を含むことが好ましく、ポリエチレンテレフタレートを含むことがより好ましい。
　また、本開示に係るフィルムは、光学特性、耐溶剤性及び耐熱性の観点から、ポリエステル樹脂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。
　更に、本開示に係るフィルムは、透明性、及び、搬送時のシワ発生抑制性の効果をより発揮する観点から、延伸フィルムであることが好ましく、二軸延伸フィルムであることがより好ましい。 The details of the configuration of the preferred embodiment of the film according to the present disclosure are the same as the details of the configuration of the preferred embodiment of the temporary support in the photosensitive transfer material according to the present disclosure, except for the embodiments described later.
The film according to the present disclosure preferably contains a polyester resin, more preferably polyethylene terephthalate, from the viewpoint of optical properties, solvent resistance, and heat resistance.
The film according to the present disclosure is preferably a polyester resin film, more preferably a polyethylene terephthalate film, from the viewpoint of optical properties, solvent resistance and heat resistance.
Furthermore, the film according to the present disclosure is preferably a stretched film, and more preferably a biaxially stretched film, from the viewpoint of exhibiting the effect of transparency and the property of suppressing the generation of wrinkles during transportation.
　本開示に係るフィルムの製造方法としては、特に制限はないが、第一延伸方向に延伸された一軸延伸フィルム上に、粒子を含有する層を形成する工程、及び、上記一軸延伸フィルム及び上記一軸延伸フィルム上に形成された上記粒子を含有する層を、上記一軸延伸フィルムにおけるフィルム面に沿って上記第一延伸方向と直交する第二延伸方向に延伸する工程を含む製造方法であることが好ましく、第一延伸方向に延伸された一軸延伸ポリエチレンテレフタレートフィルム上に、粒子を含有する層を形成する工程、及び、上記一軸延伸ポリエチレンテレフタレートフィルム及び上記一軸延伸ポリエチレンテレフタレートフィルム上に形成された上記粒子を含有する層を、上記一軸延伸ポリエチレンテレフタレートフィルムにおけるフィルム面に沿って上記第一延伸方向と直交する第二延伸方向に延伸する工程を含む製造方法であることがより好ましい。
　上記延伸時の延伸倍率、及び、延伸温度等については、特に制限はなく、所望に応じ、公知の延伸方法を参照して行うことができる。
　また、本開示に係るフィルムの製造方法は、上記粒子を含有する層を形成する工程の前に、未延伸フィルムを一軸延伸し一軸延伸フィルムを作製する工程を更に含んでいてもよい。
　また、本開示に係るフィルムの製造方法は、上述した以外の他の工程を更に含んでいてもよい。 The method for producing a film according to the present disclosure is not particularly limited, on the uniaxially stretched film stretched in the first stretching direction, a step of forming a layer containing particles, and the uniaxially stretched film and the uniaxially stretched film. A layer containing the particles formed on a stretched film is preferably a manufacturing method including a step of stretching in a second stretching direction orthogonal to the first stretching direction along the film surface of the uniaxially stretched film. A step of forming a layer containing particles on the uniaxially stretched polyethylene terephthalate film stretched in the first stretching direction, and the uniaxially stretched polyethylene terephthalate film and the particles formed on the uniaxially stretched polyethylene terephthalate film. It is more preferable that the manufacturing method includes a step of stretching the contained layer in the second stretching direction orthogonal to the first stretching direction along the film surface of the uniaxially stretched polyethylene terephthalate film.
The stretching ratio and the stretching temperature during the stretching are not particularly limited, and a known stretching method can be referred to if desired.
The method for producing a film according to the present disclosure may further include a step of uniaxially stretching an unstretched film to produce a uniaxially stretched film before the step of forming the layer containing the particles.
Further, the method for producing a film according to the present disclosure may further include steps other than the above.
　以下に実施例を挙げて本開示に係る実施形態を更に具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、及び、処理手順等は、本開示の趣旨を逸脱しない限り、適宜、変更することができる。したがって、本開示に係る実施形態の範囲は以下に示す具体例に限定されない。なお、特に断りのない限り、「部」、「％」は質量基準である。 The embodiments according to the present disclosure will be described more specifically with reference to the following examples. The materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present disclosure. Therefore, the scope of the embodiments according to the present disclosure is not limited to the specific examples shown below. In addition, "part" and "%" are based on mass unless otherwise specified.
＜製造例１＞
　以下の方法で基材として用いるポリエステルフィルムの一方の面に塗布液１を塗布し、下記条件により延伸することによって仮支持体を作製した。 <Production Example 1>
Coating solution 1 was applied to one surface of a polyester film used as a substrate by the following method, and stretched under the following conditions to prepare a temporary support.
〔粒子含有層形成用の塗布液の調製〕
　下記に示す配合量で、各成分を混合し、塗布液１を得た。塗布液１の調製後塗布までに、塗布液１に対して孔径６μｍフィルター（Ｆ２０、（株）マーレフィルターシステムズ製）でのろ過、及び、膜脱気（２×６ラジアルフロースーパーフォビック、ポリポア（株）製）を実施した。 [Preparation of coating liquid for forming particle-containing layer]
Coating liquid 1 was obtained by mixing the components in the amounts shown below. After preparation of the coating liquid 1 and before coating, the coating liquid 1 is filtered with a filter having a pore size of 6 μm (F20, manufactured by Mare Filter Systems Co., Ltd.) and membrane degassing (2×6 radial flow superphobic, polypore). (Manufactured by KK).
－塗布液１－
・アクリルポリマー（ＡＳ－５６３Ａ、ダイセルファインケム（株）製、固形分２７．５質量％）：１６７部
・ノニオン系界面活性剤（ナロアクティーＣＬ９５、三洋化成工業（株）製、固形分１００質量％）：０．７部
・アニオン系界面活性剤（ラピゾールＡ－９０、日油（株）製、固形分１質量％水希釈）：１１４．４部
・カルナバワックス分散物（セロゾール５２４、中京油脂（株）製、固形分３０質量％）７部
・カルボジイミド化合物（カルボジライトＶ－０２－Ｌ２、日清紡（株）製、固形分１０質量％水希釈）：２０．９部
・シリカ粒子（スノーテックスＸＬ、日産化学（株）製、固形分４０質量％、算術平均粒径５０ｎｍ）：２．８部
・水：６９０．２部 -Coating liquid 1-
-Acrylic polymer (AS-563A, manufactured by Daicel Finechem Ltd., solid content 27.5% by mass): 167 parts-Nonionic surfactant (Naloacty CL95, manufactured by Sanyo Chemical Industry Co., Ltd., solid content 100% by mass) ): 0.7 part-anionic surfactant (rapizole A-90, manufactured by NOF Corporation, solid content 1 mass% diluted with water): 114.4 parts-carnauba wax dispersion (Cerosol 524, Chukyo Yushi ( Ltd., solid content 30 mass%) 7 parts carbodiimide compound (Carbodilite V-02-L2, Nisshinbo Co., Ltd., solid content 10 mass% water dilution): 20.9 parts Silica particles (Snowtex XL, Nissan Chemical Co., Ltd., solid content 40% by mass, arithmetic mean particle size 50 nm): 2.8 parts, water: 690.2 parts
〔押出成形〕
　特許第５５７５６７１号公報の実施例１に記載のクエン酸キレート有機チタン錯体を重合触媒としたポリエチレンテレフタレートのペレットを、含水率５０ｐｐｍ以下に乾燥させた後、直径３０ｍｍの１軸混練押出し機のホッパーに投入し、２８０℃で溶融して押出した。この溶融体（メルト）を、濾過器（孔径３μｍ）に通した後、ダイから２５℃の冷却ロールに押出し、未延伸フィルムを得た。なお、押出されたメルトは、静電印加法を用い冷却ロールに密着させた。 [Extrusion molding]
Pellets of polyethylene terephthalate using the citric acid chelate organic titanium complex described in Example 1 of Japanese Patent No. 5575671 as a polymerization catalyst were dried to a water content of 50 ppm or less, and then placed in a hopper of a uniaxial kneading extruder having a diameter of 30 mm. It was charged, melted at 280° C. and extruded. This melt (melt) was passed through a filter (pore size: 3 μm) and then extruded from a die onto a cooling roll at 25° C. to obtain an unstretched film. The extruded melt was brought into close contact with a cooling roll using an electrostatic application method.
