WO2022102101A1 - Élément photosensible, procédé de production d'article durci, procédé de production d'un motif d'article durci, et procédé de production de carte de câblage - Google Patents

Élément photosensible, procédé de production d'article durci, procédé de production d'un motif d'article durci, et procédé de production de carte de câblage Download PDF

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Publication number
WO2022102101A1
WO2022102101A1 PCT/JP2020/042510 JP2020042510W WO2022102101A1 WO 2022102101 A1 WO2022102101 A1 WO 2022102101A1 JP 2020042510 W JP2020042510 W JP 2020042510W WO 2022102101 A1 WO2022102101 A1 WO 2022102101A1
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Prior art keywords
mass
support film
less
cured product
film
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PCT/JP2020/042510
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English (en)
Japanese (ja)
Inventor
壮和 粂
剛 黒澤
陽介 賀口
健一 岩下
真生 成田
哲也 加藤
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昭和電工マテリアルズ株式会社
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Application filed by 昭和電工マテリアルズ株式会社 filed Critical 昭和電工マテリアルズ株式会社
Priority to PCT/JP2020/042510 priority Critical patent/WO2022102101A1/fr
Priority to CN202180038977.0A priority patent/CN116830037A/zh
Priority to PCT/JP2021/041406 priority patent/WO2022102675A1/fr
Priority to KR1020227038217A priority patent/KR20230107474A/ko
Priority to JP2022561974A priority patent/JPWO2022102675A1/ja
Priority to TW110141999A priority patent/TW202225837A/zh
Publication of WO2022102101A1 publication Critical patent/WO2022102101A1/fr

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    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/14—Esters having no free carboxylic acid groups, e.g. dialkyl maleates or fumarates
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1545—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material

Definitions

  • This disclosure relates to a photosensitive element, a method for manufacturing a cured product, a method for manufacturing a cured product pattern, a method for manufacturing a wiring board, and the like.
  • a resist material used for etching, plating, etc. in the field of manufacturing a wiring board for example, a printed wiring board
  • a layer made of a support film and a photosensitive resin composition hereinafter, "photosensitive layer”
  • photosensitive layer a photosensitive resin composition
  • a photosensitive element composed of a protective film is widely used.
  • the wiring board is manufactured as follows, for example. First, the protective film of the photosensitive element is peeled off from the photosensitive layer, and then the photosensitive layer is laminated on the substrate. Next, after pattern exposure is applied to the photosensitive layer, the unexposed portion is removed with a developing solution to form a resist (resist pattern). Then, a wiring board is formed by performing an etching treatment or a plating treatment via this resist.
  • a support film having a specific haze value, a support film having a specific lubricant particle size, and the like are known (see, for example, Patent Documents 1 and 2 below).
  • One aspect of the present disclosure is to provide a photosensitive element capable of suppressing the occurrence of resist defects.
  • Another aspect of the present disclosure is to provide a method for producing a cured product, a method for producing a cured product pattern, and a method for producing a wiring board using such a photosensitive element.
  • particles having a diameter of 5 ⁇ m or more and agglomerates having a diameter of 5 ⁇ m or more contained in the support film cause resist defect.
  • the present inventor has found that small defects such as a maximum diameter of 1 ⁇ m increase the number of resist defects as defects contained inside the support film, and then reduce the number of defects having a maximum diameter of 1 ⁇ m or more. By doing so, it was found that the occurrence of resist deficiency can be suppressed.
  • One aspect of the present disclosure comprises a support film and a photosensitive layer arranged on the support film, and the number of defects having a maximum diameter of 1 ⁇ m or more inside the support film is 100 or less per 0.225 mm 2 .
  • the present invention relates to a photosensitive element, wherein the photosensitive layer contains a binder polymer, a photopolymerizable compound having an ethylenically unsaturated bond, and a photopolymerization initiator.
  • the occurrence of resist defect can be suppressed.
  • Another aspect of the present disclosure comprises an exposure step of irradiating the photosensitive layer with an active ray through the support film in a state where the above-mentioned photosensitive element is laminated on a substrate to obtain a cured product.
  • an exposure step of irradiating the photosensitive layer with an active ray through the support film in a state where the above-mentioned photosensitive element is laminated on a substrate to obtain a cured product Regarding the manufacturing method of things.
  • Another aspect of the present disclosure is a method for producing a cured product pattern, comprising a step of removing at least a part of a portion other than the cured product in the photosensitive layer after the exposure step in the above-mentioned method for producing a cured product.
  • Another aspect of the present disclosure is the manufacture of a wiring board comprising a step of etching or plating a laminate provided on the substrate with the cured product pattern obtained by the above-mentioned method for producing a cured product pattern. Regarding the method.
  • a photosensitive element capable of suppressing the occurrence of resist defect. Further, according to another aspect of the present disclosure, it is possible to provide a method for producing a cured product, a method for producing a cured product pattern, and a method for producing a wiring board using such a photosensitive element.
  • a or more in the numerical range means A and a range exceeding A.
  • a or less in the numerical range means A and a range less than A.
  • the upper or lower limit of the numerical range at one stage may be optionally combined with the upper or lower limit of the numerical range at another stage.
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
  • “A or B” may include either A or B, and may include both. Unless otherwise specified, the materials exemplified in the present specification may be used alone or in combination of two or more.
  • each component in the composition means the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified.
  • layer and “film” include not only a structure having a shape formed on the entire surface but also a structure having a shape partially formed when observed as a plan view.
  • process is included in this term not only in an independent process but also in the case where the intended action of the process is achieved even if it cannot be clearly distinguished from other processes.
  • (meth) acrylate is meant at least one of the acrylate and the corresponding methacrylate. The same applies to other similar expressions such as “(meth) acrylic acid”.
  • the photosensitive element according to the present embodiment includes a support film and a photosensitive layer arranged on the support film, and the number of defects having a maximum diameter of 1 ⁇ m or more inside the support film is 100 per 0.225 mm 2 .
  • the photosensitive layer contains (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator.
