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WO2018143220A1 - Composition de résine photodurcissable, film sec, produit durci et carte imprimée - Google Patents

Composition de résine photodurcissable, film sec, produit durci et carte imprimée Download PDF

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Publication number
WO2018143220A1
WO2018143220A1 PCT/JP2018/003042 JP2018003042W WO2018143220A1 WO 2018143220 A1 WO2018143220 A1 WO 2018143220A1 JP 2018003042 W JP2018003042 W JP 2018003042W WO 2018143220 A1 WO2018143220 A1 WO 2018143220A1
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Prior art keywords
resin composition
photocurable resin
group
resin
parts
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Ceased
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PCT/JP2018/003042
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English (en)
Japanese (ja)
Inventor
岡田　和也
知哉 工藤
千穂 植田
信人 伊藤
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Taiyo Holdings Co Ltd
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Taiyo Ink Mfg Co Ltd
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Priority to JP2018565577A priority Critical patent/JP7181094B2/ja
Publication of WO2018143220A1 publication Critical patent/WO2018143220A1/fr
Anticipated expiration legal-status Critical
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    • 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings

Definitions

  • the present invention relates to a photocurable resin composition, a dry film, a cured product, and a printed wiring board.
  • a photocurable resin composition is generally employed for the formation of a permanent film such as a solder resist.
  • a photocurable resin composition a dry film type composition or a liquid composition is used. Things are being developed.
  • an alkali development type photocurable resin composition using a dilute alkaline aqueous solution as a developing solution has become the mainstream, and several composition systems have been conventionally proposed (for example, Patent Document 1).
  • a permanent film such as a solder resist formed on a printed wiring board (also referred to as a package substrate) used in such an IC package is required.
  • an object of the present invention is to provide a photocurable resin composition capable of forming a cured product excellent in appearance and surface smoothness and capable of alkali development with excellent sensitivity and resolution, and obtained from the composition.
  • Another object of the present invention is to provide a dry film having a resin layer, a cured product of the composition or the resin layer of the dry film, and a printed wiring board having the cured product.
  • the present inventors have found that the above problem can be solved by combining a blue colorant having an average particle size of a specific value or less and an inorganic filler having an average particle size of a specific value or less.
  • the present invention has been completed.
  • the photocurable resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a blue colorant, and (D) an alkali-developable light containing an inorganic filler.
  • the photocurable resin composition of the present invention preferably further contains an organic filler having an amino group having an average particle size of 1 ⁇ m or less and a maximum particle size of 6 ⁇ m or less as a thermosetting catalyst.
  • the photocurable resin composition of the present invention contains an oxime ester photopolymerization initiator as the photopolymerization initiator (B), and the blending amount of the oxime ester photopolymerization initiator is based on the total amount of the photopolymerization initiator.
  • the solid content is preferably 8% by mass or more.
  • the blending amount of the (C) blue colorant is preferably 0.18 to 0.50% by mass in terms of solid content per total amount of the photocurable resin composition. .
  • the dry film of the present invention has a resin layer obtained from the photocurable resin composition.
  • the cured product of the present invention is obtained by curing the photocurable resin composition or the resin layer of the dry film.
  • the printed wiring board of the present invention is characterized by having the cured product.
  • a cured product excellent in appearance and surface smoothness can be formed, and an alkali developable photocurable resin composition excellent in sensitivity and resolution can be obtained from the composition.
  • a dry film having a resin layer, a cured product of the resin layer of the composition or the dry film, and a printed wiring board having the cured product can be provided.
  • the photocurable resin composition of the present invention comprises (A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a blue colorant, and (D) an alkali-developable photocurable resin containing an inorganic filler.
  • the resin composition is characterized in that the average particle size of the (C) blue colorant is 300 nm or less, and the average particle size of the (D) inorganic filler is 1.0 ⁇ m or less.
  • the average particle size of the blue colorant is 300 nm or less
  • (D) the average particle size of the inorganic filler is 1.0 ⁇ m or less, so that light (particularly i-line (365 nm)) The transmittance is improved.
  • the sensitivity is unlikely to decrease and light easily reaches the deep part, so that undercutting in the deep part is unlikely to occur, and good resolution is considered to be obtained.
  • a thin part for example, a base material on which a copper circuit is formed, halation hardly occurs on the copper circuit, and good resolution can be obtained from this point.
  • the resin composition is apply
  • the sensitivity is further improved while minimizing the increase in absorbance. Thereby, it is possible to easily form a cured film with high sensitivity and excellent resolution without undercut.
  • (meth) acrylate is a term which generically refers to acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.
  • (A) Alkali-soluble resin examples include compounds having two or more phenolic hydroxyl groups, carboxyl group-containing resins, compounds having phenolic hydroxyl groups and carboxyl groups, and compounds having two or more thiol groups.
  • the alkali-soluble resin is a carboxyl group-containing resin or a phenol resin because adhesion with the base is improved.
  • the alkali-soluble resin is more preferably a carboxyl group-containing resin.