〔延伸、及び、塗布〕
　上記方法で冷却ロール上に押出し、固化した未延伸フィルムに対し、以下の方法で逐次２軸延伸を施し、厚み２５μｍの基材（ポリエステルフィルム）と厚み４０ｎｍの粒子含有層とを有する仮支持体を得た。 [Stretching and coating]
A temporary support having a base material (polyester film) having a thickness of 25 μm and a particle-containing layer having a thickness of 40 nm, which is obtained by sequentially biaxially stretching an unstretched film which is extruded onto a cooling roll and solidified by the above method by the following method. Got
（ａ）縦延伸
　未延伸フィルムを周速の異なる２対のニップロールの間に通し、縦方向（搬送方向）に延伸した。なお、予熱温度を７５℃、延伸温度を９０℃、延伸倍率を３．４倍、延伸速度を１，３００％／秒として実施した。 (A) Longitudinal stretching The unstretched film was passed between two pairs of nip rolls having different peripheral speeds and stretched in the longitudinal direction (conveying direction). The preheating temperature was 75° C., the stretching temperature was 90° C., the stretching ratio was 3.4 times, and the stretching speed was 1,300%/sec.
（ｂ）塗布
　縦延伸したフィルムの片面に、上記塗布液１を、製膜後４０ｎｍの厚みとなるように、バーコーターで塗布した。 (B) Coating The coating solution 1 was coated on one surface of the longitudinally stretched film with a bar coater so as to have a thickness of 40 nm after film formation.
（ｃ）横延伸
　上記縦延伸と塗布を行ったフィルムに対し、テンターを用いて下記条件にて横延伸した。
＜＜条件＞＞
　予熱温度：１１０℃
　延伸温度：１２０℃
　延伸倍率：４．２倍
　延伸速度：５０％／秒 (C) Transverse Stretching The film subjected to the above-mentioned longitudinal stretching and coating was transversely stretched under the following conditions using a tenter.
<< conditions >>
Preheating temperature: 110℃
Stretching temperature: 120°C
Draw ratio: 4.2 times Draw speed: 50%/sec
〔熱固定、及び、熱緩和〕
　続いて、縦延伸及び横延伸を終えた後の延伸フィルムを下記条件で熱固定した。更に、熱固定した後、テンター幅を縮め下記条件で熱緩和した。
－熱固定条件－
　熱固定温度：２２７℃
　熱固定時間：６秒
－熱緩和条件－
　熱緩和温度：１９０℃
　熱緩和率：４％ [Heat fixation and heat relaxation]
Subsequently, the stretched film after longitudinal stretching and transverse stretching was heat-set under the following conditions. Furthermore, after heat fixing, the tenter width was reduced and heat relaxation was performed under the following conditions.
-Heat fixation conditions-
Heat setting temperature: 227℃
Heat setting time: 6 seconds-Heat relaxation condition-
Thermal relaxation temperature: 190℃
Thermal relaxation rate: 4%
〔巻き取り〕
　熱固定及び熱緩和の後、両端をトリミングし、端部に幅１０ｍｍで押出し加工（ナーリング）を行った後、張力４０ｋｇ／ｍで巻き取った。なお、幅は１．５ｍ、巻長は６３００ｍであった。得られたフィルムロールを、製造例１の仮支持体とした。
　得られた仮支持体の基材は、ヘーズ値：０．２、１５０℃、３０分加熱による熱収縮率は、ＭＤ（搬送方向、Ｍａｃｈｉｎｅ　Ｄｉｒｅｃｔｉｏｎ）：１．０％、ＴＤ（フィルムの面上において搬送方向と直交する方向、Ｔｒａｎｓｖｅｒｓｅ　Ｄｉｒｅｃｔｉｏｎ）：０．２％であった。塗布層の膜厚は断面ＴＥＭ写真から測定し、４０ｎｍであった。ヘーズ値はヘーズメーター（日本電色工業（株）製、ＮＤＨ２０００）を用いて全光ヘーズの値として測定した。 〔Winding〕
After heat setting and heat relaxation, both ends were trimmed, the ends were extruded (knurling) with a width of 10 mm, and then wound at a tension of 40 kg/m. The width was 1.5 m and the winding length was 6300 m. The obtained film roll was used as the temporary support of Production Example 1.
The heat-shrinkage ratio of the obtained temporary support is 0.2% at 150° C. for 30 minutes, MD (conveying direction, Machine Direction): 1.0%, TD (on the surface of the film). In the direction orthogonal to the transport direction, Transverse Direction: 0.2%. The thickness of the coating layer was 40 nm as measured from the TEM photograph of the cross section. The haze value was measured as a value of total light haze using a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.).
〔粒子の算術平均粒径の測定方法〕
　（株）日立ハイテクノロジーズ製ＨＴ－７７００型透過型電子顕微鏡（ＴＥＭ）を用いて、加速電圧１００ｋＶで観察し、任意に抽出した粒子４００個の直径の平均値（算術平均粒径）を求めた。なお、実施例で使用した仮支持体において、明らかに大きい凝集物（異物、ゴミ等）はカウントしなかった。 [Measurement method of arithmetic mean particle size of particles]
Using an HT-7700 transmission electron microscope (TEM) manufactured by Hitachi High-Technologies Corporation, observation was performed at an accelerating voltage of 100 kV, and an average value (arithmetic mean particle diameter) of 400 particles arbitrarily extracted was calculated. .. In the temporary support used in the examples, obviously large aggregates (foreign matter, dust, etc.) were not counted.
〔粒子含有層の片面又は両面における存在位置の判定〕
　仮支持体を断面切削し、断面を上記ＴＥＭにて観察して、粒子含有層が存在するか否かを、仮支持体の両面それぞれにおいて判定した。 [Determination of the existence position on one side or both sides of the particle-containing layer]
The cross section of the temporary support was cut, and the cross section was observed with the TEM to determine whether or not the particle-containing layer was present on each side of the temporary support.
〔ヘーズ値の測定〕
　ヘーズメーターＮＤＨ４００（日本電色工業（株）製）を用いて、仮支持体の面方向の１０箇所においてヘーズ値を測定し、その平均値を求めた。 [Measurement of haze value]
A haze meter NDH400 (manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the haze value at 10 positions in the surface direction of the temporary support, and the average value was obtained.
〔Ｒａの測定方法〕
　仮支持体の測定面について、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、仮支持体の表面プロファイルを得た。なお、測定及び解析ソフトには、ＭｅｔｒｏＰｒｏ　ｖｅｒ８．３．２のＭｉｃｒｏｓｃｏｐｅ　Ａｐｐｌｉｃａｔｉｏｎを用いた。次に、上記解析ソフト（ＭｅｔｒｏＰｒｏ　ｖｅｒ８．３．２－Ｍｉｃｒｏｓｃｏｐｅ　Ａｐｐｌｉｃａｔｉｏｎ）にて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た。得られたヒストグラムデータから、算術平均粗さを算出し、得られる値を表面粗さＲａとする。 [Method of measuring Ra]
Regarding the measurement surface of the temporary support, a three-dimensional optical profiler (New View7300, manufactured by Zygo) was used to obtain a surface profile of the temporary support under the following conditions. As the measurement and analysis software, the Microscope Application of MetroPro ver 8.3.2 was used. Next, the Surface Map screen was displayed by the above-mentioned analysis software (MetroPro ver 8.3.2-Microscope Application), and histogram data was obtained on the Surface Map screen. The arithmetic mean roughness is calculated from the obtained histogram data, and the obtained value is defined as the surface roughness Ra.
－測定条件－
　対物レンズ：５０倍
　Ｚｏｏｍ：０．５倍
　測定領域：１．００ｍｍ×１．００ｍｍ
　（解析条件）
　Ｒｅｍｏｖｅｄ：ｐｌａｎｅ
　Ｆｉｌｔｅｒ：ｏｆｆ
　ＦｉｌｔｅｒＴｙｐｅ：ａｖｅｒａｇｅ
　Ｒｅｍｏｖｅ　ｓｐｉｋｅｓ：ｏｎ
　Ｓｐｉｋｅ　Ｈｅｉｇｈｔ（ｘＲＭＳ）：７．５ -Measurement condition-
Objective lens: 50 times Zoom: 0.5 times Measurement area: 1.00 mm x 1.00 mm
(Analysis conditions)
Removed: plane
Filter: off
FilterType: average
Remove spikes: on
Spike Height (xRMS): 7.5
＜製造例２＞
　塗布液１を塗布する際のバーを調整して製膜後膜厚を６０ｎｍに変えた以外は、製造例１と同様にして、製造例２の仮支持体を得た。 <Production Example 2>
A temporary support of Production Example 2 was obtained in the same manner as in Production Example 1 except that the bar at the time of applying the coating liquid 1 was adjusted and the film thickness after film formation was changed to 60 nm.
