JPWO2018143220A1 - Photocurable resin composition, dry film, cured product, and printed wiring board - Google Patents

Abstract

Provided is a photocurable resin composition capable of forming a cured product excellent in appearance and surface smoothness and capable of alkali development that is excellent in sensitivity and resolution. (A) An alkali-soluble resin, (B) a photopolymerization initiator, (C) a blue colorant, and (D) an alkali-developable photo-curable resin composition containing an inorganic filler, wherein (C) An average particle size of the blue colorant is 300 nm or less, and an average particle size of the inorganic filler (D) is 1.0 μm or less.

Description

  The present invention relates to a photocurable resin composition, a dry film, a cured product, and a printed wiring board.

  In the production of a printed wiring board, a photocurable resin composition is generally employed for the formation of a permanent film such as a solder resist. As such a photocurable resin composition, a dry film type composition or a liquid composition is used. Things are being developed. Among these, in consideration of environmental problems, 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).

  In recent years, with the rapid progress of semiconductor components, electronic devices tend to be lighter, thinner, higher performance, and multifunctional. Following this trend, miniaturization and multi-pin semiconductor packages have been put into practical use. Specifically, instead of IC packages called QFP (Quad Flat Pack Package), SOP (Small Outline Package), etc., BGA (Ball Grid Array), CSP (Chip Scale Package), etc. IC package called is used. In recent years, FC-BGA (Flip Chip Ball Grid Array) has been put to practical use as an IC package with higher density.

  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 to be further thinned.

JP 61-243869 (Claims)

However, in the case of a dry film, repelling occurs when the resin composition is thinly applied to the carrier film in the dry film manufacturing process, and the repelling impairs the smoothness of the surface of the permanent film after curing. There was a problem.
Moreover, in the photocurable resin composition containing a blue colorant used for a solder resist or the like, the blue colorant absorbs ultraviolet rays of exposure light, so the sensitivity is lowered, and as a result, the productivity is lowered. Cheap. If the photoinitiator is increased in an attempt to solve the decrease in sensitivity, it is difficult for light to pass deeper in the thickest part of the coating film, for example, the part directly formed on the substrate instead of on the copper circuit. In addition, degradation of resolution due to occurrence of undercut becomes a problem.
Furthermore, there also existed a problem that the external appearance of hardened | cured material was impaired by the coarse grain which arises on the surface of hardened | cured material.

  Accordingly, 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.

  As a result of intensive studies in view of the above, 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.

  That is, 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. A curable resin composition, wherein the (C) blue colorant has an average particle size of 300 nm or less, and the (D) inorganic filler has an average particle size of 1.0 μm or less. .

  The photocurable resin composition of the present invention preferably further contains an organic filler having an amino group having an average particle diameter of 1 μm or less and a maximum particle diameter of 6 μm 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.

  In the photocurable resin composition of the present invention, 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 this invention has the said hardened | cured material, It is characterized by the above-mentioned.

  According to the present invention, 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 μm or less. Although the detailed mechanism is not clear, the above-mentioned problems of sensitivity and resolution are remarkable when a colorant having a strong ultraviolet absorption property such as a blue colorant is used. In the present invention, (C) the average particle size of the blue colorant is 300 nm or less, and (D) the average particle size of the inorganic filler is 1.0 μm or less, so that light (particularly i-line (365 nm)) The transmittance is improved. As a result, even when a blue colorant is used, 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. . Further, in the case of 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. Furthermore, by setting it as the said structure, the resin composition is apply | coated to a carrier film in the manufacturing process of a dry film, and the repellency which arises when forming a thin resin layer also decreases, and the hardened | cured material excellent in surface smoothness is formed. You can also. Furthermore, there are few fine particles that can be generated on the surface of the cured product, and a cured product having an excellent surface appearance can be formed.

  Further, by blending an oxime ester photopolymerization initiator as a photopolymerization initiator, sensitivity is further improved while minimizing an increase in absorbance. Thereby, it is possible to easily form a cured film with high sensitivity and excellent resolution without undercut.

  Below, each component of the photocurable resin composition of this invention is demonstrated. In addition, in this specification, (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 of the (A) alkali-soluble resin 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. Among these, it is preferable that the alkali-soluble resin is a carboxyl group-containing resin or a phenol resin because adhesion with the base is improved. In particular, since the developability is excellent, 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.

  Specific examples of the carboxyl group-containing resin include compounds listed below (any of oligomers and polymers).

  (1) 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, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.

  (2) 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 A 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.

  (3) Diisocyanate compounds such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, aromatic diisocyanate, polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A type 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.

  (4) 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.

  (5) During the synthesis of the resin of the above (2) or (4), a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added, and the terminal ( (Meth) acrylic carboxyl group-containing urethane resin.

  (6) During the synthesis of the resin of the above (2) or (4), 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.

  (7) A carboxyl group obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride to the hydroxyl group present in the side chain Containing resin.

  (8) A carboxyl group-containing resin in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin obtained by epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin, and a dibasic acid anhydride is added to the resulting hydroxyl group. .

  (9) 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.

  (10) 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.

  (12) 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.

