TWI744470B - Light-curing resin composition, dry film, cured product, and printed circuit board - Google Patents

Abstract

The present invention provides an alkali-developable photocurable resin composition, which can form a cured product with excellent appearance and smoothness, and excellent sensitivity and resolution. The photocurable resin composition and the like are composed of alkali-developable photocurable resin containing (A) alkali-soluble resin, (B) photopolymerization initiator, (C) blue colorant and (D) inorganic filler The product is characterized in that the average particle size of the aforementioned (C) blue coloring agent is 300 nm or less, and the average particle size of the aforementioned (D) inorganic filler is 1.0 μm or less.

Description

Light-curing resin composition, dry film, cured product, and printed circuit board

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

In the manufacture of printed circuit boards, photocurable resin compositions are generally used in the formation of permanent coatings such as solder resists. As such photocurable resin compositions, dry film-type compositions and liquid compositions have been developed. . Among these, based on concerns about environmental issues, an alkali-developable photocurable resin composition using a dilute alkali aqueous solution as a developer is the mainstream. In the past, several composition systems have been proposed (for example, Patent Document 1).

In recent years, due to the rapid progress of semiconductor components, electronic machines have tended to be lighter, thinner, shorter, smaller, higher performance, and more versatile. The miniaturization and pinning of semiconductor packages following this trend has been put into practical use. Specifically, instead of IC packages called QFP (quad flat pack package), SOP (small outline package: small outline package), etc., and use called BGA (ball grid array: ball grid array), CSP (chip scale package: chip scale package) and other IC packages. In addition, in recent years, as an even higher density IC package, FC-BGA (flipchip ball grid array) has also been put into practical use.

For such permanent coatings such as solder resist formed on printed circuit boards (also called package substrates) used for IC packaging, further thinning is required. [Prior Technical Documents] [Patent Documents]

Patent Document 1: Japanese Patent Application Laid-Open No. 61-243869 (Scope of Patent Application)

[The problem to be solved by the invention]

However, in the case of dry film, during the manufacturing process of dry film, non-sticking occurs when the resin composition is thinly coated on the carrier film. Due to the non-sticking, the surface of the permanent film after curing will be damaged. The problem of smoothness. "Furthermore, in the photocurable resin composition containing the blue coloring agent used for solder resist, etc., since the blue coloring agent absorbs ultraviolet rays of exposure light, the photosensitivity is reduced, and the productivity tends to be reduced as a result. In order to solve the decrease in sensitivity, when the photopolymerization initiator is added, the thick part of the coating film, such as the part directly formed on the substrate not formed on the copper circuit, will not easily pass through to reach the deep part. Undercutting and reducing the resolution becomes a problem.　　Furthermore, there is also the problem that the appearance of the hardened product is impaired by the coarse particles generated on the surface of the hardened product.

Therefore, the object of the present invention is to provide a photocurable resin composition capable of forming a cured product having excellent appearance and smoothness, and excellent sensitivity and resolution, and a dry film having a resin layer obtained from the composition. , The composition or the cured product of the resin layer of the dry film, and the printed circuit board with the cured product. [Means to solve the problem]

In view of the results of the above-mentioned active review, the inventors found that by combining a blue colorant with an average particle diameter below a specific value and an inorganic filler with an average particle diameter below a specific value, the aforementioned problems can be solved, thus completing the present invention.

That is, the photocurable resin composition of the present invention contains (A) alkali-soluble resin, (B) photopolymerization initiator, (C) blue colorant, and (D) inorganic filler for alkali-developing light The curable resin composition is characterized in that the average particle size of the aforementioned (C) blue colorant is 300 nm or less, and the average particle size of the aforementioned (D) inorganic filler is 1.0 μm or less.

The photocurable resin composition of the present invention preferably further contains an organic filler having an amine 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 is preferably used as the aforementioned (B) photopolymerization initiator, containing an oxime ester-based photopolymerization initiator, and based on the total amount of the photopolymerization initiator, the aforementioned oxime ester-based photopolymerization initiator The blending amount of the agent is 8% by mass or more in terms of solid content.

The photocurable resin composition of the present invention is preferably based on the total amount of the photocurable resin composition, and the blending amount of the aforementioned (C) blue colorant is 0.18 to 0.50% by mass in terms of solid content.