＜製造例３＞
　塗布液１のシリカ粒子をスノーテックスＺＬ（シリカ粒子、日産化学（株）製、固形分４０質量％、算術平均粒径８５ｎｍ）に変更し、塗布液を塗布する際のバーを調整して製膜後膜厚を５０ｎｍに変えた以外は、製造例１と同様にして、製造例３の仮支持体を得た。 <Production Example 3>
The silica particles of the coating liquid 1 are changed to Snowtex ZL (silica particles, manufactured by Nissan Chemical Co., Ltd., solid content 40% by mass, arithmetic mean particle diameter 85 nm), and the bar used when coating the coating liquid is adjusted. A temporary support of Production Example 3 was obtained in the same manner as Production Example 1 except that the film thickness after the film was changed to 50 nm.
＜製造例４＞
　塗布液１のシリカ粒子の量を増やし、塗布液を塗布する面を両面にし、塗布する際のバーを調整して製膜後膜厚を５０ｎｍに変えた以外は、製造例１と同様にして、製造例４の仮支持体を得た。 <Production Example 4>
In the same manner as in Production Example 1 except that the amount of silica particles in the coating liquid 1 was increased, the surfaces to be coated with the coating liquid were set to both sides, and the bar during coating was adjusted to change the thickness after film formation to 50 nm. A temporary support of Production Example 4 was obtained.
＜製造例５＞
　ダイから押出した未延伸フィルムの厚みを４／５倍に変更した以外は、製造例１と同様にして、製造例５の仮支持体を得た。 <Production Example 5>
A temporary support of Production Example 5 was obtained in the same manner as Production Example 1 except that the thickness of the unstretched film extruded from the die was changed to 4/5 times.
＜製造例６＞
　実施例１３に用いた仮支持体は、以下の方法で、基材として用いるポリエステルフィルムを準備し、このポリエステルフィルムの片面に、粒子含有層形成用の塗布液２を塗布して、延伸することによって得た。 <Production Example 6>
For the temporary support used in Example 13, a polyester film to be used as a substrate is prepared by the following method, and one side of the polyester film is coated with the coating liquid 2 for forming a particle-containing layer and stretched. Got by
〔押出成形〕
　特許第５５７５６７１号公報に記載のチタン化合物を重合触媒としたポリエチレンテレフタレートのペレットを、含水率５０ｐｐｍ以下に乾燥させた後、直径３０ｍｍの１軸混練押出し機のホッパーに投入し、２８０℃で溶融して押出した。この溶融体（メルト）を、濾過器（孔径３μｍ）を通した後、ダイから２５℃の冷却ロールに押出し、未延伸フィルムを得た。なお、押出されたメルトは、静電印加法を用い冷却ロールに密着させた。 [Extrusion molding]
Pellets of polyethylene terephthalate using a titanium compound as a polymerization catalyst described in Japanese Patent No. 5575671 were dried to a water content of 50 ppm or less, then charged into a hopper of a uniaxial kneading extruder having a diameter of 30 mm and melted at 280°C. And extruded. This melt (melt) was passed through a filter (pore size: 3 μm) and then extruded from a die onto a cooling roll at 25° C. to obtain an unstretched film. The extruded melt was brought into close contact with a cooling roll using an electrostatic application method.
〔延伸及び塗布〕
　上記方法で冷却ロール上に押出し、固化した未延伸フィルムに対し、以下の方法で逐次２軸延伸を施し、厚み３０μｍの基材（ポリエステルフィルム）と厚み５０ｎｍの粒子含有層を有する仮支持体を得た。 [Stretching and coating]
The unstretched film extruded on the cooling roll by the above method and solidified was sequentially biaxially stretched by the following method to obtain a temporary support having a base material (polyester film) having a thickness of 30 μm and a particle-containing layer having a thickness of 50 nm. Obtained.
（ａ）縦延伸
　未延伸フィルムを周速の異なる２対のニップロールの間に通し、縦方向（搬送方向）に延伸した。なお、予熱温度を７５℃、延伸温度を９０℃、延伸倍率を３．４倍、延伸速度を１３００％／秒として実施した。 (A) Longitudinal stretching The unstretched film was passed between two pairs of nip rolls having different peripheral speeds and stretched in the longitudinal direction (conveying direction). The preheating temperature was 75° C., the stretching temperature was 90° C., the stretching ratio was 3.4 times, and the stretching speed was 1300%/sec.
（ｂ）塗布
　縦延伸したフィルムの上に、下記の粒子含有層形成用の塗布液２を、５．６ｇ／ｍ２となるように、バーコーターで塗布した。 (B) Application On the longitudinally stretched film, the following coating solution 2 for forming a particle-containing layer was applied with a bar coater so as to have a concentration of 5.6 g/m 2 .
（ｃ）横延伸
　縦延伸と塗布を行ったフィルムに対し、テンターを用いて下記条件にて横延伸した。
－条件－
　予熱温度：１１０℃
　延伸温度：１２０℃
　延伸倍率：４．２倍
　延伸速度：５０％／秒 (C) Horizontal Stretching The film that has been longitudinally stretched and applied was laterally stretched using a tenter under the following conditions.
-conditions-
Preheating temperature: 110℃
Stretching temperature: 120°C
Draw ratio: 4.2 times Draw speed: 50%/sec
〔熱固定及び熱緩和〕
　続いて、縦延伸及び横延伸を終えた後の延伸フィルムを下記条件で熱固定した。更に、熱固定した後、テンター幅を縮め下記条件で熱緩和した。
－熱工程条件－
　熱固定温度：２２７℃
　熱固定時間：６秒
－熱緩和条件－
　熱緩和温度：１９０℃
　熱緩和率：４％ [Heat fixation and heat relaxation]
Subsequently, the stretched film after longitudinal stretching and transverse stretching was heat-set under the following conditions. Furthermore, after heat fixing, the tenter width was reduced and heat relaxation was performed under the following conditions.
-Thermal process conditions-
Heat setting temperature: 227℃
Heat setting time: 6 seconds-Heat relaxation condition-
Thermal relaxation temperature: 190℃
Thermal relaxation rate: 4%
〔巻き取り〕
　熱固定及び熱緩和の後、両端をトリミングし、端部に幅１０ｍｍで押出し加工（ナーリング）を行った後、張力４０ｋｇ／ｍで巻き取った。なお、幅は１．５ｍ、巻長は６３００ｍであった。得られたフィルムロールを、実施例１３の仮支持体とした。 〔Winding〕
After heat setting and heat relaxation, both ends were trimmed, the ends were extruded (knurling) with a width of 10 mm, and then wound at a tension of 40 kg/m. The width was 1.5 m and the winding length was 6300 m. The obtained film roll was used as the temporary support of Example 13.
＜粒子含有層形成用の塗布液２＞
　下記に示す配合で、各成分を混合し、粒子含有層形成用の塗布液２を得た。その塗布液２を調製後塗布までに６μｍフィルター（Ｆ２０、マーレフィルターシステムズ（株）製）でのろ過及び膜脱気（２ｘ６ラジアルフロースーパーフォビック、ポリポア（株）製）を実施した。
・アクリルポリマー（ＡＳ－５６３Ａ、ダイセルファインケム（株）製、固形分２７．５質量％）：１６７部
・ノニオン系界面活性剤（ナロアクティーＣＬ９５、三洋化成工業（株）製、固形分１００質量％）：０．７部
・アニオン系界面活性剤（ラピゾールＡ－９０、日油（株）製、固形分１質量％水希釈）：５５．７部
・カルナバワックス分散物（セロゾール５２４、中京油脂（株）製、固形分３０質量％）：７部
・カルボジイミド化合物（カルボジライトＶ－０２－Ｌ２、日清紡（株）製、固形分１０質量％水希釈）:２０．９部
・マット剤（シリカ粒子：スノーテックスＸＬ、日産化学（株）製、固形分４０質量％）：２．８部
・マット剤（アエロジルＯＸ５０、日本アエロジル（株）製、固形分１０質量％、水分散、メジアン径０．２μｍ）：２．９５部
・水：７４３部 <Coating liquid 2 for forming particle-containing layer>
The components were mixed in the following formulation to obtain a coating liquid 2 for forming a particle-containing layer. After the coating liquid 2 was prepared and before coating, filtration with a 6 μm filter (F20, manufactured by Mare Filter Systems Co., Ltd.) and membrane degassing (2×6 radial flow superphobic, manufactured by Polypore Co., Ltd.) were performed.