  • the carboxyl group-containing resin is preferably a carboxyl group-containing photosensitive resin having an ethylenically unsaturated double bond, but may be a carboxyl group-containing resin having no ethylenically unsaturated double bond.
  • carboxyl group-containing resin examples include the compounds listed below (any of oligomers and polymers).
  • a carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, ⁇ -methylstyrene, lower alkyl (meth) acrylate, and isobutylene.
  • Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers
  • carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
  • Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems
  • a terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.
  • Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its partial acid anhydride modified product, carboxyl group-containing dialcohol compound and diol compound.
  • one isocyanate group and one or more (meth) acryloyl groups are introduced into the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate.
  • the carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.
  • a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride
  • a carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.
  • Reaction product obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide, with an unsaturated group-containing monocarboxylic acid.
  • a carboxyl group-containing resin obtained by reacting a polybasic acid anhydride with a product.
  • (11) Obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a reaction product obtained by reacting a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with an unsaturated group-containing monocarboxylic acid.
  • a carboxyl group-containing resin obtained by reacting a reaction product with a polybasic acid anhydride.
  • An epoxy compound having a plurality of epoxy groups in one molecule a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as p-hydroxyphenethyl alcohol, and (meth) Reaction with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and with respect to the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, anhydrous A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride such as adipic acid.
  • carboxyl group-containing resins the carboxyl group-containing resins described in (1), (7), (8), (10) to (13) are preferable.
  • Examples of the compound having a phenolic hydroxyl group include a compound having a biphenyl skeleton and / or a phenylene skeleton, phenol, orthocresol, paracresol, metacresol, 2,3-xylenol, 2,4-xylenol, 2 , 5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, phloroglucinol, etc. And phenol resins having various skeletons synthesized.
  • Examples of the compound having a phenolic hydroxyl group include a phenol novolac resin, an alkylphenol volac resin, a bisphenol A novolac resin, a dicyclopentadiene type phenol resin, an Xylok type phenol resin, a terpene modified phenol resin, a polyvinylphenol, and bisphenol F.
  • bisphenol S-type phenol resins poly-p-hydroxystyrene, condensates of naphthol and aldehydes, and condensates of dihydroxynaphthalene and aldehydes.
  • phenol resins examples include HF1H60 (Maywa Kasei Co., Ltd.), Phenolite TD-2090, Phenolite TD-2131 (Dai Nippon Printing Co., Ltd.), Vesmol CZ-256-A (Dic Co., Ltd.), Siyonor BRG-555, Siyonor BRG-556 (manufactured by Showa Denko), CGR-951 (manufactured by Maruzen Petroleum Co., Ltd.), polyvinylphenol CST70, CST90, S-1P and S-2P (manufactured by Maruzen Petroleum Co., Ltd.).
  • the acid value of the alkali-soluble resin is suitably in the range of 40 to 200 mgKOH / g, more preferably in the range of 45 to 120 mgKOH / g. It is preferable that the acid value of the alkali-soluble resin is 40 mgKOH / g or more because alkali development is facilitated, while normal resist pattern drawing of 200 mgKOH / g or less is facilitated.
  • the weight average molecular weight of the alkali-soluble resin varies depending on the resin skeleton, but is preferably in the range of 1,500 to 150,000, more preferably 1,500 to 100,000.
  • the weight average molecular weight is 1,500 or more, the tack-free performance is good, the moisture resistance of the coated film after exposure is good, the film loss during development can be suppressed, and the resolution can be suppressed from decreasing.
  • the weight average molecular weight is 150,000 or less, the developability is good and the storage stability is also excellent.
  • the alkali-soluble resin can be used alone or in combination of two or more.
  • the photocurable resin composition of the present invention may be any photopolymerization initiator as long as it is a known photopolymerization initiator as a photopolymerization initiator or a photoradical generator.
  • Examples of the photopolymerization initiator include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, Bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4 , 6-Trimethylbenzoyl) -phenylphosphine oxy Bisacylphosphine
  • a photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type.
  • oxime esters hereinafter also referred to as “oxime ester photopolymerization initiators”
  • ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) is more preferred.
  • the blending amount of the (B) photopolymerization initiator is, for example, 0.01 to 30 parts by mass with respect to 100 parts by mass of the solid content of the (A) alkali-soluble resin.
  • the blending amount of the oxime ester photopolymerization initiator is preferably 8% by mass or more and more preferably 12% by mass or more in terms of solid content with respect to the total amount of the photopolymerization initiator. High sensitivity can be easily achieved by containing 8 mass% or more.
  • An oxime ester photoinitiator can be used individually by 1 type or in combination of 2 or more types.
  • Any known oxime ester photopolymerization initiator can be used as the oxime ester photopolymerization initiator.
  • Commercially available products include CGI-325 manufactured by BASF Japan, Irgacure OXE01 (1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)]), Irgacure OXE02 ( Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)), ADEKA N-1919, NCI-831, Changzhou TR-PBG-304 manufactured by Strong Electronic New Materials Co., Ltd.
  • an initiator having two oxime ester groups in the molecule can also be suitably used.