  • the photosensitive element according to the present embodiment it is possible to suppress the occurrence of resist defect after exposure and development of the photosensitive layer, and even when a high-resolution exposure machine is used, the resist defect is not present. The occurrence can be suppressed. According to the photosensitive element according to the present embodiment, it is possible to suppress the occurrence of resist defects while obtaining good resolution and adhesion (developer resistance).
  • Defects inside the support film can cause resist defects after development by causing light scattering when the photosensitive layer is exposed through the support film.
  • the influence of light scattering is large, and resist defects are likely to occur after development.
  • an open defect during etching or a short defect during plating is likely to occur, and the manufacturing yield of the wiring board tends to decrease.
  • FIG. 1 is a schematic cross-sectional view showing an example of a photosensitive element.
  • the photosensitive element 1 shown in FIG. 1 includes a support film 10 and a photosensitive layer 20.
  • the photosensitive layer 20 is provided on the first main surface 10a of the support film 10.
  • the support film 10 has a second main surface 10b on the side opposite to the first main surface 10a.
  • the number of defects with a maximum diameter of 1 ⁇ m or more inside the support film is 80 or less, 50 or less, 30 or less, 20 or less, 18 per 0.225 mm 2 from the viewpoint of easily suppressing the occurrence of resist defects.
  • the number may be 16 or less, 15 or less, 10 or less, 8 or less, 5 or less, 3 or less, 2 or less, or 1 or less.
  • the number of defects may be zero.
  • the number of defects can be reduced by selectively removing components that can generate defects, and for example, the defects can be reduced by filtering the film-forming composition of the support film before film formation.
  • the number of defects inside the support film is the number of defects per 0.225 mm 2 (0.150 mm ⁇ 0.150 mm).
  • the number of defects is the average of multiple measurements.
  • the average value can be obtained as the average value of the measured values of a total of 50 regions obtained by performing the operation of measuring the number of defects in any 10 regions on the support film five times.
  • the unit area of 0.225 mm 2 with respect to the number of defects is the area in the plane parallel to the main plane of the support film.
  • the defects inside the support film are, for example, light blocking substances and may be caused by a component having a refractive index different from the bending rate of the constituent material which is the main component of the support film.
  • Factors that form the light blocker include polymer gels; raw material monomers; catalysts used during production; inorganic particles (such as lubricants), organic particles, or aggregates of particles used in the production of support films. Things can be mentioned. Examples of the inorganic component of the inorganic particles include simple substances such as calcium, magnesium, and silica; and compounds containing at least one of these.
  • the light blocker blocks the active light beam at the time of exposure without transmitting it.
  • the number of defects inside the support film has a great influence on the occurrence of resist defects.
  • the number of defects inside the support film is the number of defects inside the support film (for example, the number of light blocking objects) measured using a confocal microscope (confocal microscope).
  • the conditions under which the inside of the support film can be suitably observed may be adjusted.
  • the support film has a layer containing particles (such as a lubricant layer) on the surface layer portion, the inner layer portion of the support film is evaluated excluding the surface layer portion in order to evaluate the number of defects inside the support film.
  • the region (inner layer portion) between the portion having a depth of 0.5 ⁇ m from one surface and the portion having a depth of 0.5 ⁇ m from the other surface can be measured. .. That is, the number of defects inside the support film is the number of defects inside the support film excluding the lubricant layer when the support film has a lubricant layer on the surface. According to the findings of the present inventor, there is a possibility that a defect may occur inside the support film due to the influence of providing the lubricant layer on the surface layer portion.
  • a hybrid laser microscope OPTELICS HYBRID (Lasertec Co., Ltd., trade name) or the like can be used.
  • Observation with a confocal microscope is a measurement method for detecting reflected light from an object to be observed by a light receiving unit.
  • the object to be observed is in focus (when it is in focus)
  • the reflected light is strongly obtained, and the intensity of the light is strongly observed (often observed in white).
  • the object to be observed is out of focus (out of focus)
  • the light intensity is weak (often observed in black).
  • the numerical aperture (Na) of the objective lens used for observation may be 0.8 from the viewpoint of accurate and efficient observation.
  • the numerical aperture is 0.8, it is easier to prevent the lens from coming into contact with the observation object and the microscope from being soiled as compared with the case where the numerical aperture exceeds 0.8, and the magnification is excessively high. Therefore, it is easy to suppress the decrease in the amount of light in the visual field and the decrease in the detection level.
  • the numerical aperture (Na) is 0.8, the decrease in resolution is suppressed and an error is less likely to occur in the size detection of the observation object as compared with the case where the numerical aperture is less than 0.8. Therefore, it is easy to measure with high accuracy.
  • the measurement magnification may be 50 times, and the digital zoom on the software may be 2 times.
  • the measurement magnification is 50 times, the decrease in the amount of light in the visual field is suppressed and the decrease in the detection level is more likely to be suppressed, and the measurement magnification is less than 50 times, as compared with the case where the measurement magnification exceeds 50 times. It is easier to measure the size of the defect more accurately than in the case of.
  • the digital zoom is 2 times, the decrease in the amount of light in the field of view is suppressed and the decrease in the detection level is likely to be suppressed as compared with the case where the digital zoom is the same magnification (no setting).
  • the constituent material of the support film examples include polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene-2,6-naphthalate (PEN); polyolefins such as polypropylene and polyethylene.
  • the support film may have a polyester film or a PET film from the viewpoint of easily suppressing the occurrence of resist defects.
  • the support film is a light-transmitting film and may be a transparent resin film.
  • the support film may be a single layer or a multilayer.
  • the support film may have a lubricant layer disposed on at least one surface of an inner layer portion (eg, a film of the above-mentioned constituent material of the support film).
  • the support film may have a polyester film and a lubricant layer disposed on at least one surface of the polyester film.
  • the lubricant layer can be formed by using a known method such as a roll coater, a flow coater, a spray coater, a curtain flow coater, a dip coater, and a slit die coater.
  • the haze value of the support film is 0.01% or more, 0.05 from the viewpoint of easily improving the operability when laminating the photosensitive element on the substrate, the operability when forming the photosensitive layer on the support film, and the like. % Or more, 0.1% or more, 0.3% or more, 0.5% or more, or 0.7% or more.