-Acrylic polymer (AS-563A, manufactured by Daicel Finechem Ltd., solid content 27.5% by mass): 167 parts-Nonionic surfactant (Naloacty CL95, manufactured by Sanyo Chemical Industry Co., Ltd., solid content 100% by mass) ): 0.7 part-anionic surfactant (rapizole A-90, manufactured by NOF CORPORATION, solid content 1% by weight diluted with water): 55.7 parts-carnauba wax dispersion (Cerosol 524, Chukyo Yushi ( Co., Ltd., solid content 30 mass%): 7 parts Carbodiimide compound (Carbodilite V-02-L2, Nisshinbo Co., Ltd., solid content 10 mass% diluted with water): 20.9 parts Matting agent (silica particles: Snowtex XL, manufactured by Nissan Chemical Industries, Ltd., solid content 40% by mass: 2.8 parts, matting agent (Aerosil OX50, manufactured by Nippon Aerosil Co., Ltd., solid content 10% by mass, water dispersion, median diameter 0.2 μm) ): 2.95 parts, water: 743 parts
＜製造例７＞
　塗布液１の調製において、シリカ粒子を使用しなかった以外は製造例１と同様にして製造例７の仮支持体を得た。 <Production Example 7>
A temporary support of Production Example 7 was obtained in the same manner as in Production Example 1 except that silica particles were not used in the preparation of the coating liquid 1.
＜製造例８＞
　塗布液１のシリカ粒子をスノーテックスＭＰ－２０４０（シリカ粒子、日産化学（株）製、固形分４０質量％、算術平均粒径２００ｎｍ）に変更し、塗布液を塗布する面を両面にし、塗布する際のバーを調整して製膜後膜厚を１００ｎｍに変えた以外は、製造例１と同様にして、製造例８の仮支持体を得た。 <Production Example 8>
The silica particles of the coating liquid 1 are changed to Snowtex MP-2040 (silica particles, manufactured by Nissan Kagaku Co., Ltd., solid content 40 mass%, arithmetic mean particle size 200 nm), and the coating liquid is applied on both sides. A temporary support of Production Example 8 was obtained in the same manner as in Production Example 1 except that the bar at the time of adjustment was adjusted to change the film thickness after film formation to 100 nm.
＜＜ＡＴＨＦの合成＞＞
　国際公開第２０１８／１５５１９３号の段落０１７８に従って合成した。 <<Synthesis of ATHF>>
It was synthesized according to paragraph 0178 of WO2018/155193.
＜＜重合体Ａ－１の合成例＞＞
３つ口フラスコに酢酸イソプロピル（７５．０部）を入れ、窒素雰囲気下において９０℃に昇温した。ＡＴＨＦ（アクリル酸テトラヒドロ－２Ｈ－フラン－２－イル、３０．０部）、ＭＭＡ（メタクリル酸メチル、４０．０部）、ＥＡ（アクリル酸エチル、３０．０部）、Ｖ－６０１（Dimethyl 2,2'-azobis(2-methylpropionate)、富士フイルム和光純薬（株）製、４．０部）、酢酸イソプロピル（７５．０部）を加えた溶液を、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％）を得た。 <<Synthesis Example of Polymer A-1>>
Isopropyl acetate (75.0 parts) was placed in a three-necked flask, and the temperature was raised to 90° C. under a nitrogen atmosphere. ATHF (tetrahydro-2H-furan-2-yl acrylate, 30.0 parts), MMA (methyl methacrylate, 40.0 parts), EA (ethyl acrylate, 30.0 parts), V-601 (Dimethyl 2 A solution containing 2,2'-azobis(2-methylpropionate), FUJIFILM Wako Pure Chemical Industries, Ltd. (4.0 parts) and isopropyl acetate (75.0 parts) was maintained at 90°C ± 2°C. The solution was dropped into the one-necked flask solution over 2 hours. After the dropping was completed, the mixture was stirred at 90° C.±2° C. for 2 hours to obtain a polymer A-1 (solid content concentration 40.0%).
＜＜重合体Ａ－２～Ａ－４の合成例＞＞
　モノマーの種類等を下記表１に示す通りに変更し、その他の条件については、重合体Ａ－１と同様の方法で合成した。重合体Ａ－２～Ａ－４の固形分濃度はそれぞれ、４０質量％とした。
　なお、表１のモノマーの量の単位は、質量％である。 <<Synthesis Examples of Polymers A-2 to A-4>>
The kinds of monomers and the like were changed as shown in Table 1 below, and the other conditions were the same as those for the polymer A-1. The solid content concentration of each of the polymers A-2 to A-4 was 40% by mass.
The unit of the amount of the monomer in Table 1 is% by mass.
Figure JPOXMLDOC01-appb-T000005
 
Figure JPOXMLDOC01-appb-T000005
 
　上述した以外の表１に記載の略語の詳細を、以下に示す。
　ＡＡ：アクリル酸
　ＣＨＡ：アクリル酸シクロヘキシル
　ＰＭＰＭＡ：メタクリル酸１，２，２，６，６－ペンタメチル－４－ピペリジル Details of the abbreviations described in Table 1 other than the above are shown below.
AA: Acrylic acid CHA: Cyclohexyl acrylate PMPMA: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate
＜感光性樹脂組成物１～７の調製＞
　下記表２に示す固形分比（なお、表２における各成分の数値の単位は、質量部である。）となるように、重合体、光酸発生剤、塩基性化合物、添加剤、及び、界面活性剤をプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）に固形分濃度１０質量％になるように溶解混合し、孔径０．２μｍのポリテトラフルオロエチレン製フィルターで濾過して、感光性樹脂組成物１～７をそれぞれ得た。 <Preparation of Photosensitive Resin Compositions 1 to 7>
The polymer, the photoacid generator, the basic compound, the additive, and the solid content ratio shown in Table 2 below (where the unit of the numerical value of each component in Table 2 is parts by mass), The surfactant was dissolved and mixed in propylene glycol monomethyl ether acetate (PGMEA) so that the solid content concentration was 10% by mass, and the mixture was filtered through a polytetrafluoroethylene filter having a pore size of 0.2 μm to obtain a photosensitive resin composition 1 to 7 were obtained respectively.
Figure JPOXMLDOC01-appb-T000006
 
Figure JPOXMLDOC01-appb-T000006
 
　上述した以外の表２に記載の略語の詳細を、以下に示す。
　Ｂ－１：下記化合物
　Ｂ－２：下記化合物
　Ｃ－１：１，２，３－ベンゾトリアゾール（東京化成工業（株）製）
　Ｃ－２：Ｎ－シクロヘキシル－Ｎ’－［２－（４－モルホリニル）エチル］チオ尿素（ＣＭＴＵ、東洋化成工業（株）製）
　Ｅ－１：Ｆ－５５４、パーフルオロアルキル基含有ノニオン系界面活性剤（ＤＩＣ（株）製）
　Ｆ－１：９，１０－ジブトキシアントラセン Details of the abbreviations described in Table 2 other than the above are shown below.
B-1: The following compound B-2: The following compound C-1: 1,2,3-benzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
C-2: N-cyclohexyl-N'-[2-(4-morpholinyl)ethyl]thiourea (CMTU, manufactured by Toyo Kasei Co., Ltd.)