  (13) In addition to the carboxyl group-containing resins described in the above (1) to (12) and the like, in the molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate, one epoxy group and one or more ( A carboxyl group-containing resin obtained by adding a compound having a (meth) acryloyl group.

  Among the carboxyl group-containing resins, the carboxyl group-containing resins described in (1), (7), (8), and (10) to (13) are preferable.

  Examples of the compound having a phenolic hydroxyl group include a compound having a biphenyl skeleton or a phenylene skeleton or both of them, 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 novolak resin, an alkylphenol volac resin, a bisphenol A novolak 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 resin, poly-p-hydroxystyrene, condensates of naphthol and aldehydes, and condensates of dihydroxynaphthalene and aldehydes.

  Examples of commercially available phenol resins include HF1H60 (Maywa Kasei Co., Ltd.), Phenolite TD-2090, Phenolite TD-2131 (Dai Nippon Printing Co., Ltd.), Vesmol CZ-256-A (Dic Corporation), Siyonor BRG-555, Siyonor BRG-556 (manufactured by Showa Denko KK), CGR-951 (manufactured by Maruzen Petroleum Co., Ltd.), polyvinylphenol CST70, CST90, S-1P, S-2P (manufactured by Maruzen Petroleum Co., Ltd.) are exemplified.

  (A) 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.

  (A) 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. When 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. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is good and the storage stability is also excellent.

  (A) Alkali-soluble resin can be used individually by 1 type or in combination of 2 or more types.

[(B) Photopolymerization initiator]
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. (B) Examples of the photopolymerization initiator include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and 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 oxides such as id (IRGACURE819 manufactured by BASF Japan); 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphine Monoacylphosphine oxide such as acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (IRGACURE TPO manufactured by BASF Japan Ltd.) 1-hydroxy-cyclohexyl phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl- -Propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-hydroxy- Hydroxyacetophenones such as 2-methyl-1-phenylpropan-1-one; benzoins such as benzoin, benzyl, benzoin methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether; Alkyl ethers; benzophenones such as benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone; acetophenone, 2,2-dimethone Xyl-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl) -1- [ Acetophenones such as 4- (4-morpholinyl) phenyl] -1-butanone and N, N-dimethylaminoacetophenone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethyl Thioxanthone, 2-chlorothioxanthone, 2, Thioxanthones such as diisopropylthioxanthone; anthraquinones such as anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone; acetophenone Ketals such as dimethyl ketal and benzyl dimethyl ketal; benzoates such as ethyl-4-dimethylaminobenzoate, 2- (dimethylamino) ethyl benzoate and p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1 -[4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] Oxime esters such as 1- (O-acetyloxime); bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) Phenyl) titanium, titanocenes such as bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- (1-pyr-1-yl) ethyl) phenyl] titanium; phenyl disulfide 2-nitrofluorene , Butyroin, anisoin ethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide and the like. A photoinitiator may be used individually by 1 type and may be used in combination of 2 or more type. Of these, oxime esters (hereinafter also referred to as “oxime ester photopolymerization initiators”) are preferable, and ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) is more preferred.
(B) The compounding quantity of a photoinitiator is 0.01-30 mass parts with respect to 100 mass parts of solid content of (A) alkali-soluble resin, for example. Further, 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.

  As the oxime ester photopolymerization initiator, any known oxime ester photopolymerization initiator can be used. 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.

（式中、Ｘは、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）を表し、Ｙ、Ｚはそれぞれ、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基またはジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、結合か、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルを表し、ｎは０か１の整数である。）In addition, 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.

(In the 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). Group, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms or a dialkylamino group, a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms), Represents an amino group, an alkylamino group having a C 1-8 alkyl group or a dialkylamino group, and Y and Z are each a hydrogen atom, a C 1-17 alkyl group, and a carbon number 1 Alkoxy group having ˜8 alkoxy group, halogen group, phenyl group, phenyl group (alkyl group having 1 to 17 carbon atoms, alkoxy group having 1 to 8 carbon atoms, amino group, alkyl group having 1 to 8 carbon atoms) Substituted with a mino group or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having an alkyl group having 1 to 8 carbon atoms) Or substituted with a dialkylamino group), anthryl group, pyridyl group, benzofuryl group, benzothienyl group, Ar is a bond or alkylene having 1 to 10 carbon atoms, vinylene, phenylene, biphenylene, pyridylene, naphthylene, Represents thiophene, anthrylene, thienylene, furylene, 2,5-pyrrole-diyl, 4,4′-stilbene-diyl, 4,2′-styrene-diyl, and n is an integer of 0 or 1)

  In particular, in the above general formula, 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

（式中、Ｒ^１は、炭素原子数１〜４のアルキル基、または、ニトロ基、ハロゲン原子もしくは炭素原子数１〜４のアルキル基で置換されていてもよいフェニル基を表す。
Ｒ^２は、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基、または、炭素原子数１〜４のアルキル基もしくはアルコキシ基で置換されていてもよいフェニル基を表す。
Ｒ^３は、酸素原子または硫黄原子で連結されていてもよく、フェニル基で置換されていてもよい炭素原子数１〜２０のアルキル基、炭素原子数１〜４のアルコキシ基で置換されていてもよいベンジル基を表す。
Ｒ^４は、ニトロ基、または、Ｘ−Ｃ（＝Ｏ）−で表されるアシル基を表す。Ｘは、炭素原子数１〜４のアルキル基で置換されていてもよいアリール基、チエニル基、モルホリノ基、チオフェニル基、または、下記式で示される構造を表す。）

Moreover, the compound which can be represented by the following general formula can also be mentioned as a preferable carbazole oxime ester compound.