  • Specific examples include oxime ester compounds having a carbazole structure represented by the following general formula.
  • X is a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms).
  • Y and Z are each a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, or a carbon number of 1), and is substituted by an alkylamino group having a C 1-8 alkyl group or a dialkylamino group.
  • X and Y are each a methyl group or an ethyl group
  • Z is a methyl group or a phenyl group
  • n is 0,
  • Ar is a bond, phenylene, naphthylene, thiophene or thienylene. It is preferable that
  • the compound which can be represented by the following general formula can also be mentioned as a preferable carbazole oxime ester compound.
  • R 1 represents an alkyl group having 1 to 4 carbon atoms, or a phenyl group optionally substituted with a nitro group, a halogen atom, or an alkyl group having 1 to 4 carbon atoms).
  • R 2 represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group.
  • R 3 may be linked with an oxygen atom or a sulfur atom, and may be substituted with an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 4 carbon atoms which may be substituted with a phenyl group.
  • R 4 represents a nitro group or an acyl group represented by X—C ( ⁇ O) —.
  • X represents an aryl group, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula, which may be substituted with an alkyl group having 1 to 4 carbon atoms.
  • the photocurable resin composition of the present invention contains a blue colorant having an average particle size of 300 nm or less.
  • the average particle size is preferably 280 nm or less, and more preferably 250 nm or less.
  • the average particle diameter of the blue colorant is a value of D50 measured by a laser diffraction method.
  • An example of a measuring apparatus using the laser diffraction method is Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd.
  • the maximum particle size (D100) of the blue colorant is preferably 800 nm or less, more preferably 700 nm or less, and even more preferably 600 nm or less. When it is 800 nm or less, coarse grains are reduced and the appearance of the cured product becomes better. Specifically, when the cured film is observed by the method described in the examples below, it is possible to prevent generation of particles of 10 ⁇ m or more.
  • the photocurable resin composition of the present invention even if (C) the blue colorant is blended in a relatively large amount of 0.18% by mass or more in terms of solid content, sensitivity and resolution are unlikely to decrease. In particular, it is possible to achieve both sensitivity, resolution, and concealment of the cured product, which are difficult to achieve at the time of thinning. In the case of 0.50 mass% or less, the resolution is more excellent. More preferably, it is 0.20 mass% to 0.40 mass%.
  • the type of the blue colorant is not particularly limited, and a known and commonly used blue colorant can be used, and any of a pigment, a dye, and a pigment may be used, but among them, those containing no halogen atom are preferable.
  • Blue colorants include phthalocyanine and anthraquinone, and pigments include compounds classified as Pigment, specifically, Pigment Blue 15 and 15: 1. , 15: 2, 15: 3, 15: 4, 15: 6, 16, 60.
  • Solvent Blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70 and the like can be used.
  • a metal-substituted or unsubstituted phthalocyanine compound can also be used.
  • a blue colorant may be used individually by 1 type, and may use 2 or more types together.
  • the method for adjusting the average particle diameter of the blue colorant is not particularly limited, but it is preferably dispersed in a solvent or the like by, for example, a bead mill or a jet mill.
  • a commercially available product having an average particle diameter in the above range may be used as it is.
  • the blue colorant is preferably blended in a slurry state.
  • a slurry state high dispersion can be easily achieved, and aggregation can be prevented to facilitate handling as a colorant having an average particle size in the specific range.
  • the blue colorant preferably has an absorbance at a wavelength of 365 nm of 0.5 to 1.0 by the following measurement method.
  • the measurement method is as follows. First, 0.1 part of a blue colorant is added to 100 parts of the nonvolatile solid content of the alkali-soluble resin A-3 described in the Examples having no absorption at a wavelength of 365 nm to prepare a composition. After drying the composition on glass with an applicator at 80 ° C. for 30 minutes, a dried coating film is formed to a thickness of 15 ⁇ m, and the absorbance is measured with an ultraviolet-visible-near infrared spectrophotometer V-670 (manufactured by JASCO Corporation). To implement.
  • the photocurable resin composition of the present invention may contain other colorants as long as the effects of the present invention are not impaired.
  • colorants red, green, yellow, white, black, (C) known colorants such as blue colorants other than blue colorants can be used, and any of pigments, dyes, and pigments can be used. Good. Specifically, the color index (CI; issued by The Society of Dyers and Colorists) number is given. However, it is preferable that the colorant does not contain a halogen from the viewpoint of reducing environmental burden and affecting the human body.
  • the average particle diameter of colorants other than blue is also preferably small, and is preferably 300 nm or less. By reducing the average particle size of the colorant other than blue, the sensitivity, resolution, surface smoothness of the cured product, appearance, and the like are further improved.
  • red colorant examples include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone.
  • blue colorants include metal-substituted or unsubstituted phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds that are classified as pigments.
  • the green colorant includes metal-substituted or unsubstituted phthalocyanine-based, anthraquinone-based, and perylene-based materials.
  • yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone.
  • white colorant examples include rutile type, anatase type titanium oxide and the like.