The dry film of the present invention is characterized by having a resin layer obtained from the aforementioned photocurable resin composition.

The cured product of the present invention is characterized 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 aforementioned cured product. [Effects of the invention]

According to the present invention, it is possible to provide a photocurable resin composition capable of forming a cured product with excellent appearance and smoothness and excellent sensitivity and resolution, and a dry film having a resin layer obtained from the composition, and the The composition or the cured product of the resin layer of the dry film, and the printed circuit board having the cured product.

The photocurable resin composition of the present invention contains (A) alkali-soluble resin, (B) photopolymerization initiator, (C) blue colorant, and (D) inorganic filler, which can be alkali-developed photocurable resin The composition is characterized in that the average particle size of the aforementioned (C) blue coloring agent is 300 nm or less, and the average particle size of the aforementioned (D) inorganic filler is 1.0 μm or less. Although the detailed mechanism is unknown, the above-mentioned sensitivity and resolution problems are significant when using a coloring agent with strong ultraviolet absorption such as a blue coloring agent. In the present invention, the average particle size of (C) blue colorant is 300nm or less, and the average particle size of (D) inorganic filler is 1.0μm or less, thereby increasing the light (especially i-line (365nm)) Transmittance. Thereby, even when the blue colorant is used, the sensitivity is not easy to decrease, and light can reach the deep part, so it is considered that it is not easy to produce deep undercuts, and good resolution is obtained. Moreover, when it comes to thin parts such as a substrate on which a copper circuit is formed, it is not easy to produce halos on the copper circuit, and based on this point, good resolution is also obtained. Furthermore, by adopting the above-mentioned structure, the resin composition is applied to the carrier film in the manufacturing step of the dry film, and the non-sticking when forming a thin resin layer is reduced, and the surface smoothness is excellent. Hardened object. Moreover, there are few fine particles that may be produced on the surface of the hardened product, and a hardened product with excellent surface appearance can also be formed.

In addition, by blending the oxime ester-based photopolymerization initiator as the photopolymerization initiator, the increase in absorbance can be suppressed to a minimum, and the sensitivity is further improved. Thereby, a cured film with excellent resolution without undercutting can be easily formed with high sensitivity.

Hereinafter, each component of the photocurable resin composition of the present invention will be described. In addition, in this specification, the so-called (meth)acrylate is the general term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

[(A) Alkali-soluble resin] "(A) Alkali-soluble resin is exemplified by, for example, a compound having two or more phenolic hydroxyl groups, a resin containing a carboxyl group, a compound having a phenolic hydroxyl group and a carboxyl group, and a compound having two or more thiol groups. Compound. Among them, when the alkali-soluble resin is a carboxyl group-containing resin or a phenol resin, it is preferred because of improved adhesion to the substrate. In particular, since it is excellent in developability, the alkali-soluble resin is more preferably a carboxyl group-containing resin. The carboxyl group-containing resin is preferably a carboxyl group-containing resin having an ethylenic double bond, but may also be a carboxyl group-containing resin that does not have an ethylenic double bond.

As a specific example of the resin containing a carboxyl group, the compound (any one of an oligomer and a polymer may be sufficient) as enumerated below is illustrated.

(1) It is obtained by copolymerizing unsaturated carboxylic acid such as (meth)acrylic acid and unsaturated group-containing compounds such as styrene, α-methylstyrene, lower alkyl (meth)acrylate, isobutylene, etc. Resins containing carboxyl groups.

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, etc. and carboxyl-containing groups such as dimethylol propionic acid and dimethylol butyric acid Alcohol compounds and polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A-based alkylene oxide adduct diols, phenolic hydroxyl groups Carboxyl group-containing urethane resin obtained by polyaddition reaction of glycol compounds such as compounds with alcoholic hydroxyl groups.

(3) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, etc. and polycarbonate polyols, polyether polyols, polyester polyols, and polyolefins Polyol, acrylic polyol, bisphenol A-based alkylene oxide adduct, diol, compound having phenolic hydroxyl group and alcoholic hydroxyl group, etc. Polyaddition reaction of urethane A urethane resin containing a terminal carboxyl group formed by the reaction of the end of the resin with an acid anhydride.

(4) Diisocyanate and 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, diphenol (Meth)acrylates of bifunctional epoxy resins such as type epoxy resins or partial acid anhydride modified products, carboxyl-containing diol compounds and diol compounds obtained by the polyaddition reaction of carboxyl-containing urethane formic acid Ester resin.