(In the formula, R ¹ represents an alkyl group or a nitro group, a halogen atom or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms 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 which may be 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 and an alkoxy group having 1 to 4 carbon atoms which may be substituted with a phenyl group. Represents a good benzyl 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. )

  In addition, JP-A-2004-359639, JP-A-2005-097141, JP-A-2005-220097, JP-A-2006-160634, JP-A-2008-094770, JP-A-2008-509967, Examples thereof include carbazole oxime ester compounds described in JP-A-2009-040762 and JP-A-2011-80036.

[(C) Blue colorant]
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. When the average particle size is 300 nm or less, the appearance of the surface of the cured product is improved.
Here, 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.

  (C) 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 μm or more.

  Moreover, it is preferable to contain 0.18-0.50 mass% in conversion of solid content per photocurable resin composition whole quantity from a viewpoint of improving the concealment property of hardened | cured material. When the solid content is 0.18% by mass or more, the circuit concealability is excellent. In 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%-0.40 mass%.

  (C) 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 colorant may be used, and 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, 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 etc. can be used as the dye system. In addition to the above, 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.

  (C) Although the adjustment method of the average particle diameter of a blue colorant is not specifically limited, For example, it is preferable to disperse | distribute to a solvent etc. with a bead mill, a jet mill, etc. In addition, as the (C) blue colorant, a commercially available product having an average particle diameter in the above range may be used as it is.

  (C) The blue colorant is preferably blended in a slurry state. By blending in 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.

  (C) The blue colorant preferably has an absorbance at a wavelength of 365 nm of 0.5 to 1.0 by the following measurement method. First, 0.1 part of a blue colorant is added to 100 parts of the non-volatile 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 for 30 minutes at 80 ° C., a dried coating film is formed to a thickness of 15 μm, 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. As other 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.
In the photocurable resin composition of the present invention, 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.

  Examples of the red colorant include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Examples of blue colorants include metal-substituted or unsubstituted phthalocyanine-based and anthraquinone-based compounds, and pigment-based compounds that are classified as pigments. Similarly, the green colorant includes metal-substituted or unsubstituted phthalocyanine-based, anthraquinone-based, and perylene-based materials. Examples of yellow colorants include monoazo, disazo, condensed azo, benzimidazolone, isoindolinone, and anthraquinone. Examples of the white colorant 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. In addition, a colorant such as purple, orange or brown may be added for the purpose of adjusting the color tone.

[(D) inorganic filler]
The photocurable resin composition of the present invention contains an inorganic filler having an average particle size of 1.0 μm or less and preferably an average particle size of 0.8 μm or less. Here, (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.

  (D) 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. Among these, 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.

  (D) The inorganic filler may be surface-treated. Here, 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. Here, 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. Examples of 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. What is necessary is just to process the surface of an inorganic filler with the coupling agent etc. which have as. As the coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, or the like can be used. Examples of 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.

  (D) Although the adjustment method of the average particle diameter of an inorganic filler is not specifically limited, For example, pre-dispersion with a bead mill or a jet mill is preferable. Moreover, you may use the commercial item which has an average particle diameter in the said range as (D) inorganic filler as it is.

  (D) The inorganic filler is preferably blended in a slurry state. By blending 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.

  (D) An inorganic filler can be used individually by 1 type or in combination of 2 or more types. (D) It is preferable that the compounding quantity of an inorganic filler is 80-450 mass parts with respect to 100 mass parts of solid content of (A) alkali-soluble resin, and it is more preferable that it is 100-200 mass parts. 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. For example, known thermosetting components such as melamine resins, benzoguanamine resins, melamine derivatives, amino resins such as benzoguanamine derivatives, isocyanate compounds, block isocyanate compounds, cyclocarbonate compounds, epoxy compounds, oxetane compounds, episulfide resins, bismaleimides, carbodiimide resins, etc. Can be used. Particularly preferred is a thermosetting component having a plurality of cyclic ether groups or cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in the molecule.

  The 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 novolac type epoxy resin; Tetraphenylol ethane type epoxy resin; Heterocyclic epoxy resin; Diglycidyl Taleate resin; Tetraglycidylxylenoylethane resin; Naphthalene group-containing epoxy resin; Epoxy resin having dicyclopentadiene skeleton; Glycidyl methacrylate copolymer epoxy resin; Copolymer epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Polybutadiene rubber derivatives; CTBN-modified epoxy resins and the like can be mentioned, but are not limited thereto. These epoxy resins can be used alone or in combination of two or more. Among these, 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.

  Examples of the polyfunctional oxetane compound 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-hydroxystyrene), cardo-type bis Phenol ethers, calixarenes, calix resorcin arenes or etherified products such as the resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  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. It is preferable that it is 0.6-2.5 equivalent with respect to an equivalent, More preferably, it is 0.8-2.0 equivalent.