E-1: F-554, perfluoroalkyl group-containing nonionic surfactant (manufactured by DIC Corporation)
F-1: 9,10-dibutoxyanthracene
Figure JPOXMLDOC01-appb-C000007
 
Figure JPOXMLDOC01-appb-C000007
 
（実施例１）
　製造例１で作製した仮支持体の粒子含有層を有する面とは反対側に、感光性樹脂組成物１を、スリット状ノズルを用いて乾燥膜厚が３．０μｍとなるように塗布した。その後、１００℃のコンベクションオーブンで２分間乾燥させ、最後に保護フィルムとしてポリエチレンフィルム（トレデガー社製、ＯＳＭ－Ｎ）を圧着して実施例１の感光性転写材料（ドライフィルムレジスト）を作製した。 (Example 1)
The photosensitive resin composition 1 was applied to the side opposite to the surface having the particle-containing layer of the temporary support produced in Production Example 1 using a slit nozzle so that the dry film thickness was 3.0 μm. Then, it was dried in a convection oven at 100° C. for 2 minutes, and finally a polyethylene film (OSM-N, manufactured by Tredegar Co., Ltd.) was pressure-bonded as a protective film to prepare a photosensitive transfer material (dry film resist) of Example 1.
（実施例２）
＜中間層用組成物１の作製＞
　下記組成となるように各成分を混合して中間層用組成物１を作製した。 (Example 2)
<Preparation of Composition 1 for Intermediate Layer>
Each component was mixed so as to have the following composition to prepare a composition 1 for intermediate layer.
－組成－
・蒸留水：３７．２部
・メタノール：５５．８部
・ヒドロキシプロピルセルロース（商品名：ＨＰＣ－ＳＳＬ、日本曹達（株）製）：７．０部 -composition-
-Distilled water: 37.2 parts-Methanol: 55.8 parts-Hydroxypropyl cellulose (trade name: HPC-SSL, manufactured by Nippon Soda Co., Ltd.): 7.0 parts
　製造例１で作製した仮支持体の上に、中間層用組成物１を乾燥膜厚２．４μｍとなるようにスリットコートし、１００℃のコンベクションオーブンで２分間乾燥させた。次に感光性樹脂組成物１を、この中間層上に、スリット状ノズルを用いて乾燥膜厚が３．０μｍとなるように塗布した。その後、１００℃のコンベクションオーブンで２分間乾燥させ、最後に保護フィルムとしてポリエチレンフィルム（トレデガー社製、ＯＳＭ－Ｎ）を圧着して実施例２の感光性転写材料を作製した。 The composition 1 for intermediate layer was slit-coated on the temporary support prepared in Production Example 1 to a dry film thickness of 2.4 μm, and dried in a convection oven at 100° C. for 2 minutes. Next, the photosensitive resin composition 1 was applied onto this intermediate layer using a slit nozzle so that the dry film thickness was 3.0 μm. Then, it was dried in a convection oven at 100° C. for 2 minutes, and finally a polyethylene film (OSM-N manufactured by Tredegar Co., Ltd.) was pressure-bonded as a protective film to prepare a photosensitive transfer material of Example 2.
（実施例３～６、及び、１３）
　製造例１で作製した仮支持体の代わりに、製造例２～６で作製した仮支持体を用いた以外は、実施例２と同様にして、実施例３～６、及び、実施例１３の感光性転写材料をそれぞれ作製した。 (Examples 3 to 6 and 13)
In the same manner as in Example 2 except that the temporary supports prepared in Production Examples 2 to 6 were used in place of the temporary supports prepared in Production Example 1, the same processes as in Examples 3 to 6 and Example 13 were performed. Each photosensitive transfer material was prepared.
（実施例７）
　製造例１で作製した仮支持体の代わりに、厚さ１６μｍのポリエステルフィルム１６ＫＳ４０（東レ（株）製）を用いた以外は、実施例２と同様にして、実施例７の感光性転写材料を作製した。
　なお、ポリエステルフィルム１６ＫＳ４０は、フィルムの両面に粒子含有層を有するものであり、上記中間層等が形成される面における粒子含有層に含まれる粒子の算術平均粒径は５０ｎｍであり、他方の面における粒子含有層に含まれる粒子の算術平均粒径は４００ｎｍの粒子であった。 (Example 7)
The photosensitive transfer material of Example 7 was prepared in the same manner as in Example 2 except that a 16 μm thick polyester film 16KS40 (manufactured by Toray Industries, Inc.) was used instead of the temporary support prepared in Production Example 1. It was made.
The polyester film 16KS40 has a particle-containing layer on both sides of the film, and the arithmetic average particle diameter of the particles contained in the particle-containing layer on the surface on which the intermediate layer and the like are formed is 50 nm and the other surface. The arithmetic average particle diameter of the particles contained in the particle-containing layer was 400 nm.
（実施例８～１２）
　感光性樹脂組成物１の代わりに、上記感光性樹脂組成物２～６を用いたこと以外は、実施例２と同様にして、実施例８～１２の感光性転写材料をそれぞれ作製した。 (Examples 8 to 12)
Photosensitive transfer materials of Examples 8 to 12 were produced in the same manner as in Example 2 except that the above-mentioned photosensitive resin compositions 2 to 6 were used instead of the photosensitive resin composition 1.
（実施例１４）
　製造例１で作製した仮支持体の代わりに、厚さ１６μｍのポリエステルフィルム　コスモシャインＡ－１５１７（東洋紡（株）製）を用いた以外は、実施例２と同様にして、実施例１４の感光性転写材料を作製した。
　なお、ポリエステルフィルム　コスモシャインＡ－１５１７は、フィルムの片面に粒子含有層を有するものである。 (Example 14)
The sensitization of Example 14 was performed in the same manner as in Example 2 except that a polyester film having a thickness of 16 μm, Cosmoshine A-1517 (manufactured by Toyobo Co., Ltd.) was used in place of the temporary support produced in Production Example 1. A sex transfer material was prepared.
The polyester film Cosmoshine A-1517 has a particle-containing layer on one surface of the film.
（比較例１）
　製造例１で作製した仮支持体の代わりに、粒子含有層のない製造例７で作製した仮支持体を用いた以外は、実施例２と同様にして、比較例１の感光性転写材料を得た。 (Comparative Example 1)
The photosensitive transfer material of Comparative Example 1 was prepared in the same manner as in Example 2 except that the temporary support prepared in Production Example 7 having no particle-containing layer was used in place of the temporary support prepared in Production Example 1. Obtained.
（比較例２）
　製造例１で作製した仮支持体の代わりに、製造例８で作製した仮支持体を用いた以外は、実施例２と同様にして、比較例２の感光性転写材料を得た。 (Comparative example 2)
A photosensitive transfer material of Comparative Example 2 was obtained in the same manner as in Example 2 except that the temporary support produced in Production Example 8 was used in place of the temporary support produced in Production Example 1.
＜エッジラフネス評価＞
〔樹脂パターン及び回路配線の製造〕
　各実施例又は比較例の感光性転写材料から保護フィルムを剥離し、銅層を片面上に有する回路形成基板上に上記保護フィルムを剥離した感光性転写材料を感光性樹脂層と銅層が接触するように１００℃、４ｍ／ｍｉｎの速度、線圧０．６ＭＰａの条件でラミネートし、銅層上に感光性樹脂層、（中間層を有する場合は中間層）、及び、仮支持体、が積層した積層体を作製した。
　この積層体に対し、仮支持体を剥離せずに、線幅６μｍのラインアンドスペース配線パターン（開口部：遮光部の幅比は１：１）を設けたフォトマスクを用いてコンタクトパターン露光を行った。露光にはｉ線（３６５ｎｍ）を露光主波長とする高圧水銀灯を用いた。
　露光後の積層体から仮支持体を剥離後、２５℃の１．０質量％炭酸ナトリウム水溶液を用い、シャワー現像で４０秒間現像し、水洗を行って、樹脂パターンを得た。
　次いで銅エッチング液（関東化学（株）製Ｃｕ－０２）を用いて銅層をエッチングし、銅配線基板を得た。得られた回路配線を、各実施例又は比較例の回路配線とした。 <Evaluation of edge roughness>
[Manufacture of resin pattern and circuit wiring]
The protective film is peeled from the photosensitive transfer material of each Example or Comparative Example, and the photosensitive resin material and the copper layer are in contact with the photosensitive transfer material obtained by peeling the protective film on the circuit forming substrate having a copper layer on one surface. So that the photosensitive resin layer, the intermediate layer in the case of having an intermediate layer, and the temporary support are laminated on the copper layer under the conditions of 100° C., a speed of 4 m/min, and a linear pressure of 0.6 MPa. A laminated body was prepared.
This laminated body is exposed to a contact pattern using a photomask provided with a line-and-space wiring pattern having a line width of 6 μm (width ratio of opening:light-shielding portion is 1:1) without peeling the temporary support. went. For the exposure, a high pressure mercury lamp having an i-line (365 nm) as a main exposure wavelength was used.