  • the haze value of the support film may be 3.0% or less, 1.5% or less, 0.8% or less, or 0.7% or less from the viewpoint of easily obtaining good sensitivity and resolution. From these viewpoints, the haze value of the support film is 0.01 to 3.0%, 0.01 to 1.5%, 0.01 to 0.8%, or 0.01 to 0.7%. It may be there. "Haze value" means cloudiness.
  • turbidity meter for example, trade name "NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd.
  • JIS K7105 JIS K7105
  • the light transmittance of the support film (for example, the light transmittance in the entire range of wavelengths of 380 to 780 nm) may be in the following range.
  • the light transmittance of the support film may be 80% or more, 85% or more, 87% or more, 88% or more, or 89% or more.
  • the light transmittance of the support film may be 95% or less, 93% or less, 90% or less, or 89% or less. From these viewpoints, the light transmittance of the support film may be 80 to 95%.
  • the light transmittance of the support film can be measured using a commercially available cloudiness meter (for example, trade name "NDH-5000" manufactured by Nippon Denshoku Industries Co., Ltd.).
  • the thickness of the support film or the thickness of the polyester film may be in the following range.
  • the thickness may be 5 ⁇ m or more, 10 ⁇ m or more, 11 ⁇ m or more, 12 ⁇ m or more, 15 ⁇ m or more, or 16 ⁇ m or more from the viewpoint that the support film is not easily torn when the support film is peeled from the photosensitive element.
  • the thickness may be 200 ⁇ m or less, 100 ⁇ m or less, 50 ⁇ m or less, 40 ⁇ m or less, 30 ⁇ m or less, 20 ⁇ m or less, or 18 ⁇ m or less from the viewpoint of easily ensuring the focal margin at the time of exposure. From these viewpoints, the thickness may be 5 to 200 ⁇ m, 11 to 100 ⁇ m, 12 to 50 ⁇ m, or 15 to 40 ⁇ m.
  • the photosensitive layer is a layer made of a photosensitive resin composition.
  • the photosensitive layer and the photosensitive resin composition constituting the photosensitive layer contain (A) a binder polymer, (B) a photopolymerizable compound having an ethylenically unsaturated bond, and (C) a photopolymerization initiator. ..
  • the photosensitive layer can be obtained by removing at least a part of the solvent in the film-forming resin composition (photosensitive resin composition).
  • the photosensitive layer may have negative photosensitive.
  • the constituent material of the binder polymer as the component (A) examples include acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, and phenol resin.
  • the component (A) may contain an acrylic resin from the viewpoint of easily obtaining good alkaline developability.
  • a binder polymer used in a conventional photosensitive resin composition can be used as the component (A).
  • the component (A) can be obtained by polymerizing a polymerizable monomer (for example, radical polymerization). That is, the component (A) has a polymerizable monomer as a monomer unit.
  • a polymerizable monomer for example, radical polymerization
  • the polymerizable monomer include (meth) acrylic acid, alkyl (meth) acrylate ((meth) methyl acrylate, etc.), benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and (meth) acrylic.
  • Examples thereof include glycidyl acid acid, styrene compounds (styrene and styrene derivatives (vinyltoluene, ⁇ -methylstyrene, etc.)), and maleic acid.
  • a substituent may be bonded to the aromatic ring of benzyl (meth) acrylate.
  • the component (A) may have a carboxyl group in the molecule from the viewpoint of easily obtaining good alkali developability.
  • the binder polymer having a carboxyl group can be obtained by polymerizing (for example, radical polymerization) a polymerizable monomer having a carboxyl group.
  • the component (A) may have a polymerizable monomer having a carboxyl group as a monomer unit and (meth) acrylic acid as a monomer unit from the viewpoint of easily obtaining good alkaline developability. It's okay.
  • the content of the monomer unit of (meth) acrylic acid is good resist peeling. From the viewpoint of easily obtaining characteristics and developability, the range may be as follows based on the total amount of the monomer units constituting the component (A).
  • the content of the monomer unit of (meth) acrylic acid may be 10% by mass or more, 15% by mass or more, 20% by mass or more, or 25% by mass or more.
  • the content of the monomer unit of (meth) acrylic acid may be 40% by mass or less, 35% by mass or less, or 30% by mass or less. From these viewpoints, the content of the monomer unit of (meth) acrylic acid may be 10 to 40% by mass, 15 to 35% by mass, 20 to 35% by mass, or 20 to 30% by mass.
  • the component (A) may have an alkyl (meth) acrylate as a monomer unit (a structural unit derived from an alkyl (meth) acrylate) from the viewpoint of easily obtaining good alkali developability and peeling characteristics. It may have (meth) acrylic acid and alkyl (meth) acrylic acid as a monomer unit.
  • the alkyl (meth) acrylate may contain methyl (meth) acrylate from the viewpoint of easily obtaining good alkali developability and peeling properties.
  • the content of the monomer unit of the alkyl (meth) acrylate is the total amount of the monomer units constituting the component (A).
  • the standard may be in the following range.
  • the content of the monomer unit of alkyl (meth) acrylate may be 1% by mass or more, 3% by mass or more, or 5% by mass or more from the viewpoint of easily obtaining good peeling characteristics.
  • the content of the monomer unit of alkyl (meth) acrylate is 40% by mass or less, 30% by mass or less, 20% by mass or less, 10% by mass or less, or from the viewpoint of easily obtaining good resolution and adhesion. It may be 8% by mass or less. From these viewpoints, the content of the monomer unit of alkyl (meth) acrylate may be 1 to 40% by mass, 3 to 30% by mass, or 5 to 20% by mass.
  • the component (A) may have benzyl (meth) acrylate as a monomer unit (a structural unit derived from benzyl (meth) acrylate) from the viewpoint of easily obtaining good adhesion and resist peeling characteristics.
  • the content of the monomer unit of benzyl (meth) acrylate is described below based on the total amount of the monomer units constituting the component (A) from the viewpoint of easily obtaining good adhesion and resist peeling characteristics. It may be in the range of.
  • the content of the monomer unit of benzyl (meth) acrylate may be 10% by mass or more, 15% by mass or more, or 20% by mass or more.