  Examples of amino resins such as melamine derivatives and benzoguanamine derivatives include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds.

  As the isocyanate compound, a polyisocyanate compound can be blended. Examples of the polyisocyanate compound 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, Yuretto body and isocyanurate products thereof.

  As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent can be used. As an isocyanate compound which can react with an isocyanate blocking agent, the above-mentioned polyisocyanate compound etc. are mentioned, for example. As 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.

  A thermosetting component can be used individually by 1 type or in combination of 2 or more types. The blending amount of the thermosetting component is preferably 20 to 60 parts by mass, and 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. In the case of 20 parts by mass or more, the heat resistance is excellent. In the case of 60 parts by mass or less, the storage stability is improved.

(Compound having an ethylenically unsaturated group)
Unlike (A) alkali-soluble resin, the photocurable resin composition of this invention can contain what functions as a reactive diluent, specifically, the compound which has an ethylenically unsaturated group. As the compound having an ethylenically unsaturated group, a photopolymerizable oligomer, a photopolymerizable vinyl monomer or the like, which 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.

  As the photopolymerizable vinyl monomer, known and commonly used monomers, for example, styrene derivatives such as styrene, chlorostyrene and α-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-ethoxymethylacrylate (Meth) acrylamides such as luamide and N-butoxymethylacrylamide; allyl compounds such as triallyl isocyanurate, diallyl phthalate and diallyl isophthalate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl Esters of (meth) acrylic acid such as (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol Hydroxyalkyl (meth) acrylates such as tri (meth) acrylate; alcohols such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate Xylalkylene glycol mono (meth) acrylates; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylates, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylol Alkylene polyol poly (meth) acrylates such as propane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxy Polyoxyalkylene glycol poly (methyl) such as trimethylolpropane triacrylate and propoxylated trimethylolpropane tri (meth) acrylate ) Acrylates; poly (meth) acrylates such as hydroxypivalic acid neopentyl glycol ester di (meth) acrylate; isocyanurate-type poly (meth) acrylates such as tris [(meth) acryloxyethyl] isocyanurate It is done. These can be used alone or in combination of two or more according to the required properties.

  The compound which has an ethylenically unsaturated group can be used individually by 1 type or in combination of 2 or more types. It is preferable that the compounding quantity of the compound which has an ethylenically unsaturated group is 3-25 mass parts with respect to 100 mass parts of solid content of (A) alkali-soluble resin, and it is more preferable that it is 5-20 mass parts. . 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. Examples of such 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. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. A compound that also functions in combination with a thermosetting catalyst. Moreover, 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 μm or less and a maximum particle size (D100) of 6 μm or less. In particular, the average particle size is preferably 800 nm or less, and more preferably 600 nm or less. The maximum particle size is preferably 5 μm or less, more preferably 4 μm or less. As the average particle size and the maximum particle size become smaller, the resistance to gold plating improves. Here, the average particle diameter 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.

  As the thermosetting catalyst, an organic filler having an amino group is preferable, and specifically, at least one of melamine and dicyandiamide (DICY) is preferable.

  A thermosetting catalyst can be used individually by 1 type or in combination of 2 or more types. It is preferable that the compounding quantity of a thermosetting catalyst is 0.5-10 mass parts with respect to 100 mass parts of solid content of (A) alkali-soluble resin, and it is more preferable that it is 1-8 mass parts. In the case of 0.5 parts by mass or more, the heat resistance is excellent. In the case of 10 parts by mass or less, the storage stability is improved.

(Organic solvent)
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. Examples of 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, carbitol acetate, butylcarby Tall acetate, propylene glycol monomethyl ether acetate, dip Propylene glycol monomethyl ether acetate, esters such as propylene carbonate; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, and petroleum solvents such as solvent naphtha, organic solvents conventionally known can be used. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

(Other optional ingredients)
Furthermore, you may mix | blend the other hardening component and other additive well-known and usual in the field of an electronic material with the photocurable resin composition of this invention. Examples of other curing components include cyanate ester resins, active ester resins, maleimide compounds, and alicyclic olefin polymers. Other 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 μm thickness of the dried coating film.

  Next, the dry film of this invention has a resin layer obtained by apply | coating and drying the photocurable resin composition of this invention on a carrier film. When forming a dry film, first, 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. Then, the resin layer can be formed by drying the applied composition at a temperature of 40 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is a film thickness after drying, and is suitably selected in the range of 3-150 micrometers, Preferably it is 5-60 micrometers.

  As the carrier film, a plastic film is used. For example, 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. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers. More preferably, it is the range of 15-130 micrometers.

  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. 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. As 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.

  In the present invention, a resin layer may be formed by applying and drying the photocurable resin composition of the present invention on the cover film and laminating a carrier film on the surface thereof. 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 this invention has the hardened | cured material obtained from the resin layer of the photocurable resin composition or dry film of this invention. As a method for producing a printed wiring board of the present invention, for example, 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. After coating by a method such as flow coating, roll coating, bar coater, screen printing or curtain coating, the organic solvent contained in the composition is volatilized and dried at a temperature of 60 to 100 ° C. (temporary drying) By doing so, a tack-free resin layer is formed. Moreover, in the case of a dry film, after bonding together on a base material so that a resin layer may contact a base material with a laminator etc., 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. It is made of materials such as copper-clad laminates for high-frequency circuits using synthetic fiber epoxy, fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc., and copper-clad laminates of all grades (FR-4 etc.) Examples thereof include a plate, a metal substrate, a polyimide film, a PET film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, and a wafer plate.