After peeling the temporary support from the laminated body after exposure, it was developed by shower development for 40 seconds using a 1.0% by mass sodium carbonate aqueous solution at 25° C., and washed with water to obtain a resin pattern.
Then, the copper layer was etched using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Inc.) to obtain a copper wiring board. The obtained circuit wiring was used as the circuit wiring of each Example or Comparative Example.
〔パターン直線性（ＬＷＲ）〕
　得られた各実施例又は比較例の回路配線を有する回路配線基板のラインアンドスペースパターン、及び、感光性樹脂層から形成された樹脂パターンについて、アトランダムに選んだ箇所のパターン幅を２０箇所測定した。得られた線幅データから標準偏差σを算出し、標準偏差σを３倍した値をＬＷＲ（Ｌｉｎｅ　Ｗｉｄｔｈ　Ｒｏｕｇｈｎｅｓｓ）と定義し、パターン直線性の指標とした。
　ＬＷＲは定義上、小さいほど線幅変動が小さいこととなり好ましい。６μｍ線幅のパターンに対しては、ＬＷＲの値によって以下のように評価される。ＬＷＲの値が小さいほどパターン直線性に優れるといえる。また、パターン直線性に優れるほど、線幅のぎざつき（エッジラフネス）に優れるともいえる。評価Ａ～Ｃであることが好ましく、評価Ａ又はＢであることがより好ましく、評価Ａであることが特に好ましい。
－評価基準－
　　Ａ：ＬＷＲ＜３００ｎｍ：回路配線基板として非常に好ましい。
　　Ｂ：３００ｎｍ≦ＬＷＲ＜５００ｎｍ：回路配線基板として好ましい。
　　Ｃ：５００ｎｍ≦ＬＷＲ＜７００ｎｍ：回路配線基板として使用可能。
　　Ｄ：７００ｎｍ≦ＬＷＲ：線幅変動が大きく回路不良に繋がり、好ましくない。 [Pattern linearity (LWR)]
For the line and space pattern of the circuit wiring board having the circuit wiring of each of the obtained Examples or Comparative Examples and the resin pattern formed from the photosensitive resin layer, the pattern width of 20 randomly selected locations was measured. did. A standard deviation σ was calculated from the obtained line width data, and a value obtained by multiplying the standard deviation σ by 3 was defined as LWR (Line Width Roughness) and used as an index of pattern linearity.
By definition, the smaller LWR is, the smaller the line width variation is, which is preferable. For a pattern having a line width of 6 μm, the value of LWR is evaluated as follows. It can be said that the smaller the value of LWR, the better the pattern linearity. It can also be said that the more excellent the pattern linearity, the more excellent the line width is jagged (edge roughness). The evaluations A to C are preferable, the evaluations A and B are more preferable, and the evaluation A is particularly preferable.
-Evaluation criteria-
A: LWR<300 nm: Very preferable as a circuit wiring board.
B: 300 nm≦LWR<500 nm: preferable as a circuit wiring board.
C: 500 nm≦LWR<700 nm: Can be used as a circuit wiring board.
D: 700 nm≦LWR: Large variation in line width leads to circuit failure, which is not preferable.
＜ロールツーロール適性（搬送時のシワ発生抑制性）＞
　作製した感光性転写材料から保護フィルムを剥離したものを、下記の条件に従って、図４のように感光性転写材料のラミネート方向とは逆方向に引張力（感光性転写材料テンション）、銅層付基材にはラミネート方向（搬送方向）とは逆方向に引張力（銅層付基材テンション）をかけ、１００℃、４ｍ／ｍｉｎ、線圧０．６ＭＰａの条件で銅層付基材の両面にラミネートした。
　　銅層付基材テンション：１２５Ｎ／ｍ
　　感光性転写材料テンション：７５Ｎ／ｍ
　図４は、実施例において使用したラミネート装置の模式断面図である。
　図４に記載のラミネート装置２０においては、銅層付基材２２の両面にそれぞれ、保護フィルムを剥離した感光性転写材料２４ａ及び２４ｂを一対のラミネートロール２６によりラミネートし、積層体２８が作製され、巻き取りロール３０により巻き取る。また、保護フィルムを剥離した感光性転写材料２４ａ及び２４ｂにはそれぞれ、ラミネート方向とは逆方向Ｔ１及びＴ２に感光性転写材料テンションがかかっており、銅層付基材２２にはラミネート方向と逆方向Ｔ３に銅層付基材テンションがかかっている。感光性転写材料２４ａ及び２４ｂは、それぞれ搬送ロール３２ａ及び３２ｂにより搬送され、ラミネート後の積層体は搬送ロール３２ｃ及び搬送ロール３２ｄによって搬送される。
　得られた積層体を平面に置き、平面からの浮き（周囲よりも盛り上がった部分）の高さをシワの高さとして測定した。
　　Ａ：シワの高さが２ｍｍ未満
　　Ｂ：シワの高さが２ｍｍ以上４ｍｍ未満
　　Ｃ：シワの高さが４ｍｍ以上６ｍｍ未満
　　Ｄ：シワの高さが６ｍｍ以上
　評価Ａ又はＢであることが好ましく、評価Ａであることが特に好ましい。 <Roll-to-roll suitability (wrinkle generation control during transport)>
After peeling off the protective film from the prepared photosensitive transfer material, a tensile force (photosensitive transfer material tension) and a copper layer were applied in the direction opposite to the laminating direction of the photosensitive transfer material as shown in FIG. 4 according to the following conditions. A tensile force (base material tension with copper layer) is applied to the base material in the direction opposite to the laminating direction (conveying direction), and both sides of the base material with copper layer are applied at 100° C., 4 m/min, and linear pressure of 0.6 MPa Laminated to.
Base material tension with copper layer: 125 N/m
Photosensitive transfer material tension: 75 N/m
FIG. 4 is a schematic cross-sectional view of the laminating apparatus used in the examples.
In the laminating apparatus 20 illustrated in FIG. 4, the photosensitive transfer materials 24a and 24b from which the protective film has been peeled off are laminated on both sides of the copper layer-attached base material 22 by a pair of laminating rolls 26 to form a laminate 28. It is wound by the winding roll 30. Further, the photosensitive transfer materials 24a and 24b from which the protective film has been peeled are respectively subjected to the photosensitive transfer material tensions in the directions T1 and T2 opposite to the laminating direction, and the copper layer base material 22 is opposite to the laminating direction. The substrate tension with the copper layer is applied in the direction T3. The photosensitive transfer materials 24a and 24b are transported by the transport rolls 32a and 32b, respectively, and the laminated body after lamination is transported by the transport rolls 32c and 32d.
The obtained laminated body was placed on a flat surface, and the height of the floating (the portion raised from the surroundings) from the flat surface was measured as the height of wrinkles.
A: Wrinkle height is less than 2 mm B: Wrinkle height is 2 mm or more and less than 4 mm C: Wrinkle height is 4 mm or more and less than 6 mm D: Wrinkle height is 6 mm or more Evaluation A or B is preferable, Evaluation A is particularly preferable.
＜露光後の経時安定性（ＰＥＤ）＞
　露光後の経時安定性（Ｐｏｓｔ　Ｅｘｐｏｓｕｒｅ　Ｄｅｌａｙ　ｓｔａｂｉｌｉｔｙ：ＰＥＤ）を以下のように評価した。
　樹脂パターンの製造において、パターン露光したロール状積層体を、温度２３℃、湿度５５％の環境下で３時間、又は、２４時間経時させた。以下、「ＰＥＤ」の後に記載した時間は、露光後、現像開始までの経時時間を意味する。その後、上記樹脂パターンの製造に従って現像を行い、樹脂パターンを形成した。得られた樹脂パターンの解像度パターンを光学顕微鏡にて観察評価した。６μｍラインアンドスペースの解像度パターンの線幅を測定した。
　ＰＥＤ３時間で形成した樹脂パターンの線幅に対するＰＥＤ２４時間で形成した樹脂パターンの線幅の変化量を評価した。評価Ａ～Ｃであることが好ましく、評価Ａ又はＢであることがより好ましく、評価Ａであることが特に好ましい。
　　Ａ：線幅の変動値が１．０μｍ未満
　　Ｂ：線幅の変動値が１．０μｍ以上１．５μｍ未満
　　Ｃ：線幅の変動値が１．５μｍ以上２．０μｍ未満
　　Ｄ：線幅の変動値が２．０μｍ以上３．０μｍ未満
　　Ｅ：線幅の変動値が３．０μｍ以上 <Stability after exposure (PED)>
The stability over time after exposure (Post Exposure Delay stability: PED) was evaluated as follows.