  • the content of the monomer unit of benzyl (meth) acrylate may be 60% by mass or less, 55% by mass or less, 35% by mass or less, or 30% by mass or less. From these viewpoints, the content of the monomer unit of benzyl (meth) acrylate may be 10 to 60% by mass, 15 to 55% by mass, 15 to 35% by mass, or 20 to 30% by mass. ..
  • the component (A) may have a styrene compound as a monomer unit (structural unit derived from the styrene compound) from the viewpoint of easily obtaining good resolution and adhesion.
  • the content of the monomer unit of the styrene compound may be in the following range based on the total amount of the monomer units constituting the component (A).
  • the content of the monomer unit of the styrene compound may be 10% by mass or more, 20% by mass or more, 30% by mass or more, or 40% by mass or more from the viewpoint of easily obtaining good resolution.
  • the content of the monomer unit of the styrene compound may be 60% by mass or less, 50% by mass or less, or 45% by mass or less from the viewpoint of easily obtaining good peeling characteristics. From these viewpoints, the content of the monomer unit of the styrene compound is 10 to 60% by mass, 10 to 50% by mass, 20 to 45% by mass, 30 to 45% by mass, or 40 to 45% by mass. It's okay.
  • the weight average molecular weight (Mw) of the component (A) may be 10,000 or more, 20,000 or more, 25,000 or more, 30,000 or more, 35,000 or more, 40,000 or more, or 45,000 or more from the viewpoint of easily obtaining good adhesion.
  • the weight average molecular weight of the component (A) may be 80,000 or less, 50,000 or less, or 45,000 or less from the viewpoint of easily obtaining good developability. From these viewpoints, the weight average molecular weight of the component (A) may be 10,000 to 80,000, 20,000 to 50,000, or 25,000 to 45,000.
  • the dispersity (Mw / Mn) of the component (A) may be 1.5 or more or 2.0 or more.
  • the dispersity (Mw / Mn) of the component (A) may be 3.5 or less or 3.3 or less from the viewpoint of easily obtaining good adhesion and resolution.
  • the weight average molecular weight (Mw) and the degree of dispersion (Mw / Mn) can be obtained, for example, by measuring by gel permeation chromatography (GPC) and converting using a standard polystyrene calibration curve. More specifically, it can be measured by the method described in Examples. When it is difficult to measure a compound having a low molecular weight by such a measuring method, the molecular weight can be measured by another method and the average value can be calculated.
  • GPC gel permeation chromatography
  • the acid value of the component (A) is 60 mgKOH / g or more, 65 mgKOH / g or more, 70 mgKOH / g or more, 75 mgKOH / g or more, 80 mgKOH / g or more, 85 mgKOH / g or more, 90 mgKOH from the viewpoint of easily obtaining good developability. It may be / g or more, 95 mgKOH / g or more, 100 mgKOH / g or more, or 105 mgKOH / g or more.
  • the acid value of the component (A) is 250 mgKOH / g or less, 240 mgKOH / g or less, 230 mgKOH / g or less, 200 mgKOH / g or less, 150 mgKOH / g or less, or 120 mgKOH / g or less from the viewpoint of easily obtaining good adhesion. May be. From these viewpoints, it may be 60 to 250 mgKOH / g, 65 to 250 mgKOH / g, 70 to 240 mgKOH / g, or 75 to 230 mgKOH / g.
  • the acid value of the component (A) can be adjusted by the content of the monomer unit constituting the component (A) (for example, the monomer unit of (meth) acrylic acid).
  • the content of the component (A) may be in the following range based on the total amount of the solid content of the photosensitive resin composition.
  • the content of the component (A) is 20% by mass or more, 30% by mass or more, 40% by mass or more, from the viewpoint that good formability of the film can be easily obtained and that the cured product is easily suppressed from becoming brittle. Alternatively, it may be 50% by mass or more.
  • the content of the component (A) may be 90% by mass or less, 80% by mass or less, 65% by mass or less, or 60% by mass or less from the viewpoint of easily obtaining good sensitivity and resolution. From these viewpoints, the content of the component (A) may be 20 to 90% by mass, 30 to 80% by mass, or 40 to 65% by mass.
  • the content of the component (A) may be in the following range with respect to 100 parts by mass of the total amount of the component (A) and the component (B).
  • the content of the component (A) is 30 parts by mass or more, 35 parts by mass or more, 40 parts by mass or more, from the viewpoint that good formability of the film can be easily obtained and that the cured product is easily suppressed from becoming brittle. Alternatively, it may be 50 parts by mass or more.
  • the content of the component (A) may be 70 parts by mass or less, 65 parts by mass or less, or 60 parts by mass or less from the viewpoint of easily obtaining good sensitivity and resolution. From these viewpoints, the content of the component (A) may be 30 to 70 parts by mass, 35 to 70 parts by mass, 40 to 70 parts by mass, 40 to 65 parts by mass, or 50 to 60 parts by mass.
  • the component (B) (photopolymerizable compound having an ethylenically unsaturated bond) may be a compound having an ethylenically unsaturated bond and polymerizing by light.
  • the component (B) may contain a bisphenol A type di (meth) acrylate compound from the viewpoint of easily obtaining good alkali developability, resolution and peeling characteristics.
  • Examples of the bisphenol A type di (meth) acrylate compound include 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane (2,2-bis (4-((meth) acryloxypentaethoxy)). Phenyl) propane, etc.), 2,2-bis (4-((meth) acryloxypolypropoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypolybutoxy) phenyl) propane, 2, 2-Bis (4-((meth) acryloxipolyethoxypolypropoxy) phenyl) propane and the like can be mentioned.
  • the components (B) are 2,2-bis (4-((meth) acryloxipentethoxy) phenyl) propane and 2,2-bis (4-(, from the viewpoint of easily obtaining good resolution and peeling characteristics. It may contain at least one selected from the group consisting of (meth) acryloxidiethoxy) phenyl) propane, including 2,2-bis (4-((meth) acryloxypentethoxy) phenyl) propane and 2,2-. Bis (4-((meth) acryloxidiethoxy) phenyl) propane may be used in combination.