  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).

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. Furthermore, 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 subjected to final finish curing (main curing) only by heat-curing, thereby allowing adhesion. A cured film having excellent properties such as properties and hardness is formed.
In addition, when the photocurable resin composition of this invention contains a photobase generator, it is preferable to heat before image development after exposure, As heating conditions before image development after exposure, it is 1 at 60-150 degreeC, for example. Heating for ~ 60 minutes is preferred.

As an exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, and the like may be used as long as the apparatus irradiates ultraviolet rays in a range of 350 to 450 nm. Furthermore, 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) can also be used. 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 amount of exposure for image formation varies depending on the film thickness and the like, but is generally 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. In addition, according to the photocurable resin composition of the present invention, 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.

  In particular, 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 μm, more preferably 5 to 30 μm.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following description, “parts” and “%” are all based on mass unless otherwise specified.

(Synthesis of alkali-soluble resin A-1)
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device, 119.4 parts of a novolac type cresol resin (trade name “Shonol CRG951”, manufactured by Showa Denko KK, OH equivalent: 119.4), 1.19 parts of potassium hydroxide and 119.4 parts of toluene were introduced, the inside of the system was replaced with nitrogen while stirring, and the temperature was raised by heating. Next, 63.8 parts of propylene oxide was gradually added dropwise and reacted at 125 to 132 ° C. and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the 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.
293.0 parts of a propylene oxide reaction solution of the obtained novolac-type cresol resin, 43.2 parts of acrylic acid, 11.53 parts of methanesulfonic acid, 0.18 part of methylhydroquinone and 252.9 parts of toluene were mixed with a stirrer and a temperature. It was introduced into a reactor equipped with a meter and an air blowing tube, and air was blown at a rate of 10 ml / min and reacted at 110 ° C. for 12 hours while stirring. 12.6 parts of water was distilled from the water produced by the reaction as an azeotrope with toluene. Thereafter, the 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. Next, 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. Then, 60.8 parts of tetrahydrophthalic anhydride was gradually added with stirring, reacted at 95 to 101 ° C. for 6 hours, cooled, and taken out. In this way, a solution of photosensitive carboxyl group-containing resin A-1 having a solid content of 65% and a solid content acid value of 87.7 mgKOH / g was obtained. Hereinafter, this carboxyl group-containing photosensitive resin solution is referred to as a resin solution A-1.

(Synthesis of alkali-soluble resin A-2)
A flask equipped with a condenser and a stirrer was charged with 456 parts of bisphenol A, 228 parts of water, and 649 parts of 37% formalin, and kept at a temperature of 40 ° C. or lower, and 228 parts of 25% aqueous sodium hydroxide solution was added. The reaction was performed at 0 ° C. for 10 hours. After completion of the reaction, the reaction mixture was cooled to 40 ° C. and neutralized to pH 4 with a 37.5% phosphoric acid aqueous solution while maintaining the temperature at 40 ° C. or lower. Thereafter, the mixture was allowed to stand to separate the aqueous layer. After separation, 300 parts of methyl isobutyl ketone was added and dissolved uniformly, and then washed three times with 500 parts of distilled water, and water, solvent, and the like were removed under reduced pressure at a temperature of 50 ° C. or lower. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1230 parts of a methanol solution of the polymethylol compound.
When a part of the methanol solution of the obtained polymethylol compound was dried at room temperature in a vacuum dryer, the solid content was 55.2%.
A flask equipped with a condenser and a stirrer was charged with 500 parts of a methanol solution of the obtained polymethylol compound and 440 parts of 2,6-xylenol, and uniformly dissolved at 50 ° C. After dissolving uniformly, methanol was removed under reduced pressure at a temperature of 50 ° C. or lower. Thereafter, 8 parts of oxalic acid was added and reacted at 100 ° C. for 10 hours. After completion of the reaction, the distillate was removed under reduced pressure at 180 ° C. and 50 mmHg to obtain 550 parts of novolak resin A.
In an autoclave equipped with a thermometer, a nitrogen introduction device / alkylene oxide introduction device, and a stirring device, 130 parts of novolak resin A, 2.6 parts of 50% aqueous sodium hydroxide, toluene / methyl isobutyl ketone (mass ratio = 2/1) 100 parts were charged, and the system was purged with nitrogen while stirring. Next, the temperature was raised by heating, and 60 parts of propylene oxide was gradually introduced and reacted at 150 ° C. and 8 kg / cm ² . The reaction was continued for about 4 hours until the gauge pressure reached 0.0 kg / cm ^2, and then cooled to room temperature. To this reaction solution, 3.3 parts of 36% aqueous hydrochloric acid was added and mixed to neutralize sodium hydroxide. The neutralized reaction product was diluted with toluene, washed with water three times, and the solvent was removed with an evaporator. The hydroxyl value was 189 g / eq. A propylene oxide adduct of novolak resin A was obtained. This was an average of 1 mole of propylene oxide added per equivalent of phenolic hydroxyl group.
Propylene oxide adduct 189 parts of the obtained novolak resin A, 36 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 part of hydroquinone monomethyl ether and 140 parts of toluene were stirred, a thermometer, an air blowing tube Was stirred while blowing air, heated to 115 ° C., reacted for an additional 4 hours while distilling off the water produced by the reaction as an azeotrope with toluene, and then brought to room temperature. Cooled down. The obtained reaction solution was washed with 5% NaCl aqueous solution and toluene was removed by distillation under reduced pressure, and then diethylene glycol monoethyl ether acetate was added to obtain an acrylate resin solution having a solid content of 67%.
Next, in a four-necked flask equipped with a stirrer and a reflux condenser, 322 parts of the obtained acrylate resin solution, 0.1 part of hydroquinone monomethyl ether, and 0.3 part of triphenylphosphine were charged. Then, 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. Hereinafter, this carboxyl group-containing photosensitive resin solution is referred to as Resin Solution A-2.