  • Black colorants include titanium black, carbon black, graphite, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, and aniline. Examples thereof include pigments, molybdenum sulfide, and bismuth sulfide.
  • a colorant such as purple, orange or brown may be added for the purpose of adjusting the color tone.
  • the photocurable resin composition of the present invention contains an inorganic filler having an average particle size of 1.0 ⁇ m or less and preferably an average particle size of 0.8 ⁇ m or less.
  • (D) The average particle diameter of the inorganic filler is a value of D50 measured by a laser diffraction method.
  • An example of a measuring apparatus using the laser diffraction method is Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd.
  • the inorganic filler is not particularly limited and is a known and commonly used inorganic filler such as silica, crystalline silica, Neuburg silica, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, synthetic Inorganic fillers such as mica, aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, and zinc white can be used.
  • silica is preferable, and since the surface area is small and stress is dispersed throughout, it is difficult to become a starting point of cracks, and thus spherical silica is more preferable.
  • the inorganic filler may be surface-treated.
  • the surface treatment of the inorganic filler refers to a treatment for improving the compatibility with the resin component.
  • the surface treatment of the inorganic filler may be either a surface treatment that can introduce a curable reactive group on the surface of the inorganic filler or a surface treatment that does not introduce it.
  • the curable reactive group is not particularly limited as long as it is a group that undergoes a curing reaction with a curable compound such as (A) an alkali-soluble resin or a thermosetting component, and even a photocurable reactive group is a thermosetting reactive group. But you can.
  • photocurable reactive groups include methacrylic groups, acrylic groups, vinyl groups, styryl groups, and thermosetting reactive groups include epoxy groups, amino groups, hydroxyl groups, carboxyl groups, isocyanate groups, imino groups, oxetanyl. Group, mercapto group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group, oxazoline group and the like.
  • the method for introducing the curable reactive group into the surface of the inorganic filler is not particularly limited, and may be introduced using a known and commonly used method.
  • a surface treatment agent having a curable reactive group for example, a curable reactive group is converted into an organic group.
  • an inorganic filler with the coupling agent etc. which have as above.
  • a silane coupling agent a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, or the like can be used.
  • the surface-treated inorganic filler having no curable reactive group include silica-alumina surface treatment, titanate coupling agent treatment, aluminate coupling agent treatment, and organic treatment inorganic filler. Can be mentioned.
  • the method for adjusting the average particle diameter of the inorganic filler is not particularly limited, for example, it is preferably predispersed by a bead mill or a jet mill. Moreover, you may use the commercial item which has an average particle diameter in the said range as (D) inorganic filler as it is.
  • the inorganic filler is preferably blended in a slurry state.
  • high dispersion is easy, and aggregation is prevented and handling as an inorganic filler having an average particle diameter in the specific range is facilitated.
  • the blending amount of the (D) inorganic filler is preferably 80 to 450 parts by weight, and more preferably 100 to 200 parts by weight with respect to 100 parts by weight of the solid content of the (A) alkali-soluble resin. In the case of 80 parts by mass or more, the heat resistance is excellent. In the case of 450 parts by mass or less, the resolution is more excellent.
  • thermosetting component The photocurable resin composition of the present invention preferably contains a thermosetting component. It can be expected that heat resistance is improved by adding a thermosetting component.
  • a thermosetting component can be used individually by 1 type or in combination of 2 or more types. Any known thermosetting component can be used.
  • known thermosetting components such as melamine resins, benzoguanamine resins, melamine derivatives, amino resins such as benzoguanamine derivatives, isocyanate compounds, blocked isocyanate compounds, cyclocarbonate compounds, epoxy compounds, oxetane compounds, episulfide resins, bismaleimides, carbodiimide resins, etc.
  • a thermosetting component having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.
  • thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is a compound having a plurality of 3, 4 or 5-membered cyclic (thio) ether groups in the molecule.
  • a compound having an epoxy group that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, that is, an episulfide resin.
  • Polyfunctional epoxy compounds include epoxidized vegetable oils; bisphenol A type epoxy resins; hydroquinone type epoxy resins; bisphenol type epoxy resins; thioether type epoxy resins; brominated epoxy resins; novolac type epoxy resins; biphenol novolac type epoxy resins; Type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; hydantoin type epoxy resin; alicyclic epoxy resin; trihydroxyphenylmethane type epoxy resin; bixylenol type or biphenol type epoxy resin or a mixture thereof; Bisphenol S type epoxy resin; Bisphenol A novolak type epoxy resin; Tetraphenylol ethane type epoxy resin; Heterocyclic epoxy resin; Phthalate resin; Tetraglycidylxylenoylethane resin; Naphthalene group-containing epoxy resin; Epoxy resin having dicyclopentadiene skeleton; Glycidyl methacrylate copolymer epoxy resin; Copolymer epoxy resin of
  • epoxy resins can be used alone or in combination of two or more.
  • novolak type epoxy resins bisphenol type epoxy resins, bixylenol type epoxy resins, biphenol type epoxy resins, biphenol novolac type epoxy resins, naphthalene type epoxy resins or mixtures thereof are particularly preferable.