(5) In the resin synthesis of (2) or (4) above, the terminal (former Group) acrylated carboxyl-containing urethane resin.

(6) In the resin synthesis of (2) or (4) above, a molar reactant such as isophorone diisocyanate and pentaerythritol triacrylate is added. The molecule has one isocyanate group and more than one (methyl) The terminal (meth)acrylated carboxyl-containing urethane resin of acryl-based compounds.

(7) Addition of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. to the hydroxyl groups present on the side chain by reacting multifunctional epoxy resin with (meth)acrylic acid A carboxyl group-containing resin of basal acid anhydride.

(8) Using epichlorohydrin to further react the hydroxy-epoxidized polyfunctional epoxy resin of the difunctional epoxy resin with (meth)acrylic acid, and add dibasic acid anhydride to the carboxyl group-containing resin to the resulting hydroxy group.

(9) The polyfunctional oxetane resin is reacted with a dicarboxylic acid, and a dibasic acid anhydride is added to the produced first-stage hydroxyl group. The carboxyl group-containing polyester resin.

(10) The reaction product obtained by reacting a compound having plural phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide and propylene oxide is reacted with an unsaturated group-containing monocarboxylic acid to obtain A carboxyl-containing resin obtained by reacting the reaction product with a polybasic acid anhydride.

(11) The reaction product obtained by reacting a compound having plural phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate and propylene carbonate is reacted with an unsaturated group-containing monocarboxylic acid, A carboxyl group-containing resin obtained by reacting the obtained reaction product with a polybasic acid anhydride.

(12) Compounds containing at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule, such as epoxy compounds having plural epoxy groups in one molecule and p-hydroxyphenethyl alcohol, and (meth)acrylic acid, etc. The unsaturated group-containing monocarboxylic acid reacts with the alcoholic hydroxyl group of the resulting reaction product with maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, etc. A carboxyl-containing resin obtained by the reaction of acid anhydride.

(13) Add glycidyl (meth)acrylate, α-methylglycidyl (meth)acrylate, etc. to the carboxyl-containing resin described in (1) to (12) above A carboxyl group-containing resin composed of a compound of epoxy group and one or more (meth)acrylic groups.

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

Examples of the compound having a phenolic hydroxyl group include compounds having a biphenyl skeleton or a phenylene skeleton or both skeletons, or using phenol, o-cresol, p-cresol, m-cresol, 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 and other synthetic phenol resins with various skeletons.

In addition, examples of compounds having a phenolic hydroxyl group include phenol novolak resin, alkylphenol novolak resin, bisphenol A novolak resin, dicyclopentadiene type phenol resin, Xylok type phenol resin, and terpene-modified phenol resin. Resin, polyvinylphenols, bisphenol F, bisphenol S-type phenol resin, poly-p-hydroxystyrene, condensate of naphthol and aldehydes, condensate of dihydroxy naphthalene and aldehydes, etc. Resin.

Examples of commercially available phenol resins include HF1H60 (manufactured by Meiwa Chemical Co., Ltd.), Phenolite TD-2090, Phenolite TD-2131 (manufactured by Dainippon Printing Co., Ltd.), Besmol CZ-256-A (manufactured by DIC Corporation), Shonol BRG -555, Shonol BRG-556 (manufactured by Showa Denko Corporation), CGR-951 (manufactured by Maruzen Petrochemical Co., Ltd.), or CST70, CST90, S-1P, S-2P (manufactured by Maruzen Oil Co., Ltd.) of polyvinylphenol.

(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. When the acid value of the alkali-soluble resin is 40 mgKOH/g or more, alkali development becomes easier. On the other hand, when the acid value is 200 mgKOH/g or less, it is preferable because it is easy to draw a resist pattern.