In the production of the resin pattern, the pattern-exposed roll-shaped laminate was aged for 3 hours or 24 hours in an environment of a temperature of 23° C. and a humidity of 55%. Hereinafter, the time described after “PED” means the elapsed time from the exposure to the start of development. Then, development was performed according to the production of the resin pattern to form a resin pattern. The resolution pattern of the obtained resin pattern was observed and evaluated with an optical microscope. The line width of a 6 μm line and space resolution pattern was measured.
The amount of change in the line width of the resin pattern formed in 24 hours of PED was evaluated with respect to the line width of the resin pattern formed in 3 hours of PED. The evaluations A to C are preferable, the evaluations A and B are more preferable, and the evaluation A is particularly preferable.
A: Variation of line width is less than 1.0 μm B: Variation of line width is 1.0 μm or more and less than 1.5 μm C: Variation of line width is 1.5 μm or more and less than 2.0 μm D: Variation of line width Value is 2.0 μm or more and less than 3.0 μm E: Line width fluctuation value is 3.0 μm or more
　評価結果をまとめて表３に示す。 Table 3 summarizes the evaluation results.
Figure JPOXMLDOC01-appb-T000008
 
Figure JPOXMLDOC01-appb-T000008
 
　上記表３より、実施例１～１４の感光性転写材料は、搬送時のシワ発生抑制性及びＰＥＤのいずれの評価項目においてもＣ以上の評価であり、比較例１又は２の感光性転写材料と比べ、搬送時のシワ発生抑制性、及び、露光後の経時安定性を両立していることがわかる。
　また、上記表３より、実施例１～１４の感光性転写材料は、得られるパターンの直線性、及び、作製した回路配線パターンの直線性にも優れることがわかる。 From Table 3 above, the photosensitive transfer materials of Examples 1 to 14 were evaluated as C or higher in any of the evaluation items of wrinkle generation suppressing property during transport and PED, and the photosensitive transfer materials of Comparative Examples 1 and 2 were obtained. Compared with the above, it can be seen that both the suppression of wrinkle generation during transport and the stability over time after exposure are achieved.
Further, it can be seen from Table 3 above that the photosensitive transfer materials of Examples 1 to 14 are excellent in the linearity of the obtained patterns and the linearity of the circuit wiring patterns produced.
（実施例１０１）
　１００μｍ厚ＰＥＴ基材上に、第２層の導電層としてＩＴＯをスパッタリングで１５０ｎｍ厚にて成膜し、その上に第１層の導電層として銅を真空蒸着法で２００ｎｍ厚にて成膜して、回路形成用基板とした。
　銅層上に実施例１で得られた感光性転写材料を、保護フィルムを剥離して、基板に貼り合わせて（ラミネートロール温度１００℃、線圧０．８ＭＰａ、線速度３．０ｍ／ｍｉｎ．）、積層体とした。得られた積層体を、仮支持体を剥離せずに一方向に導電層パッドが連結された構成を持つ図２に示すパターンＡを設けたフォトマスクを用いてコンタクトパターン露光した。露光にはｉ線（３６５ｎｍ）を露光主波長とする高圧水銀灯を用いた。
　その後仮支持体を剥離し、現像、水洗を行ってパターンＡを得た。次いで銅エッチング液（関東化学（株）製Ｃｕ－０２）を用いて銅層をエッチングした後、ＩＴＯエッチング液（関東化学（株）製ＩＴＯ－０２）を用いてＩＴＯ層をエッチングすることで、銅とＩＴＯが共にパターンＡで描画された基板を得た。
　次いで、残存しているレジスト上に保護層として実施例１と同様の仮支持体をラミネートした。この状態で、アライメントを合わせ、パターンＢの開口部を設けたフォトマスクを用いてパターン露光し、仮支持体を剥離した後、現像、水洗を行った。その後、Ｃｕ－０２を用いて銅配線をエッチングし、残った感光性樹脂層を剥離液（関東化学（株）製ＫＰ－３０１）を用いて剥離し、回路配線基板を得た。
　得られた回路配線基板を、顕微鏡で観察したところ、剥がれや欠けなどは無く、きれいなパターンであった。 (Example 101)
On a PET substrate having a thickness of 100 μm, ITO was deposited as a second conductive layer to a thickness of 150 nm by sputtering, and copper was deposited thereon as a first conductive layer to a thickness of 200 nm by a vacuum deposition method. And used as a circuit forming substrate.
On the copper layer, the photosensitive transfer material obtained in Example 1 was peeled off from the protective film and bonded to a substrate (laminating roll temperature 100° C., linear pressure 0.8 MPa, linear velocity 3.0 m/min. ) And a laminated body. The obtained laminated body was subjected to contact pattern exposure using a photomask provided with a pattern A shown in FIG. 2 having a configuration in which conductive layer pads were connected in one direction without peeling off the temporary support. For the exposure, a high pressure mercury lamp having an i-line (365 nm) as a main exposure wavelength was used.
Thereafter, the temporary support was peeled off, developed and washed with water to obtain pattern A. Then, after etching the copper layer using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Inc.), the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.). A substrate in which both copper and ITO were drawn in the pattern A was obtained.
Then, the same temporary support as in Example 1 was laminated as a protective layer on the remaining resist. In this state, alignment was performed, pattern exposure was performed using a photomask provided with an opening for pattern B, and the temporary support was peeled off, followed by development and washing with water. Then, the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was peeled off using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board.
When the obtained circuit wiring board was observed with a microscope, there was no peeling or chipping, and it was a clean pattern.
（実施例１０２）
　実施例１０１と同様にして、パターンＡで描画された基板を得た後に、残存しているレジスト上に、実施例１で得られた感光性転写材料を、保護フィルムを剥離して、実施例１０１と同様の条件で再度貼り合わせた。アライメントを合わせた状態で、仮支持体を剥離せずにパターンＢの開口部を設けたフォトマスクを用いてパターン露光し、その後仮支持体を剥離し、現像、水洗を行ってパターンＢを得た。次いで、実施例１０１と同様の条件で銅配線をエッチング、残った感光性樹脂層を剥離し、導電パターンを有する回路配線基板を得た。
　得られた回路配線基板を、顕微鏡で観察したところ、剥がれ、欠けなどは無く、きれいなパターンであった。 (Example 102)
In the same manner as in Example 101, after obtaining the substrate on which the pattern A was drawn, the protective film was peeled off the photosensitive transfer material obtained in Example 1 onto the remaining resist to obtain the example. The pieces were reattached under the same conditions as 101. In the aligned state, pattern exposure is performed using a photomask provided with an opening for pattern B without peeling the temporary support, and then the temporary support is peeled off, and development and washing are performed to obtain pattern B. It was Then, the copper wiring was etched under the same conditions as in Example 101, and the remaining photosensitive resin layer was peeled off to obtain a circuit wiring board having a conductive pattern.
When the obtained circuit wiring board was observed with a microscope, there was no peeling or chipping, and it was a clean pattern.
（実施例１０３）
　感光性樹脂組成物１の代わりに感光性樹脂組成物７を用い、露光時の高圧水銀灯の代わりにレーザー光線（露光主波長：４０５ｎｍ）を用いたこと以外は、実施例１０１と同様にして回路配線基板を得た。
　得られた回路配線基板を、顕微鏡で観察したところ、剥がれ、欠けなどは無く、きれいなパターンであった。 (Example 103)
Circuit wiring in the same manner as in Example 101 except that the photosensitive resin composition 7 was used in place of the photosensitive resin composition 1, and a laser beam (exposure main wavelength: 405 nm) was used in place of the high-pressure mercury lamp during exposure. A substrate was obtained.
When the obtained circuit wiring board was observed with a microscope, there was no peeling or chipping, and it was a clean pattern.
　２０１９年１月２９日に出願された日本国特許出願２０１９－１２９８２号の開示及び２０１９年６月２５日に出願された日本国特許出願２０１９－１１６９５２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、および技術規格は、個々の文献、特許出願、およ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、本明細書中に参照により取り込まれる。 The disclosures of Japanese Patent Application No. 2019-129282 filed on January 29, 2019 and Japanese Patent Application No. 2019-116952 filed on June 25, 2019 are hereby incorporated by reference in their entirety. It is incorporated into the calligraphy.