  • the content of the bisphenol A type di (meth) acrylate compound may be in the following range based on the total amount of the component (B) from the viewpoint of easily obtaining a good resolution.
  • the content of the bisphenol A type di (meth) acrylate compound may be 60% by mass or more, 70% by mass or more, or 80% by mass or more.
  • the content of the bisphenol A type di (meth) acrylate compound may be 99% by mass or less, 95% by mass or less, or 90% by mass or less. From these viewpoints, the content of the bisphenol A type di (meth) acrylate compound may be 60 to 99% by mass.
  • the component (B) is composed of trimethylolpropane tri (meth) acrylate, tetramethylolmethanetri (meth) acrylate, and alkylene oxide-modified products thereof from the viewpoint of easily obtaining good peeling properties, adhesion and flexibility. It may contain at least one compound X selected from the group.
  • alkylene oxide-modified product of trimethylolpropane tri (meth) acrylate and tetramethylolmethanetri (meth) acrylate include EO-modified product, PO-modified product, and EO / PO-modified product.
  • the content of compound X may be in the following range based on the total amount of component (B).
  • the content of the compound X may be 1% by mass or more, 5% by mass or more, or 10% by mass or more from the viewpoint of easily obtaining good developability, adhesion and pattern shape.
  • the content of compound X may be 30% by mass or less, 25% by mass or less, 20% by mass or less, or 15% by mass or less from the viewpoint of easily obtaining good peeling characteristics. From these viewpoints, the content of compound X may be 1 to 30% by mass.
  • the content of the component (B) may be in the following range based on the total solid content of the photosensitive resin composition.
  • the content of the component (B) is 1% by mass or more, 3% by mass or more, 10% by mass or more, 20% by mass or more, 25% by mass or more, 30% by mass or more, from the viewpoint of easily obtaining good sensitivity and resolution. Alternatively, it may be 40% by mass or more.
  • the content of the component (B) is 70% by mass or less, 60% by mass or less, or 50% by mass from the viewpoint that good formability of the film can be easily obtained and that the cured product is easily suppressed from becoming brittle. It may be as follows. From these viewpoints, the content of the component (B) may be 1 to 70% by mass.
  • the content of the component (B) may be in the following range with respect to 100 parts by mass of the total amount of the component (A) and the component (B).
  • the content of the component (B) may be 30 parts by mass or more, 35 parts by mass or more, or 40 parts by mass or more from the viewpoint of easily obtaining good sensitivity and resolution.
  • the content of the component (B) is 70 parts by mass or less, 65 parts by mass or less, 60 parts by mass or less, from the viewpoint that good formability of the film can be easily obtained and that the cured product is easily suppressed from becoming brittle. Alternatively, it may be 50 parts by mass or less. From these viewpoints, the content of the component (B) may be 30 to 70 parts by mass, 30 to 65 parts by mass, 30 to 60 parts by mass, 35 to 60 parts by mass, or 40 to 50 parts by mass.
  • photopolymerization initiator examples include benzophenone; N, N'-tetraalkyl- such as N, N, N', N'-tetramethyl-4,4'-diaminobenzophenone (also known as Michler ketone).
  • Aromatic ketones such as -1, quinone compounds such as alkylanthraquinone; benzoin ether compounds such as benzoin alkyl ethers; benzoin compounds such as benzoin and alkylbenzoins; benzyl derivatives such as benzyldimethyl ketal; 2- (o-chlorophenyl) -4 , 5-Diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2,4,5-Triarylimidazole dimer such as 2- (o-meth
  • the component (C) may contain a 2,4,5-triarylimidazole dimer from the viewpoint of easily obtaining good adhesion and sensitivity.
  • the content of the component (C) may be in the following range based on the total solid content of the photosensitive resin composition.
  • the content of the component (C) is 0.1% by mass or more, 0.2% by mass or more, 0.5% by mass or more, 1% by mass or more, 2% by mass or more, or from the viewpoint of easily obtaining good sensitivity. , 2.5% by mass or more.
  • the content of the component (C) is 20% by mass or less and 10% by mass from the viewpoint that the light absorption on the surface of the photosensitive layer is suppressed from being excessively increased during exposure and the inside of the photosensitive layer is easily sufficiently cured. % Or less, 5% by mass or less, or 3% by mass or less. From these viewpoints, the content of the component (C) may be 0.1 to 20% by mass, 0.2 to 10% by mass, or 0.5 to 5% by mass.
  • the content of the component (C) may be in the following range with respect to 100 parts by mass of the total amount of the component (A) and the component (B).
  • the content of the component (C) is 0.1 parts by mass or more, 0.2 parts by mass or more, 0.5 parts by mass or more, 1 part by mass or more, 2 parts by mass or more, or from the viewpoint of easily obtaining good sensitivity. , 2.5 parts by mass or more.
  • the content of the component (C) is 20 parts by mass or less and 10 parts by mass from the viewpoint that the light absorption on the surface of the photosensitive layer is suppressed from being excessively increased during exposure and the inside of the photosensitive layer is easily sufficiently cured. It may be 5 parts by mass or less, or 3 parts by mass or less. From these viewpoints, the content of the component (C) may be 0.1 to 20 parts by mass, 0.2 to 10 parts by mass, or 0.5 to 5 parts by mass.
  • the photosensitive layer and the photosensitive resin composition for forming the photosensitive layer have at least one component in the molecule as a component different from the component (A), the component (B) and the component (C), if necessary.
  • Photopolymerizable compounds having a cationically polymerizable cyclic ether group oxetane compounds, etc.), cationic polymerization initiators, dyes (malakite green, etc.), sensitizers (1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) pyrazoline, etc.), photocolor-developing agent (tribromophenyl sulfone, leucocrystal violet, etc.), thermal color-developing inhibitor, plasticizer (p-toluene sulfone amide, etc.), polymerization inhibitor (4-t-butyl) Contains additives such as catechol, etc.), pigments, fillers, defoaming agents, flame retardants, stabilizer
  • the photosensitive resin composition is, if necessary, a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixture of these solvents.
  • a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixture of these solvents.
  • the constituent components of the photosensitive layer can be dissolved in a solvent to prepare a solution having a solid content of about 30 to 60% by mass.