(A) Although the weight average molecular weight of the alkali-soluble resin varies depending on the resin skeleton, it is preferably in the range of 1,500 to 150,000, more preferably in the range of 1,500 to 100,000. When the weight average molecular weight is above 1,500, the non-tackiness performance is good, the moisture resistance of the coating film after exposure is good, the film loss during development can be suppressed, and the reduction of resolution can be suppressed. 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] 　　 In the photocurable resin composition of the present invention, as the (B) photopolymerization initiator, as long as it is a photopolymerization known as a photopolymerization initiator or a photoradical generator As the initiator, any one can be used. As (B) the photopolymerization initiator is exemplified, for example, bis-(2,6-dichlorobenzyl)phenyl phosphine oxide, bis-(2,6-dichlorobenzyl)-2,5- Dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzyl)-4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzyl)-1-naphthalene Phosphine oxide, bis-(2,6-dimethoxybenzyl) phenyl phosphine oxide, bis-(2,6-dimethoxybenzyl)-2,4,4-trimethyl Pentyl phosphine oxide, bis-(2,6-dimethoxybenzyl)-2,5-dimethylphenyl phosphine oxide, bis-(2,4,6-trimethylbenzyl) Yl) phenyl phosphine oxide (made by BASF (Japan), IRGACURE 819) and other bisphenol phosphine oxides; 2,6-dimethoxybenzyl diphenyl phosphine oxide, 2,6-dichlorobenzene Formyl diphenyl phosphine oxide, 2,4,6-trimethylbenzyl phenyl phosphinic acid methyl ester, 2-methyl benzyl diphenyl phosphine oxide, p-pentyl phenyl Monoisopropyl phosphinate, 2,4,6-trimethylbenzyl diphenyl phosphine oxide (manufactured by BASF Japan, IGRACURE TPO), etc.; 1-hydroxy-ring Hexyl phenyl ketone, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1-{4-[4 -(2-Hydroxy-2-methylpropanyl)benzyl)phenyl)-2-methylpropane-1-one, 2-hydroxy-2-methyl-1-phenylpropane-1-one, etc. Hydroxyacetophenones; benzidine, biphenyl, benzidine methyl ether, benzidine ethyl ether, benzine n-propyl ether, benzine isopropyl ether, benzine n-butyl ether, etc. Factors; benzidine alkyl ethers; benzophenone, p-methylbenzophenone, Michler’s ketone, methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4 '-Diethylaminobenzophenone and other benzophenones; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine- 1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1, 2-(dimethylamino)-2-[(4-methyl Phenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone and other acetophenones; thioxanthone , 2-Ethylthioxanthone, 2-isopropylthioxanthone, 2,4-Dimethylthioxanthone, 2,4-Diethylthioxanthone, 2-Chlorothioxanthone, 2,4 -Thioxanthones such as diisopropylthioxanthone; anthraquinone, chloroanthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone , 2-Amylanthraquinone, 2-aminoanthraquinone and other anthraquinones; acetophenone dimethyl acetal, benzyl dimethyl acetal and other acetals; 4-dimethylamino benzoic acid Benzoic acid esters such as ethyl ester, 2-(dimethylamino)ethyl benzoate, and ethyl p-dimethylbenzoate; 1,2 -Octanediol, 1-[4-(phenylthio)-, 2-(O-benzyloxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl) Oxime esters such as acetone)-9H-carbazol-3-yl]-,1-(O-acetyloxime); bis(η5-2,4-cyclopentadien-1-yl)-bis (2,6-Difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, bis(cyclopentadienyl)-bis[2,6-difluoro-3-(2-(1- Pyridin-1-yl) ethyl) phenyl) titanium and other titanocenes; phenyl disulfide 2-nitropyridine, butyroin, anisoin ethyl ether (anisoin ethyl ether), azobis Isobutyronitrile, tetramethylthiuram disulfide, etc. The above-mentioned photopolymerization initiators may be used singly or in combination of two or more kinds. Among them, oxime esters (hereinafter also referred to as "oxime ester-based photopolymerization initiators") are preferred, and ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl) is more preferred. -9H-carbazol-3-yl]-,1-(O-acetyloxime). "(B) The blending amount of the photopolymerization initiator is, for example, 0.01-30 parts by mass relative to 100 parts by mass of the solid content of the (A) alkali-soluble resin. In addition, the blending amount of the oxime ester-based photopolymerization initiator is preferably 8% by mass or more in terms of solid content, more preferably 12% by mass or more based on the total amount of the photopolymerization initiator. By containing 8% by mass or more, high sensitivity can be easily achieved. The oxime ester-based photopolymerization initiator may be used singly or in combination of two or more kinds.