All publications, patent applications, and technical standards mentioned herein are to the same extent as if each individual publication, patent application, and technical standard were specifically and individually noted to be incorporated by reference, Incorporated herein by reference.

Claims (16)

  1. 　仮支持体と、
    　前記仮支持体上に設けられた感光性樹脂層とを有し、
    　前記仮支持体が、粒子を含有する粒子含有層を有し、
    　前記仮支持体の感光性樹脂層を有する側の面とは反対側の面の表面粗さＲａが、０．０２μｍ～０．２０μｍであり、
    　前記感光性樹脂層が、酸分解性基で保護された酸基を有する構成単位を含有する重合体、及び、光酸発生剤を含有する
    　感光性転写材料。     A temporary support,
    A photosensitive resin layer provided on the temporary support,
    The temporary support has a particle-containing layer containing particles,
    The surface roughness Ra of the surface of the temporary support opposite to the surface having the photosensitive resin layer is 0.02 μm to 0.20 μm,
    A photosensitive transfer material, wherein the photosensitive resin layer contains a polymer containing a structural unit having an acid group protected by an acid-decomposable group, and a photo-acid generator.
  2. 　前記仮支持体のヘーズ値が、０．２％以下である請求項１に記載の感光性転写材料。 The photosensitive transfer material according to claim 1, wherein the temporary support has a haze value of 0.2% or less.
  3. 　前記粒子含有層の厚さが、１０ｎｍ～１００ｎｍである請求項１又は請求項２に記載の感光性転写材料。 The photosensitive transfer material according to claim 1 or 2, wherein the particle-containing layer has a thickness of 10 nm to 100 nm.
  4. 　前記粒子含有層が、前記仮支持体の片面のみに設けられている請求項１～請求項３のいずれか１項に記載の感光性転写材料。 The photosensitive transfer material according to any one of claims 1 to 3, wherein the particle-containing layer is provided only on one surface of the temporary support.
  5. 　前記粒子の算術平均粒径が、１００ｎｍ未満である請求項１～請求項４のいずれか１項に記載の感光性転写材料。 The photosensitive transfer material according to any one of claims 1 to 4, wherein the arithmetic average particle diameter of the particles is less than 100 nm.
  6. 　前記仮支持体の感光性樹脂層を有する側の面とは反対側の面の表面粗さＲａが、０．０５μｍ～０．１０μｍである請求項１～請求項５のいずれか１項に記載の感光性転写材料。 The surface roughness Ra of the surface of the temporary support opposite to the surface having the photosensitive resin layer is 0.05 μm to 0.10 μm. Photosensitive transfer material.
  7. 　前記仮支持体の厚さが、１８μｍを超え３０μｍ以下である請求項１～請求項６のいずれか１項に記載の感光性転写材料。 The photosensitive transfer material according to any one of claims 1 to 6, wherein the temporary support has a thickness of more than 18 µm and 30 µm or less.
  8. 　前記仮支持体が、ポリエステル樹脂を含む請求項１～請求項７のいずれか１項に記載の感光性転写材料。 The photosensitive transfer material according to any one of claims 1 to 7, wherein the temporary support contains a polyester resin.
  9. 　前記酸分解性基で保護された酸基が、アセタール型酸分解性基で保護されたカルボキシ基である請求項１～請求項８のいずれか１項に記載の感光性転写材料。 The photosensitive transfer material according to any one of claims 1 to 8, wherein the acid group protected by the acid-decomposable group is a carboxy group protected by an acetal-type acid-decomposable group.
  10. 　前記重合体の酸価が、１０ｍｇＫＯＨ／ｇ以下である請求項１～請求項９のいずれか１項に記載の感光性転写材料。 The photosensitive transfer material according to any one of claims 1 to 9, wherein the acid value of the polymer is 10 mgKOH/g or less.
  11. 　前記光酸発生剤が、炭素数１～４のアルキルスルホン酸を発生する光酸発生剤を含む請求項１～請求項１０のいずれか１項に記載の感光性転写材料。 The photosensitive transfer material according to any one of claims 1 to 10, wherein the photo-acid generator contains a photo-acid generator that generates an alkylsulfonic acid having 1 to 4 carbon atoms.
  12. 　請求項１～請求項１１のいずれか１項に記載の感光性転写材料における前記仮支持体に対して感光性樹脂層を有する側の最外層を基板に接触させて貼り合わせる工程と、
    　前記感光性樹脂層をパターン露光する工程と、
    　露光された前記感光性樹脂層を現像して樹脂パターンを形成する工程と、をこの順に含む
    　樹脂パターンの製造方法。     A step of bringing the outermost layer on the side having the photosensitive resin layer into contact with the substrate with respect to the temporary support in the photosensitive transfer material according to any one of claims 1 to 11, and bonding the substrate.
    A step of pattern-exposing the photosensitive resin layer,
    And a step of developing the exposed photosensitive resin layer to form a resin pattern in this order.
  13. 　請求項１～請求項１１のいずれか１項に記載の感光性転写材料における前記仮支持体に対して前記感光性樹脂層を有する側の最外層を、導電層を有する基板に接触させて貼り合わせる工程と、
    　前記感光性樹脂層をパターン露光する工程と、
    　露光された前記感光性樹脂層を現像して樹脂パターンを形成する工程と、
    　前記樹脂パターンが配置されていない領域における前記導電層をエッチング処理する工程と、をこの順に含む
    　回路配線の製造方法。     The outermost layer on the side having the photosensitive resin layer with respect to the temporary support in the photosensitive transfer material according to any one of claims 1 to 11 is brought into contact with a substrate having a conductive layer and attached. The process of matching
    A step of pattern-exposing the photosensitive resin layer,
    A step of developing the exposed photosensitive resin layer to form a resin pattern,
    And a step of etching the conductive layer in a region where the resin pattern is not arranged, in this order.
  14. 　請求項１～請求項１１のいずれか１項に記載の感光性転写材料における前記仮支持体に対して前記感光性樹脂層を有する側の最外層を、導電層を有する基板に接触させて貼り合わせる工程と、
    　前記感光性樹脂層をパターン露光する工程と、
    　露光された前記感光性樹脂層を現像して樹脂パターンを形成する工程と、
    　前記樹脂パターンが配置されていない領域における前記導電層をエッチング処理する工程と、をこの順に含む
    　タッチパネルの製造方法。     The outermost layer on the side having the photosensitive resin layer with respect to the temporary support in the photosensitive transfer material according to any one of claims 1 to 11 is brought into contact with a substrate having a conductive layer and attached. The process of matching
    A step of pattern-exposing the photosensitive resin layer,
    A step of developing the exposed photosensitive resin layer to form a resin pattern,
    And a step of etching the conductive layer in a region where the resin pattern is not arranged, in this order.
  15. 　粒子を含有する粒子含有層を少なくとも片面に有し、
    　ヘーズ値が、０．２％以下であり、
    　前記粒子含有層を有する側の面の表面粗さＲａが、０．０２μｍ～０．２０μｍである
    　フィルム。     Having a particle-containing layer containing particles on at least one side,
    Haze value is 0.2% or less,
    A film having a surface roughness Ra of the side having the particle-containing layer of 0.02 μm to 0.20 μm.
  16. 　第一延伸方向に延伸された一軸延伸フィルム上に、粒子を含有する層を形成する工程、及び、
    　前記一軸延伸フィルム及び前記一軸延伸フィルム上に形成された前記粒子を含有する層を、前記一軸延伸フィルムにおけるフィルム面に沿って前記第一延伸方向と直交する第二延伸方向に延伸する工程を含む請求項１５に記載のフィルムの製造方法。     On the uniaxially stretched film stretched in the first stretching direction, the step of forming a layer containing particles, and
    A step of stretching a layer containing the particles formed on the uniaxially stretched film and the uniaxially stretched film in a second stretching direction orthogonal to the first stretching direction along a film surface of the uniaxially stretched film. The method for producing a film according to claim 15.
PCT/JP2020/000277 2019-01-29 2020-01-08 Photosensitive transfer material, resin pattern production method, circuit wiring production method, touch panel production method, and, film and production method therefor WO2020158316A1 (en)

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