  • the photosensitive layer can be formed by applying the photosensitive resin composition on the support film and then removing the solvent.
  • the coating method for example, a known method such as a roll coat, a comma coat, a gravure coat, an air knife coat, a die coat, and a bar coat can be adopted.
  • the solvent can be removed by, for example, treating at 70 to 150 ° C. for about 5 to 30 minutes.
  • the amount of the residual organic solvent in the photosensitive layer may be 2% by mass or less from the viewpoint of easily preventing the diffusion of the organic solvent in a later step.
  • the thickness of the photosensitive layer may be 1 ⁇ m or more, 5 ⁇ m or more, 10 ⁇ m or more, 15 ⁇ m or more, 20 ⁇ m or more, or 25 ⁇ m or more from the viewpoint of easily obtaining good resolution and adhesion.
  • the thickness of the photosensitive layer is 300 ⁇ m or less, 200 ⁇ m or less, 100 ⁇ m or less, 80 ⁇ m or less, 70 ⁇ m or less, 60 ⁇ m or less, 50 ⁇ m or less, 40 ⁇ m or less, 30 ⁇ m or less, or , 25 ⁇ m or less. From these viewpoints, the thickness of the photosensitive layer may be 1 to 300 ⁇ m.
  • the photosensitive element according to the present embodiment may be provided with a protective film on the side opposite to the support film of the photosensitive layer.
  • a protective film a film can be used in which the adhesive force between the photosensitive layer and the protective film is smaller than the adhesive force between the support film and the photosensitive layer.
  • a low fisheye film may be used.
  • the protective film include an inert polyolefin film (polyethylene film, polypropylene film, etc.).
  • the protective film may be a polyethylene film from the viewpoint of easily obtaining good peeling characteristics from the photosensitive layer.
  • the thickness of the protective film varies depending on the application, but may be about 1 to 100 ⁇ m.
  • the photosensitive element according to the present embodiment may include an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer or a protective layer in addition to the support film, the photosensitive layer and the protective film.
  • an intermediate layer such as a cushion layer, an adhesive layer, a light absorption layer, and a gas barrier layer or a protective layer in addition to the support film, the photosensitive layer and the protective film.
  • the photosensitive element according to the present embodiment may be stored as it is, for example, or may be stored in a state where a protective film is laminated on the photosensitive layer and wound around a cylindrical core. At this time, the support film may be wound into a roll so as to be the outermost layer.
  • the method for producing a cured product according to the present embodiment includes a curing step of curing the photosensitive layer of the photosensitive element to obtain a cured product (photo-cured product).
  • a cured product photo-cured product
  • a cured product is obtained by irradiating a photosensitive layer with active light via a support film in a state where photosensitive elements are laminated on a substrate. It may be provided with an exposure process for obtaining the above.
  • a predetermined portion of the photosensitive layer is irradiated with active light rays.
  • the photosensitive element may be laminated on the substrate so that the photosensitive layer is located closer to the substrate than the support film.
  • a photomask having a negative or positive mask pattern is in close contact with the support film, and the photosensitive layer is irradiated with active light through the support film (for example, irradiated in an image) to cure.
  • the light source of the active light include a light source that emits ultraviolet rays, visible light, and the like (carbon arc lamp, mercury vapor arc lamp, high-pressure mercury lamp, xenon lamp, etc.).
  • a laser direct drawing exposure method can also be used.
  • the method for producing a cured product according to the present embodiment may include a laminating step of laminating a photosensitive element on a substrate before the curing step.
  • the photosensitive element can be laminated on the substrate so that the photosensitive layer is located closer to the substrate than the support film.
  • Examples of the method of laminating the photosensitive element on the substrate include a method of laminating the photosensitive layer on the substrate by pressure bonding at a pressure of about 0.1 to 1 MPa while heating to about 70 to 130 ° C. If the protective film is present on the photosensitive layer, the photosensitive layer may be pressure-bonded to the substrate after the protective film is removed. In the laminating step, the photosensitive elements can also be laminated under reduced pressure. From the viewpoint of improving the stackability, the substrate may be preheat-treated.
  • the constituent material of the surface of the substrate on which the photosensitive elements are laminated may be a metal or a resin material.
  • a portion (unexposed portion) other than the cured product in the photosensitive layer is used.
  • a developing step of removing at least a part thereof to obtain a cured product pattern (resist pattern) is provided.
  • the photomask is peeled off from the support film, and the support film is peeled off from the photosensitive layer.
  • wet development with a developing solution alkaline aqueous solution, aqueous developer, organic solvent, etc.
  • development is performed by removing the unexposed part (unlightened part) of the photosensitive layer by dry development or the like to form a cured product pattern.
  • Examples of the alkaline aqueous solution include 0.1 to 5% by mass sodium carbonate solution, 0.1 to 5% by mass potassium carbonate solution, 0.1 to 5% by mass sodium hydroxide solution and the like.
  • the pH of the alkaline aqueous solution may be 9-11.
  • the temperature of the alkaline aqueous solution can be adjusted according to the developability of the photosensitive layer.
  • the alkaline aqueous solution may contain a surfactant, an antifoaming agent, an organic solvent and the like.
  • Examples of the developing method include a dip method, a spray method, brushing, and slapping.
  • the cured product pattern is further heated and / or exposed as necessary after the developing step. It may be provided with a curing step. Heating may be performed, for example, at 60 to 250 ° C. or 100 to 170 ° C. for 15 to 90 minutes.
  • the exposure can be performed by irradiating ultraviolet rays with a high-pressure mercury lamp. The exposure amount may be, for example, 0.2 to 10 J / cm 2 . Heating and exposure (for example, ultraviolet irradiation) may be performed simultaneously, and one of heating and exposure may be performed and then the other. When heating and exposure are performed at the same time, it can be heated at 60 to 150 ° C. from the viewpoint of effectively imparting solder heat resistance, chemical resistance and the like.
  • a cured product pattern can be formed on a patterned conductor layer (wiring).
  • the cured product pattern can be used as a solder resist to prevent solder from adhering to unnecessary portions of the conductor layer when joining the mounted components.