As the oxime ester-based photopolymerization initiator, any one can be used as long as it is a conventional oxime ester-based photopolymerization initiator. As commercially available products, for example, CGI-325, IRGACURE OXE01 (1,2-octanediol, 1-[4-(phenylthio)-, 2-(O-benzyloxime) manufactured by BASF Corporation of Japan ]), IRGACURE OXE02 (ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime )), N-1919 and NCI-831 manufactured by ADEKA, TR-PBG-304 manufactured by Changzhou Qiangli Electronic New Material Co., Ltd., etc.

(式中，X表示氫原子、碳數1~17之烷基、碳數1~8之烷氧基、苯基、苯基(可經碳數1~17之烷基、碳數1~8之烷氧基、胺基、具有碳數1~8之烷基的烷胺基或二烷胺基取代)、萘基(可經碳數1~17之烷基、碳數1~8之烷氧基、胺基、具有碳數1~8之烷基的烷胺基或二烷胺基取代)，Y、Z分別表示氫原子、碳數1~17之烷基、碳數1~8之烷氧基、鹵基、苯基、苯基(可經碳數1~17之烷基、碳數1~8之烷氧基、胺基、具有碳數1~8之烷基的烷胺基或二烷胺基取代)、萘基(可經碳數1~17之烷基、碳數1~8之烷氧基、胺基、具有碳數1~8之烷基的烷胺基或二烷胺基取代)、蒽基、吡啶基、苯并呋喃基、苯并噻吩基，Ar表示鍵或碳數1~10之伸烷基、伸乙烯基、伸苯基、伸聯苯基、伸吡啶基、伸萘基、伸硫苯基、伸蒽基、伸噻吩基、伸呋喃基、2,5-吡咯二基、4,4’-二苯乙烯二基、4,2’-苯乙烯二基，n為0或1之整數)。In addition, a starter having two oxime ester groups in the molecule can also be preferably used. Specifically, an oxime ester compound having a carbazole structure represented by the following general formula is exemplified.

(In the formula, X represents a hydrogen atom, an alkyl group with 1 to 17 carbons, an alkoxy group with 1 to 8 carbons, a phenyl group, and a phenyl group. Alkoxy group, amino group, alkylamino group or dialkylamino group with carbon number 1~8), naphthyl group (can be substituted by alkyl group with carbon number 1~17, alkyl group with carbon number 1~8 Oxy group, amino group, alkylamino group or dialkylamino group having an alkyl group with 1 to 8 carbon atoms), Y and Z respectively represent a hydrogen atom, an alkyl group with 1 to 17 carbon atoms, and an alkyl group with 1 to 8 carbon atoms Alkoxy group, halo group, phenyl group, phenyl group Or dialkylamino group substitution), naphthyl (can be substituted by C1-C17 alkyl group, C1-C8 alkoxy group, amino group, C1-C8 alkyl group or two Alkylamino group substitution), anthracenyl, pyridyl, benzofuranyl, benzothienyl, Ar represents a bond or alkylene, vinylene, phenylene, biphenylene, and Pyridyl, naphthylene, thiophenyl, anthrylene, thienyl, furanyl, 2,5-pyrrolediyl, 4,4'-stilbene diyl, 4,2'-styrene Dibasic, n is an integer of 0 or 1).

Particularly preferably, in the aforementioned general formula, X and Y are each methyl or ethyl, Z is methyl or phenyl, n is 0, and Ar is a bond or phenylene, naphthylene, thiophenylene or phenylene Thienyl.

(式中，R¹ 為碳原子數1~4之烷基，或可經硝基、鹵原子或碳數1~4之烷基取代之苯基， 　　R² 為碳原子數1~4之烷基、碳原子數1~4之烷氧基或可經碳數1~4之烷基或碳原子數1~4之烷氧基取代之苯基， 　　R³ 表示可經氧原子或硫原子連結、可經苯基取代之碳原子數1~20之烷基、可經碳數1~4之烷基取代之苄基， 　　R⁴ 表示硝基或以X-C(=O)-表示之醯基，X表示可經碳數1~4之烷基取代之芳基、噻吩基、嗎啉基、硫苯基或以下述式表示之構造)。

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

(In the formula, R ¹ is an alkyl group with 1 to 4 carbon atoms, or a phenyl group that can be substituted by a nitro group, a halogen atom or an alkyl group with ^{1 to 4 carbon atoms, and R 2} is an alkane with 1 to 4 carbon atoms Group, alkoxy with 1 to 4 carbon atoms or phenyl which can be substituted by alkyl with 1 to 4 carbon atoms or alkoxy with 1 to 4 carbon atoms, R ³ means it can be linked via oxygen or sulfur atom , Alkyl group with 1 to 20 carbon atoms which may be substituted by phenyl, benzyl group which may be substituted with alkyl with 1 to 4 carbon atoms, R ⁴ represents a nitro group or an acyl group represented by XC(=O)-, X represents an aryl group, a thienyl group, a morpholinyl group, a thiophenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, or a structure represented by the following formula).