(Synthesis of alkali-soluble resin A-3)
Orthocresol novolak type epoxy resin (produced by DIC, EPICLON N-695, softening point 95 ° C., epoxy equivalent 214, average functional group number 7.6) 1070 g (number of glycidyl groups (total number of aromatic rings): 5) 0.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone were charged, heated and stirred at 100 ° C., and uniformly dissolved.
Next, 4.3 g of triphenylphosphine was charged, heated to 110 ° C. and reacted for 2 hours, then heated to 120 ° C. and reacted for further 12 hours. Into the obtained reaction liquid, 415 g of aromatic hydrocarbon (Sorvesso 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were added, reacted at 110 ° C. for 4 hours, cooled, and photosensitive carboxyl A group-containing resin solution was obtained. The resin solution thus obtained had a solid content of 65% and an acid value of the solid content of 89 mgKOH / g. Hereinafter, this carboxyl group-containing photosensitive resin solution is referred to as Resin Solution A-3.

(Preparation of blue colorant slurries C-1, C-2, RC-1)
(C-1)
12 parts by weight of phthalocyanine blue, 5 parts by weight of CAP (cellulose acetate propionate) resin, 83 parts by weight of DPM (dipropylene glycol monomethyl ether) are mixed and dispersed in a bead mill for 3 hours to obtain a blue colorant slurry C-1. Obtained. The average particle diameter of the obtained phthalocyanine blue was obtained by using Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. and measuring a sample obtained by diluting a blue colorant slurry with MIBK (methyl isobutyl ketone) to an appropriate concentration. As a result of measuring the sample, 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 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. As a result of measurement of this sample, the D50 value was 280 nm and the D100 value was 600 nm as measured by the laser diffraction method.
(RC-1)
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 1 hour. 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. As a result of the measurement of this sample, the value measured by laser diffraction method was D50 of 400 nm and D100 of 1 μm.

(Preparation of yellow colorant slurry)
10 parts by mass of chromophthal yellow, 5 parts by mass of CAP resin, and 85 parts by mass of DPM were mixed and dispersed with a bead mill for 2 hours to obtain a yellow colorant slurry. The average particle size of the obtained chromophthal yellow was obtained by measuring a sample diluted with MIBK to a measurement appropriate concentration using Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. As a result of the measurement of this sample, the value measured by the laser diffraction method was D50 of 150 nm and D100 of 450 nm.

(Preparation of silica slurry D-1)
(Preparation of D-1)
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 Big Chemie Japan) are 2 in a bead mill. 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 μm and D100 of 1.7 μm.

(Preparation of barium slurry D-2)
(Preparation of D-2)
70 parts by mass of barium sulfate (B-30 manufactured by Sakai Chemical Industry Co., Ltd.), 25 parts by mass of PMA (propylene glycol monomethyl ether acetate) as a solvent, and a dispersing agent (BYK-111 manufactured by BYK) ) 5 parts by mass were uniformly dispersed with a bead mill for 2 hours to obtain a barium sulfate slurry D-2. The average particle diameter of the obtained barium sulfate 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 laser diffraction method was D50 of 0.30 μm and D100 of 1.0 μm.

(Preparation of silica slurry RD-1)
(Preparation of RD-1)
2 parts by mass of 70 parts by mass of spherical silica (FB-5D manufactured by Denka), 25 parts by mass of PMA (propylene glycol monomethyl ether acetate) as a solvent, and 5 parts by mass 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 μm and the D100 value was 12.5 μm as measured by the laser diffraction method.

(Preparation of melamine dispersion 1)
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. As a result of measurement of this sample, the value measured by laser diffraction method was D50 of 600 nm and D100 of 5.0 μm.

(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 μm.

(Preparation of Dicyandiamide (DICY) Dispersion 1)
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. As a result of measurement of this sample, the value measured by laser diffraction method was D50 of 800 nm and D100 of 6.0 μm.

(Preparation of Dicyandiamide (DICY) Dispersion 2)
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 μm.

[Examples 1 to 14, Comparative Examples 1 and 2]
The components shown in Tables 1 to 3 below are 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. In addition, the compounding quantity in a table | surface shows solid content (nonvolatile content).