  • polyfunctional oxetane compound examples include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3- Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3- In addition to polyfunctional oxetanes such as oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolak resin , Poly (p-hydroxy
  • Examples of the compound having a plurality of cyclic thioether groups in the molecule include bisphenol A type episulfide resin. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.
  • the blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in such a molecule is such that the cyclic (thio) ether group is an alkali-soluble group 1 such as a carboxyl group or phenolic hydroxyl group of (A) an alkali-soluble resin.
  • the equivalent amount is preferably 0.6 to 2.5 equivalents, more preferably 0.8 to 2.0 equivalents.
  • amino resins such as melamine derivatives and benzoguanamine derivatives include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.
  • polyisocyanate compound a polyisocyanate compound can be blended.
  • Polyisocyanate compounds include 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, and Aromatic polyisocyanates such as 2,4-tolylene dimer; aliphatic polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate; Alicyclic polyisocyanates such as heptane triisocyanate; and adducts of the isocyanate compounds listed above, Yuret
  • an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used.
  • an isocyanate compound which can react with an isocyanate blocking agent the above-mentioned polyisocyanate compound etc. are mentioned, for example.
  • an isocyanate block agent for example, phenol block agent; lactam block agent; active methylene block agent; alcohol block agent; oxime block agent; mercaptan block agent; acid amide block agent; imide block agent; Examples include amine-based blocking agents; imidazole-based blocking agents; imine-based blocking agents.
  • thermosetting component can be used alone or in combination of two or more.
  • the blending amount of the thermosetting component is preferably 20 to 60 parts by mass, more preferably 30 to 50 parts by mass with respect to 100 parts by mass of the solid content of the (A) alkali-soluble resin.
  • the heat resistance is excellent.
  • the storage stability is improved.
  • the photocurable resin composition of this invention can contain what functions as a reactive diluent, specifically, the compound which has an ethylenically unsaturated group.
  • a photopolymerizable oligomer, a photopolymerizable vinyl monomer, or the like that is a known and commonly used photocurable monomer can be used.
  • Examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers.
  • Examples of (meth) acrylate oligomers include phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, epoxy (meth) acrylates such as bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meta ) Acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate, and the like.
  • photopolymerizable vinyl monomer known and commonly used monomers, for example, styrene derivatives such as styrene, chlorostyrene and ⁇ -methylstyrene; vinyl esters such as vinyl acetate, vinyl butyrate or vinyl benzoate; vinyl isobutyl ether, vinyl- vinyl ethers such as n-butyl ether, vinyl-t-butyl ether, vinyl-n-amyl ether, vinyl isoamyl ether, vinyl-n-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; acrylamide, Methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide (Meth) acrylamides such as rilamide and N-butoxymethylacrylamide; allyl compounds such as triallyl isocyan
  • the compounds having an ethylenically unsaturated group can be used singly or in combination of two or more.
  • the compounding amount of the compound having an ethylenically unsaturated group is preferably 3 to 25 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the solid content of the (A) alkali-soluble resin. . In the case of 3 parts by mass or more, it contributes to high sensitivity. In the case of 25 parts by mass or less, the resolution is good.
  • thermosetting catalyst The photocurable resin composition of the present invention can contain a thermosetting catalyst.
  • thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole.
  • Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine.
  • an organic filler may be used as long as it can be used as a thermosetting catalyst.
  • the thermosetting catalyst preferably has an average particle size (D50) of 1 ⁇ m or less and a maximum particle size (D100) of 6 ⁇ m or less.
  • the average particle size is preferably 800 nm or less, and more preferably 600 nm or less.
  • the maximum particle size is preferably 5 ⁇ m or less, more preferably 4 ⁇ m or less.
  • the average particle diameter is a value of D50 measured by a laser diffraction method.
  • An example of a measuring apparatus using a laser diffraction method is Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd.
  • thermosetting catalyst an organic filler having an amino group is preferable, and specifically, at least one of melamine and dicyandiamide (DICY) is preferable.
  • thermosetting catalyst can be used alone or in combination of two or more.
  • the blending amount of the thermosetting catalyst is preferably 0.5 to 10 parts by mass and more preferably 1 to 8 parts by mass with respect to 100 parts by mass of the solid content of the (A) alkali-soluble resin.
  • the heat resistance is excellent.
  • 10 parts by mass or less the storage stability is improved.
  • the photocurable resin composition of the present invention can contain an organic solvent for the purpose of preparing the composition and adjusting the viscosity when applied to a substrate or a carrier film.
  • organic solvents include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether , Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbito
  • additives include thermal polymerization inhibitors, UV absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, antibacterial / antifungal agents, antifoaming agents, leveling agents, thickening agents Agent, adhesion imparting agent, thixotropic agent, photoinitiator aid, sensitizer, thermoplastic resin, organic filler, mold release agent, surface treatment agent, dispersant, dispersion aid, surface modifier, stabilizer And phosphors.
  • the photocurable resin composition of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-component or two-component or more.
  • the photocurable resin composition of the present invention preferably has an absorbance at a wavelength of 365 nm of 0.3 to 0.85 per 15 ⁇ m thickness of the dried coating film.