In addition, examples include Japanese Patent Application Publication No. 2004-359639, Japanese Patent Application Publication No. 2005-097141, Japanese Patent Application Publication No. 2005-220097, Japanese Patent Application Publication No. 2006-160634, Japanese Patent Application Publication No. 2008-094770, Carbazole oxime ester compounds described in Japanese Patent Application Publication No. 2008-509967, Japanese Patent Application Publication No. 2009-040762, Japanese Patent Application Publication No. 2011-80036, and the like.

[(C) Blue Coloring Agent] "The photocurable resin composition of the present invention contains a blue coloring agent having an average particle diameter of 300 nm or less. The average particle size is preferably 280 nm or less, more preferably 250 nm or less. By setting the average particle size to 300 nm or less, the appearance of the surface of the cured product can be improved.　　 Here, the average particle size of the blue colorant is the value of D50 measured by the laser diffraction method. An example of a measuring device for the laser diffraction method is Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd.

(C) The maximum particle diameter (D100) of the blue colorant is preferably 800 nm or less, more preferably 700 nm or less, and still more preferably 600 nm or less. If it is 800 nm or less, the appearance of the cured product can be more favorable with fewer coarse particles. Specifically, when observing the cured film by the method described in the following examples, no particles of 10 μm or more were generated.

In addition, from the viewpoint of improving the concealability of the cured product, based on the total amount of the photocurable resin composition, the content is preferably 0.18 to 0.50% by mass in terms of solid content. When it is 0.18% by mass or more in terms of solid content, the circuit concealment is excellent. In the photocurable resin composition of the present invention, even if the (C) blue coloring agent is blended in a relatively large amount of 0.18% by mass or more in terms of solid content, the sensitivity and resolution are not easily reduced, so it can be used especially for thinning It is difficult to have both sensitivity, resolution and concealment of hardened objects. When it is 0.50% by mass or less, the resolution is more excellent. It is more preferably 0.20% by mass to 0.40% by mass.

(C) The type of blue coloring agent is not particularly limited, and conventionally used blue coloring agents can be used, which may be any of pigments, dyes, and pigments, but those that do not contain halogen atoms are preferred. As blue colorants, there are phthalocyanine series and anthraquinone series. The pigment series are classified as pigment compounds. Specifically, the following can be exemplified: Pigment Blue 15, 15:1, 15:2, and 15: 3. 15:4, 15:6, 16, 60. As the dye system, solvent blue 35, 63, 68, 70, 83, 87, 94, 97, 122, 136, 67, 70, etc. can be used. In addition to the above, metal-substituted or unsubstituted phthalocyanine compounds can also be used. A blue coloring agent may be used individually by 1 type, and may use 2 or more types together.

(C) The method of 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 a bead mill, a jet mill, or the like. In addition, as the (C) blue coloring agent, a commercially available product having an average particle diameter within the above range can also be used as it is.

(C) The blue coloring agent is preferably blended in a slurry state. By blending in a slurry state, it is easy to be highly dispersed, prevent aggregation, and can be easily handled as a coloring agent with an average particle size in the above-mentioned specific range.

(C) The absorbance of the blue colorant at a wavelength of 365 nm measured by the following measurement method is preferably 0.5 to 1.0. The measurement method is to first add 0.1% of the blue coloring agent to 100 parts of the non-volatile solid content of the alkali-soluble resin A-3 described in the Examples that has no absorption at a wavelength of 365 nm to prepare a composition. The composition was dried on glass with an applicator at 80°C for 30 minutes to form a dry coating film so as to be 15 μm thick, and the absorbance was measured with an ultraviolet-visible-infrared spectrophotometer V-670 (manufactured by JASCO Corporation).