(Production of dry film)
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.

(Absorbance)
According to the method described above (production of dry film), a dry film having a resin layer thickness of 15 μm after drying was produced. A dry film having a resin layer thickness of 15 μm was laminated on a glass substrate, and the PET film was peeled off. Thereafter, the absorbance was measured using a spectrophotometer V-670.

(Concealment)
According to the method described above (production of dry film), dry films having a resin layer thickness of 18 μm, 23 μm, and 28 μm after drying were prepared. Next, each dry film was laminated on a printed wiring board on which a comb thickness pattern with a Cu thickness of 6 μm and L / S = 15/20 was formed. On the other hand, whole surface exposure was performed with an optimum exposure amount of 800 mJ using an HMW680GW (metal halide lamp, scattered light) manufactured by ORC. After peeling off the PET film, it was further irradiated with ultraviolet rays with an integrated exposure amount of 1000 mJ, and then cured by heating at 160 ° C. for 1 hour.
About the printed wiring board which has the obtained cured film, the concealment property of the circuit was evaluated visually.
◎: Good when dry film thickness of resin layer after drying is 18 μm and thickness of cured film is 10 μm on copper ○: Use dry film thickness of resin layer after drying is 23 μm, Good when the cured film has a thickness of 15 μm on copper Δ: Use a dry film with a resin layer thickness of 28 μm after drying, good when the cured film has a thickness of 20 μm on copper ×: Resin layer after drying When a dry film with a film thickness of 28 μm is used and the cured film thickness is 20 μm on copper, the film is defective.

(appearance)
According to the method described above (production of dry film), a dry film having a resin layer thickness of 15 μm after drying was produced. Next, a dry film having a film thickness of 15 μm was laminated on a substrate having a CZ-treated 35 μm copper foil. On the other hand, whole surface exposure was performed with an optimum exposure amount of 800 mJ using an HMW680GW (metal halide lamp, scattered light) manufactured by ORC. After peeling off the PET film, it was further irradiated with ultraviolet rays with an integrated exposure amount of 1000 mJ, and then cured by heating at 160 ° C. for 1 hour.
About the printed wiring board which has the obtained cured film, the presence or absence of the grain on a cured film was confirmed with the optical microscope 500 times.
◎: No particle having a particle size of 5 μm or less ○: No particle having a particle size of 10 μm or less Δ: Less than 15 particles having a particle size of 10 μm or less X: 15 or more particles having a particle size of 10 μm or less

(Surface smoothness)
According to the method described above (production of dry film), a dry film having a resin layer thickness of 15 μm after drying was produced. On the surface of the dry film with the resin layer having a thickness of 15 μm, repellency was visually confirmed at 10 places in a region of 8 cm wide × 20 cm long, and crossing of the film thickness was confirmed with a micrometer.
A: No repelling, unevenness difference ± 1 μm
○: No repelling, unevenness difference ± 2 μm
Δ: No repelling, unevenness difference ± 3 μm
×: Repel

(sensitivity)
According to the method described above (production of dry film), a dry film having a resin layer thickness of 15 μm after drying was produced. Using a projection exposure machine UFX-2223M-APU01 in which a dry film having a film thickness of 15 μm is laminated on a substrate having a 35 μm copper foil subjected to CZ treatment, and a longer wavelength side is 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 Δ: 350 mJ or more and less than 500 mJ ×: 500 mJ or more

(Resolution)
According to the method described above (production of dry film), a dry film having a resin layer thickness of 15 μm after drying was produced. Using a projection exposure machine UFX-2223M-APU01 in which a dry film with a film thickness of 15 μm is laminated on a substrate having a 35 μm copper foil treated with CZ and the long wavelength side is cut from the i-line It was exposed to have a pattern. The PET film was peeled off and developed with a 1.0 wt% sodium carbonate aqueous solution to confirm the minimum opening diameter that could be formed.
A: Good opening diameter at 50 μm ○: Good opening diameter at 80 μm Δ: Good opening diameter at 100 μm ×: Good opening diameter cannot be obtained at 100 μm