  • the dry film of the present invention has a resin layer obtained by applying and drying the photocurable resin composition of the present invention on a carrier film.
  • the photocurable resin composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and then a comma coater, a blade coater, a lip coater, a rod coater, a squeeze.
  • the coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc. are used to apply a uniform thickness on the carrier film.
  • the applied composition is usually dried at a temperature of 40 to 130 ° C. for 1 to 30 minutes to form a resin layer.
  • the coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 3 to 150 ⁇ m, preferably 5 to 60 ⁇ m.
  • a plastic film is used as the carrier film.
  • a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used.
  • the thickness of the carrier film is not particularly limited, but is generally appropriately selected within the range of 10 to 150 ⁇ m. More preferably, it is in the range of 15 to 130 ⁇ m.
  • the resin layer made of the photocurable resin composition of the present invention After the resin layer made of the photocurable resin composition of the present invention is formed on the carrier film, it can be further peeled off from the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. It is preferable to laminate a cover film.
  • a cover film As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used.
  • a cover film what is necessary is just a thing smaller than the adhesive force of a resin layer and a carrier film when peeling a cover film.
  • a resin layer may be formed by applying and drying the photocurable resin composition of the present invention on the cover film, and a carrier film may be laminated on the surface. That is, as a film to which the photocurable resin composition of the present invention is applied when producing a dry film in the present invention, either a carrier film or a cover film may be used.
  • the printed wiring board of the present invention has a cured product obtained from the photocurable resin composition of the present invention or a resin layer of a dry film.
  • the photocurable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using the organic solvent, and a dip coating method is performed on a substrate.
  • the organic solvent contained in the composition is volatilized and dried (temporary drying) By doing so, a tack-free resin layer is formed.
  • a resin layer is formed on a base material by peeling a carrier film.
  • Examples of the base material include printed wiring boards and flexible printed wiring boards that have been previously formed with copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy.
  • PEN polyethylene naphthalate
  • Volatile drying performed after applying the photocurable resin composition of the present invention is performed in a dryer using a hot-air circulating drying furnace, an IR furnace, a hot plate, a convection oven or the like (equipped with a heat source of an air heating method using steam). And a method of spraying the hot air against the support from a nozzle).
  • a resin layer on the printed wiring board After forming a resin layer on the printed wiring board, it is selectively exposed with active energy rays through a photomask having a predetermined pattern, and the unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3 to 3 mass% sodium carbonate aqueous solution). ) To form a cured product pattern. Further, the cured product is irradiated with active energy rays and then heat-cured (for example, 100 to 220 ° C.), irradiated with active energy rays after heat-curing, or is subjected to final finish curing (main curing) only by heat-curing. A cured film having excellent properties such as properties and hardness is formed.
  • the photocurable resin composition of the present invention contains a photobase generator, it is preferably heated after exposure and before development. The heating conditions before development after exposure are, for example, 1 to 60 to 150 ° C. Heating for ⁇ 60 minutes is preferred.
  • the exposure apparatus used for the active energy ray irradiation may be any apparatus that irradiates ultraviolet rays in the range of 350 to 450 nm, equipped with a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, etc.
  • a direct drawing apparatus for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer
  • the lamp light source or laser light source of the direct drawing machine may have a maximum wavelength in the range of 350 to 450 nm.
  • the exposure amount for image formation varies depending on the film thickness and the like, but can be generally in the range of 10 to 1000 mJ / cm 2 , preferably 20 to 800 mJ / cm 2 .
  • the developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.
  • the photocurable resin composition of the present invention is preferably used for forming a cured film on a printed wiring board, more preferably used for forming a permanent coating film, and more preferably a solder. Used to form resists, interlayer insulation layers, and coverlays.
  • a cured product excellent in appearance and surface smoothness can be obtained even in a thin film, and since the sensitivity and resolution are excellent, the thin film has high reliability. It can be suitably used for forming a required printed wiring board, for example, a package substrate, particularly a permanent coating (particularly a solder resist) for FC-BGA.
  • the photocurable resin composition of the present invention can be suitably used for forming a thin film, preferably a cured film having a thickness of 3 to 40 ⁇ m, more preferably 5 to 30 ⁇ m.
  • reaction solution was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added to and mixed with the reaction solution to neutralize potassium hydroxide.
  • the nonvolatile content was 62.1%, and the hydroxyl value was 182.2 mgKOH / g (307. 9 g / eq.) Of a novolak-type cresol resin propylene oxide reaction solution. This was an average of 1.08 mol of propylene oxide added per equivalent of phenolic hydroxyl group.
  • reaction solution was cooled to room temperature, neutralized with 35.35 parts of a 15% aqueous sodium hydroxide solution, and then washed with water. Thereafter, toluene was distilled off while substituting 118.1 parts of diethylene glycol monoethyl ether acetate with an evaporator to obtain a novolak acrylate resin solution.
  • 332.5 parts of the obtained novolak acrylate resin solution and 1.22 parts of triphenylphosphine were introduced into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air was supplied at a rate of 10 ml / min.