  • the cured product pattern obtained by the method for producing a cured product pattern according to the present embodiment can be used as a protective film for a conductor layer after soldering, and has physical properties (tensile strength, elongation, etc.) and heat resistance. Since it has excellent impact resistance, it is effective as a permanent mask for semiconductor packages. After mounting a semiconductor element or the like (wire bonding, solder connection, etc.) on a package substrate provided with such a cured product pattern (resist pattern), it can be mounted on an electronic device (personal computer or the like).
  • the cured product pattern obtained by the method for producing a cured product pattern according to the present embodiment has excellent physical characteristics (tensile strength, elongation, etc.), and a cured resin satisfying electrolytic corrosion resistance is formed on a rigid substrate. It may be used as a solder resist (permanent mask) formed on a rigid substrate. Specifically, it can be used as a solder resist for a printed wiring board including a rigid substrate, a solder resist for a package substrate including a rigid substrate, and the like.
  • the method for manufacturing a wiring board (for example, a printed wiring board) according to the present embodiment is such that a laminate having a cured product pattern obtained by the method for producing a cured product pattern according to the present embodiment is etched or plated on a laminate. It is provided with a process for performing processing.
  • the cured product pattern can be used as a mask to perform an etching treatment or a plating treatment on the laminated body by a known method.
  • the wiring board may be a multilayer printed wiring board and may have a small diameter through hole.
  • Examples of the etching solution used for the etching process include a cupric chloride solution, a ferric chloride solution, and an alkaline etching solution.
  • Examples of the plating treatment include copper plating, solder plating, nickel plating, gold plating and the like.
  • the cured product pattern can be peeled off with a stronger alkaline aqueous solution than the alkaline aqueous solution used for development.
  • a stronger alkaline aqueous solution examples include a 1 to 10% by mass sodium hydroxide aqueous solution and a 1 to 10% by mass potassium hydroxide aqueous solution.
  • the method for peeling the cured product pattern include a dipping method and a spraying method.
  • the conductor layer other than the pattern portion can be removed.
  • a method of removing the conductor layer a method of lightly etching after peeling the cured product pattern; a method of masking the wiring part with solder by peeling off the cured product pattern after performing solder plating or the like after the plating process, and then Examples thereof include a method of treating only the conductor layer with an etching solution capable of etching.
  • the mixture e was kept warm at 80 ° C. for 3 hours with stirring. Subsequently, it was heated to 90 ° C. over 30 minutes. A binder polymer solution was obtained by incubating at 90 ° C. for 2 hours and then cooling. Toluene was added to this binder polymer solution to adjust the non-volatile component concentration (solid content concentration) to 40% by mass.
  • the weight average molecular weight of the binder polymer was 45,000.
  • the weight average molecular weight was calculated by measuring by gel permeation chromatography (GPC) under the following conditions and converting using a calibration curve of standard polystyrene.
  • the acid value of the binder polymer was 107 mgKOH / g.
  • ⁇ Preparation of photosensitive resin composition > 145 g of binder polymer solution, 28 g of EO-modified bisphenol A dimethacrylate (Hitachi Kasei Co., Ltd., trade name: FA-321M), and 10 g of EO-modified bisphenol A dimethacrylate (Shin-Nakamura Chemical Co., Ltd., trade name: BPE-200).
  • a photosensitive resin composition was obtained by mixing 5 g, 9 g of acetone, and 5 g of toluene.
  • Films A1 to A7 Biaxially oriented films having a three-layer structure having lubricant layers containing particles on the front and back of the PET film.
  • the time of the filtration treatment applied to the film-forming composition (the same film-forming composition as the FB40 PET film manufactured by Toray Industries, Inc.) before the formation of the PET film was adjusted.
  • the filtration time of the films A1 to A3 was 24 hours or more, the filtration time of the films A4 to A6 was 12 to 18 hours, and the filtration time of the films A7 was 6 hours or less.
  • Film B A biaxially oriented film having a two-layer structure having a lubricant layer containing particles on one side of a PET film. Made by Mitsubishi Chemical Corporation, Product name: R-705G Film C: Single-layer structure biaxially oriented PET film containing particles, manufactured by Teijin DuPont Film Co., Ltd., trade name: G2
  • the solvent is removed by drying in a hot air convection dryer at 100 ° C. for 2 minutes to obtain photosensitive on the PET film.
  • An evaluation laminate having a layer (thickness: 25 ⁇ m) was obtained.
  • a photosensitive layer is formed on the surface opposite to the lubricant layer.
  • Ten areas of 0.225 mm 2 (0.150 mm ⁇ 0.150 mm) of the support film of the evaluation laminate were selected, and the number of defects (light blockers) having a maximum diameter of 1 ⁇ m or more contained in each area was measured. ..
  • the region (inner layer) between the surface layer portion having a depth of 0.5 ⁇ m from one side of the support film and the surface layer portion having a depth of 0.5 ⁇ m from the other surface of the support film. Department) was evaluated.
  • a confocal microscope manufactured by Laser Tech Co., Ltd., trade name: hybrid laser microscope OPTELICS HYBRID
  • the image has a numerical aperture (Na) of 0.8, a magnification of 50 times, a digital zoom of 2 times, and the conditions shown in Table 1 below. was obtained, and the size and number of defects were measured from the pixels in the image.
  • FIG. 2A shows the results (magnification: 600 times) of observing the surface of the support film of Example 1 using a confocal microscope (manufactured by Lasertec Co., Ltd., trade name: hybrid laser microscope OPTELICS HYBRID) for comparison.
  • the result of observing the surface of the support film of Example 1 is shown in FIG. 2 (b).
  • the scales in the images of FIGS. 2 (a) and 2 (b) are the same as each other.
  • the image of the support film of Example 1 observed by the above-mentioned confocal microscope is shown in FIG. 3 (a), and the image of the support film of Comparative Example 1 is shown in FIG. 3 (b).
  • the scales in the images of FIGS. 3 (a) and 3 (b) are the same as each other.
  • the light transmittance (wavelength: 380 to 780 nm) and haze value of the support film were measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name: NDH-5000).