＊８：ＢＡＳＦジャパン社製イルガキュアＴＰＯ（２，４，６−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド）
＊９：ＢＡＳＦジャパン社製イルガキュア９０７（２−メチル−１−（４−メチルチオフェニル）−２−モルフォリノプロパン−１−オン）
＊１０：日本化薬社製カヤキュアＤＥＴＸ−Ｓ（２，４−ジエチルチオキサントン）
＊１１：上記で調製した青色着色剤（フタロシアニンブルー、平均粒径２２０ｎｍ、表面処理無し）スラリーＣ−１
＊１２：上記で調製した青色着色剤（フタロシアニンブルー、平均粒径２８０ｎｍ、表面処理無し）スラリーＣ−２
＊１３：上記で調製した青色着色剤（フタロシアニンブルー、平均粒径４００ｎｍ、表面処理無し）スラリーＲＣ−１
＊１４：上記で調製した黄色着色剤（クロモフタルイエロー、平均粒径１５０ｎｍ、表面処理無し）のスラリー
＊１５：上記で調製したシリカ（ＳＦＰ−３０Ｍ、平均粒径０．７μｍ、表面処理有り）スラリーＤ−１
＊１６：上記で調製したバリウム（Ｂ−３０、平均粒径０．３μｍ、表面処理有り）スラリーＤ−２
＊１７：上記で調製したシリカ（ＦＢ−５Ｄ、平均粒径５．０μｍ、表面処理有り）スラリーＲＤ−１
＊１８：日本化薬社製ＤＰＨＡ（ジペンタエリスリトールヘキサアクリレート）
＊１９：市販品（平均粒径：５μｍ、最大粒子径：２０μｍ）
＊２０：市販品（平均粒径：３μｍ、最大粒子径：１５μｍ）
＊２１：ビックケミージャパン社製ＢＹＫ−３６１Ｎ（レべリング剤）
＊２２：表中の配合量は、スラリー中の固形分の合計を示す。青色着色剤／スラリー中の固形分＝１２／１７
＊２３：表中の配合量は、スラリー中の固形分の合計を示す。黄色着色剤／スラリー中の固形分＝１０／１５
＊２４：表中の配合量は、スラリー中の固形分の合計を示す。無機フィラー／スラリー中の固形分＝７０／７５* 1: 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 novolac 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. (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime)
* 7:

* 8: BASF Japan Irgacure TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide)
* 9: BASF Japan Irgacure 907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one)
* 10: Nippon Kayaku Co., Ltd. Kayacure DETX-S (2,4-diethylthioxanthone)
* 11: Blue colorant (phthalocyanine blue, average particle size 220 nm, no surface treatment) slurry C-1 prepared above
* 12: Blue colorant (phthalocyanine blue, average particle size 280 nm, no surface treatment) slurry C-2 prepared above
* 13: Blue colorant (phthalocyanine blue, average particle size 400 nm, no surface treatment) slurry RC-1 prepared above
* 14: Slurry of yellow colorant prepared above (chromophthal yellow, average particle size 150 nm, no surface treatment) * 15: Silica prepared above (SFP-30M, average particle size 0.7 μm, with surface treatment) Slurry D-1
* 16: Barium (B-30, average particle size 0.3 μm, with surface treatment) slurry D-2 prepared above
* 17: Silica (FB-5D, average particle size 5.0 μm, with surface treatment) slurry RD-1 prepared above
* 18: Nippon Kayaku DPHA (dipentaerythritol hexaacrylate)
* 19: Commercial product (average particle size: 5 μm, maximum particle size: 20 μm)
* 20: Commercial product (average particle size: 3 μm, maximum particle size: 15 μm)
* 21: BYK-361N (leveling agent) manufactured by Big Chemie Japan
* 22: The blending amount in the table indicates the total solid content in the slurry. 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

＊２５：上記で調製したメラミン分散品１（平均粒径：６００ｎｍ、最大粒子径：５．０μｍ）
＊２６：上記で調製したメラミン分散品２（平均粒径：４００ｎｍ、最大粒子径：４．０μｍ）
＊２７：上記で調製したＤＩＣＹ分散品１（平均粒径：８００ｎｍ、最大粒子径：６．０μｍ）
＊２８：上記で調製したＤＩＣＹ分散品２（平均粒径：４００ｎｍ、最大粒子径：４．０μｍ）

* 25: Melamine dispersion 1 prepared above (average particle size: 600 nm, maximum particle size: 5.0 μm)
* 26: Melamine dispersion 2 prepared above (average particle size: 400 nm, maximum particle size: 4.0 μm)
* 27: DICY dispersion 1 prepared above (average particle size: 800 nm, maximum particle size: 6.0 μm)
* 28: DICY dispersion 2 prepared above (average particle size: 400 nm, maximum particle size: 4.0 μm)

  From the result shown in the said table | surface, it turns out that the photocurable resin composition of this invention can form the hardened | cured material excellent in the external appearance and surface smoothness, and is excellent in a sensitivity and resolution.

Claims (7)

(A) an alkali-soluble resin, (B) a photopolymerization initiator, (C) a blue colorant, and (D) an alkali-developable photocurable resin composition containing an inorganic filler,
The average particle size of the (C) blue colorant is 300 nm or less,
(D) The photocurable resin composition characterized by the average particle diameter of said inorganic filler being 1.0 micrometer or less.   Furthermore, the photocurable resin composition of Claim 1 containing the organic filler which has an amino group whose average particle diameter is 1 micrometer or less and whose maximum particle diameter is 6 micrometers or less as a thermosetting catalyst.   The (B) photopolymerization initiator includes an oxime ester photopolymerization initiator, and the amount of the oxime ester photopolymerization initiator is 8% by mass or more in terms of solid content per photopolymerization initiator. The photocurable resin composition according to claim 1.   2. The photocurable resin according to claim 1, wherein the blending amount of the (C) blue colorant is 0.18 to 0.50 mass% in terms of solid content per total amount of the photocurable resin composition. Composition.   A dry film comprising a resin layer obtained from the photocurable resin composition according to claim 1.   Hardened | cured material obtained by hardening | curing the resin layer of the photocurable resin composition as described in any one of Claims 1-4, or the dry film of Claim 5.   A printed wiring board comprising the cured product according to claim 6.