  • Diethylene glycol monoethyl ether acetate was added to obtain an acrylate resin solution having a solid content of 67%.
  • 322 parts of the obtained acrylate resin solution, 0.1 part of hydroquinone monomethyl ether, and 0.3 part of triphenylphosphine were charged.
  • 60 parts of tetrahydrophthalic anhydride was added, reacted for 4 hours, cooled and taken out.
  • the photosensitive carboxyl group-containing resin solution thus obtained had a solid content of 70% and a solid content acid value of 81 mgKOH / g.
  • this carboxyl group-containing photosensitive resin solution is referred to as Resin Solution A-2.
  • the D50 value was 220 nm and the D100 value was 600 nm as measured by the laser diffraction method.
  • C-2 A blue colorant slurry C-2 was obtained in the same manner as in the preparation of (C-1) except that the dispersion time of the bead mill was changed to 2 hours.
  • the average particle size of the obtained phthalocyanine blue was obtained by using a Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. and measuring a sample diluted to an appropriate measurement concentration with MIBK.
  • the D50 value was 280 nm and the D100 value was 600 nm as measured by the laser diffraction method.
  • silica slurry D-1 (Preparation of silica slurry D-1) 2 parts by weight of 70 parts by weight of spherical silica (SFP-20M manufactured by Denka), 25 parts by weight of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 5 parts by weight of a dispersant (BYK-111 manufactured by BYK Japan) Silica slurry D-1 was obtained by uniform dispersion over time.
  • the average particle diameter of the obtained spherical silica was obtained by using a Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. and measuring a sample diluted to an appropriate measurement concentration with MIBK. As a result of measuring this sample, the value measured by the laser diffraction method was D50 of 0.70 ⁇ m and D100 of 1.7 ⁇ m.
  • silica slurry RD-1 (Preparation of RD-1) 2 parts by mass of 70 parts by weight of spherical silica (FB-5D manufactured by Denka), 25 parts by weight of PMA (propylene glycol monomethyl ether acetate) as a solvent and 5 parts by weight of a dispersant (BYK-111 manufactured by BYK Japan)
  • Silica slurry D-1 was obtained by uniform dispersion over time.
  • the average particle diameter of the obtained spherical silica was obtained by using a Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. and measuring a sample diluted to an appropriate measurement concentration with MIBK. As a result of measuring this sample, the D50 value was 5.0 ⁇ m and the D100 value was 12.5 ⁇ m as measured by the laser diffraction method.
  • Melamine dispersion product 1 was obtained by mixing 55 parts by mass of melamine and 45 parts by mass of carbitol acetate and dispersing the mixture in a bead mill for 2 hours.
  • the average particle size and the maximum particle size of the obtained melamine dispersion 1 were obtained by using a Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. and measuring a sample diluted with MIBK to a measurement appropriate concentration.
  • the value measured by laser diffraction method was D50 of 600 nm and D100 of 5.0 ⁇ m.
  • (Preparation of melamine dispersion 2) Melamine dispersion product 2 was obtained by mixing 55 parts by mass of melamine and 45 parts by mass of carbitol acetate and dispersing the mixture in a bead mill for 4 hours.
  • the average particle size and the maximum particle size of the obtained melamine dispersion were obtained by using Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. and measuring a sample diluted with MIBK to an appropriate measurement concentration. As a result of measuring this sample, the value measured by laser diffraction method was D50 of 400 nm and D100 of 4.0 ⁇ m.
  • DIX Dicyandiamide
  • 70 parts by mass of dicyandiamide and 30 parts by mass of carbitol acetate were mixed and dispersed with a bead mill for 2 hours to obtain a DICY dispersion 1.
  • the average particle size and the maximum particle size of the obtained DICY dispersion 1 were obtained by using a Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. and measuring a sample diluted to an appropriate measurement concentration with MIBK.
  • the value measured by laser diffraction method was D50 of 800 nm and D100 of 6.0 ⁇ m.
  • DIX Dicyandiamide
  • 70 parts by mass of dicyandiamide and 30 parts by mass of carbitol acetate were mixed and dispersed with a bead mill for 4 hours to obtain a DICY dispersion 2.
  • the average particle size and the maximum particle size of the obtained DICY dispersion 1 were obtained by using a Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. and measuring a sample diluted to an appropriate measurement concentration with MIBK. As a result of measuring this sample, the value measured by laser diffraction method was D50 of 400 nm and D100 of 4.0 ⁇ m.
  • Examples 1 to 14 Comparative Examples 1 and 2
  • the components shown in Tables 1 to 3 below were blended in the proportions (parts by mass) shown in Tables 1 to 4, premixed with a stirrer, kneaded with a three-bead mill, and photocurable resin composition was prepared.
  • surface shows solid content (nonvolatile content).
  • the prepared photocurable resin composition was applied onto a PET film with an applicator so that the thickness of the resin layer after drying was a predetermined thickness, and dried at 80 ° C. for 30 minutes to obtain a dry film.