  • the thickness (total thickness) of the support film was measured using MH-15M (trade name) manufactured by Nikon Corporation. The results are shown in Table 2.
  • the photosensitive layer (thickness:) is removed by drying with a hot air convection dryer at 100 ° C. for 2 minutes to remove the solvent. 25 ⁇ m) was formed.
  • a photosensitive layer is formed on the surface opposite to the lubricant layer.
  • a photosensitive element was obtained by coating the photosensitive layer with a protective film made of polyethylene (manufactured by Tamapoli Co., Ltd., trade name: NF-15, thickness: 18 ⁇ m).
  • ⁇ Evaluation> (Preparation of laminated body) After forming a copper layer (electroless copper, thickness: 500 nm) by electroless plating on both sides of an interlayer insulating material (manufactured by Ajinomoto Fine-Techno Co., Ltd., trade name: GX-T31), the surface of the copper layer is acidified.
  • the substrate a was obtained by washing, washing with water and drying (air flow). After heating this substrate a to 80 ° C., the photosensitive element was laminated so that the photosensitive layer was in contact with the copper layer while peeling off the protective film of the photosensitive element described above.
  • a 41-step step tablet was placed as a negative on the support film of the above-mentioned laminate. Then, using a high-resolution projection exposure machine (manufactured by Ushio, Inc., trade name: UX-2240) equipped with a high-pressure mercury lamp, the irradiation amount is determined in order to obtain the irradiation energy amount at which the number of resist curing stages after development is 11. The photosensitive layer was exposed while adjusting.
  • a high-resolution projection exposure machine manufactured by Ushio, Inc., trade name: UX-2240
  • the photosensitive layer was spray-developed with a 1% by mass sodium carbonate aqueous solution at 30 ° C. for twice the minimum development time to remove the unexposed portion. Then, it was confirmed that the number of steps of the step tablet of the photocurable film formed on the above-mentioned substrate was 11, and the irradiation energy amount (exposure amount, mJ / cm 2 ) in the above-mentioned exposure was obtained. The results are shown in Table 2.
  • a machine UX-2240 manufactured by Ushio Denki Co., Ltd.
  • the photosensitive layer of the laminated body was exposed with an irradiation energy amount such that the number of remaining steps after development of the 41-step step tablet was 11.
  • the support film was peeled off, and a 1% by mass sodium carbonate aqueous solution was spray-developed at 30 ° C. for twice the minimum development time to remove the unexposed portion.
  • the adhesion and the resolution were evaluated by the smallest value (unit: ⁇ m) of the space width between the line widths in which the unexposed portion could be removed cleanly by the developing process. The results are shown in Table 2. The smaller the numerical value, the better the evaluation of adhesion and resolution.
  • Example 2 As shown in Table 2, when a high-resolution projection exposure machine was used, the number of resist defects was 100 or less in the examples, whereas a large number of resist defects were found in the comparative example. Was confirmed. In Example 1, although the number of defects inside the support film was 0, it is presumed that the resist was defective due to an external factor that was difficult to avoid in the evaluation process.
  • Photosensitive element 10 ... Support film, 10a ... First main surface, 10b ... Second main surface, 20 ... Photosensitive layer.

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Abstract

Un élément photosensible (1) comprend un film de support (10) et une couche photosensible (20)disposée sur le film de support (10). Le nombre de défauts ayant un diamètre maximal de 1 µm ou plus à l'intérieur du film de support (10) n'est pas supérieur à 100 pour 0,225 mm2. La couche photosensible (20) contient un polymère liant, un composé photopolymérisable ayant une liaison éthylénique insaturée, et un initiateur de photopolymérisation.
PCT/JP2020/042510 2020-11-13 2020-11-13 Élément photosensible, procédé de production d'article durci, procédé de production d'un motif d'article durci, et procédé de production de carte de câblage WO2022102101A1 (fr)

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PCT/JP2020/042510 WO2022102101A1 (fr) 2020-11-13 2020-11-13 Élément photosensible, procédé de production d'article durci, procédé de production d'un motif d'article durci, et procédé de production de carte de câblage
CN202180038977.0A CN116830037A (zh) 2020-11-13 2021-11-10 感光性元件、固化物的制造方法、固化物图案的制造方法及线路板的制造方法
PCT/JP2021/041406 WO2022102675A1 (fr) 2020-11-13 2021-11-10 Élément photosensible, procédé de production de produit durci, procédé de production de motif de produit durci, et procédé de production de carte de câblage
KR1020227038217A KR20230107474A (ko) 2020-11-13 2021-11-10 감광성 엘리먼트, 경화물의 제조 방법, 경화물 패턴의 제조 방법, 및, 배선판의 제조 방법
JP2022561974A JPWO2022102675A1 (fr) 2020-11-13 2021-11-10
TW110141999A TW202225837A (zh) 2020-11-13 2021-11-11 感光性元件、固化物之製造方法、固化物圖案之製造方法及配線板之製造方法

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PCT/JP2021/041406 WO2022102675A1 (fr) 2020-11-13 2021-11-10 Élément photosensible, procédé de production de produit durci, procédé de production de motif de produit durci, et procédé de production de carte de câblage

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018100730A1 (fr) * 2016-12-02 2018-06-07 日立化成株式会社 Élément photosensible, procédé de formation d'un motif de réserve et procédé de production de carte à câblage imprimé
JP2019101405A (ja) * 2017-12-04 2019-06-24 旭化成株式会社 感光性樹脂積層体ロール

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JP2001013681A (ja) 1999-06-28 2001-01-19 Hitachi Chem Co Ltd 感光性エレメント、レジストパターンの製造法及びプリント配線板の製造法
JP2014074764A (ja) 2012-10-03 2014-04-24 Hitachi Chemical Co Ltd 感光性エレメント及びこれを用いたレジストパターンの形成方法、プリント配線板の製造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018100730A1 (fr) * 2016-12-02 2018-06-07 日立化成株式会社 Élément photosensible, procédé de formation d'un motif de réserve et procédé de production de carte à câblage imprimé
JP2019101405A (ja) * 2017-12-04 2019-06-24 旭化成株式会社 感光性樹脂積層体ロール

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