  • sensitivity According to the method described above (production of dry film), a dry film having a resin layer thickness of 15 ⁇ m after drying was produced. Using a projection exposure machine UFX-2223M-APU01 in which a dry film with a resin layer thickness of 15 ⁇ m was laminated on a substrate having a CZ-treated 35 ⁇ m copper foil and the longer wavelength side was cut from the i-line, Exposure was made through 41 steps of a Stuffer step tablet. When the PET film was peeled off and developed with a 1.0 wt% aqueous sodium carbonate solution for 60 seconds, the exposure amount having a gloss sensitivity of 8 or more was measured. ⁇ : Less than 200 mJ ⁇ : 200 mJ or more and less than 350 mJ ⁇ : 350 mJ or more and less than 500 mJ ⁇ : 500 mJ or more
  • Alkali-soluble resin A-1 synthesized above
  • 2 Alkali-soluble resin A-2 synthesized above
  • 3 Alkali-soluble resin A-3 synthesized above
  • 4 Epicron N-870 (bisphenol A novolak type epoxy resin) manufactured by DIC; dissolved in CA (carbitol acetate); non-volatile content 75%
  • 5 Epicron N-730A (phenol novolac type epoxy resin) manufactured by DIC
  • 6 Irgacure OXE02 manufactured by BASF Japan Ltd.
  • Blue colorant / solid content in slurry 12/17 * 23: The blending amount in the table indicates the total solid content in the slurry.
  • Yellow colorant / solid content in slurry 10/15 * 24: The blending amount in the table indicates the total solid content in the slurry.
  • Inorganic filler / solid content in slurry 70/75
  • the photocurable resin composition of the present invention can form a cured product excellent in appearance and surface smoothness, and is excellent in sensitivity and resolution.

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Abstract

L'invention concerne une composition de résine photodurcissable développable en milieu alcalin ou similaire qui présente une excellente sensibilité et une excellente résolution et qui est susceptible de former un produit durci ayant un excellent aspect et un excellent lissé de surface. La composition de résine photodurcissable développable en milieu alcalin ou similaire comprend : (A) une résine soluble dans les alcalis ; (B) un initiateur de photopolymérisation ; (C) un colorant bleu ; et (D) une charge inorganique, et est caractérisée en ce que le diamètre moyen des particules du colorant bleu (C) est de 300 nm ou moins, et le diamètre moyen des particules de la charge inorganique (D) est de 1,0 µm ou moins.
PCT/JP2018/003042 2017-02-01 2018-01-30 Composition de résine photodurcissable, film sec, produit durci et carte imprimée Ceased WO2018143220A1 (fr)

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JP2022154993A (ja) * 2021-03-30 2022-10-13 互応化学工業株式会社 黒色感光性樹脂組成物、ドライフィルム、ソルダーレジスト及びプリント配線板
WO2024004619A1 (fr) * 2022-06-27 2024-01-04 富士フイルム株式会社 Composition durcissable, procédé de production de produit durci, film, élément optique, capteur d'images, capteur d'images à l'état solide, dispositif d'affichage d'images, et initiateur de polymérisation radicalaire

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WO2020045024A1 (fr) * 2018-08-27 2020-03-05 互応化学工業株式会社 Composition de résine photosensible, film sec, et carte de circuit imprimé
JP7281263B2 (ja) 2018-09-27 2023-05-25 味の素株式会社 樹脂組成物、感光性フィルム、支持体付き感光性フィルム、プリント配線板及び半導体装置
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JP7322988B2 (ja) 2018-09-27 2023-08-08 味の素株式会社 樹脂組成物、感光性フィルム、支持体付き感光性フィルム、プリント配線板及び半導体装置
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KR20200139632A (ko) * 2019-06-04 2020-12-14 다이요 잉키 세이조 가부시키가이샤 경화성 수지 조성물, 드라이 필름, 경화물, 및 프린트 배선판
JP2024133135A (ja) * 2019-06-04 2024-10-01 太陽ホールディングス株式会社 硬化性樹脂組成物、ドライフィルム、硬化物、およびプリント配線板
JP7610928B2 (ja) 2019-06-04 2025-01-09 太陽ホールディングス株式会社 硬化性樹脂組成物、ドライフィルム、硬化物、およびプリント配線板
KR102846500B1 (ko) 2019-06-04 2025-08-18 다이요 홀딩스 가부시키가이샤 경화성 수지 조성물, 드라이 필름, 경화물, 및 프린트 배선판
JP2022154993A (ja) * 2021-03-30 2022-10-13 互応化学工業株式会社 黒色感光性樹脂組成物、ドライフィルム、ソルダーレジスト及びプリント配線板
JP7333506B2 (ja) 2021-03-30 2023-08-25 互応化学工業株式会社 黒色感光性樹脂組成物、ドライフィルム、ソルダーレジスト及びプリント配線板
WO2024004619A1 (fr) * 2022-06-27 2024-01-04 富士フイルム株式会社 Composition durcissable, procédé de production de produit durci, film, élément optique, capteur d'images, capteur d'images à l'état solide, dispositif d'affichage d'images, et initiateur de polymérisation radicalaire

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