The photocurable resin composition of the present invention may contain other colorants within a range that does not impair the effects of the present invention. As the other coloring agents, conventionally used coloring agents such as red, green, yellow, white, black, and (C) blue coloring agents other than blue coloring agents can be used, and they can be any of pigments, dyes, and pigments. Specifically, for example, a color index (C.I.; issued by The Society of Dyers and Colourist) number is attached. However, from the viewpoint of reducing the environmental load and the impact on the human body, a halogen-free coloring agent is preferred. "In the photocurable resin composition of the present invention, the average particle size of coloring agents other than blue is also preferably smaller, preferably 300 nm or less. By making the average particle size of colorants other than blue also smaller, the sensitivity, resolution, surface smoothness and appearance of the cured product can be further improved.

Examples of red colorants include monoazo, bisazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridine Ketone series and so on. As blue colorants, there are metal-substituted or unsubstituted phthalocyanine series and anthraquinone series, and the pigment series include compounds classified as pigments. As green colorants, there are also metal-substituted or unsubstituted phthalocyanine, anthraquinone, and perylene systems. Examples of yellow colorants include monoazo, bisazo, condensed azo, benzimidazolone, isoindolinone, anthraquinone, and the like. Examples of white colorants include rutile, anatase, and other titanium oxides. Examples of black colorants include titanium black, carbon black, graphite, iron oxide, anthraquinone, cobalt oxide, copper oxide, manganese, antimony oxide, nickel oxide, perylene, and aniline. Pigments, molybdenum sulfide, bismuth sulfide, etc. In addition, for the purpose of adjusting the color tone, coloring agents such as orange and brown can also be added.

[(D) Inorganic filler] "In the photocurable resin composition of the present invention, as an inorganic filler, those having an average particle diameter of 1.0 μm or less are contained, and more preferably, those having an average particle diameter of 0.8 μm or less are contained. Here, (D) the average particle size of the inorganic filler is the value of D50 measured by the laser diffraction method. An example of a measuring device for the laser diffraction method is Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd.

(D) Inorganic fillers are not particularly limited, and conventional inorganic fillers can be used, such as silica, crystalline silica, Neuburg silica, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate , Calcium carbonate, natural mica, synthetic mica, aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, zinc white and other inorganic fillers . Among them, silica is preferred, which is less likely to be the starting point of cracks due to its small surface area and can disperse stress throughout the whole, and is more preferably spherical silica.

(D) Inorganic fillers can also be surface-treated. Here, the surface treatment of the inorganic filler refers to a treatment to improve the compatibility with the resin component. The surface treatment of the inorganic filler may be any one of a surface treatment liquid in which a curable reactive group is introduced on the surface of the inorganic filler, or a surface treatment in which no curable reactive group is introduced. Here, the so-called curable reactive group is not particularly limited as long as it is a group for curing reaction with a curable compound such as an alkali-soluble resin or a thermosetting component, and it may be a photocurable reactive group or a thermally reactive group. Sex-based. Examples of photocurable reactive groups include methacryl, acrylic, vinyl, and styryl groups, and examples of thermosetting reactive groups include epoxy, amino, hydroxyl, carboxyl, isocyanate, and imino groups. , Oxetanyl, mercapto, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, oxazolinyl, etc. The method of introducing a curable reactive group on the surface of the inorganic filler is not particularly limited, as long as it is introduced using a conventionally used method, as long as the surface treatment agent having a curable reactive group, for example, a coupling agent having a curable reactive group as an organic group, is used. It is sufficient to treat the surface of the inorganic filler. As the coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, etc. can be used. Examples of inorganic fillers that have been surface-treated without hardening reactive groups include, for example, silica-alumina surface treatment, titanate coupling agent treatment, aluminate coupling agent treatment, organic treatment inorganic fillers, etc. .

(D) The method for adjusting the average particle size of the inorganic filler is not particularly limited, but it is preferably pre-dispersed by, for example, a bead mill or a jet mill. In addition, as the (D) inorganic filler, a commercially available product having an average particle diameter within the above range can be used as it is.

(D) The inorganic filler is preferably blended in a slurry state. By blending in a slurry state, it is easy to highly disperse, prevent aggregation, and can be easily handled as an inorganic filler with an average particle diameter in the above-mentioned specific range.

(D) An inorganic filler can be used individually by 1 type or in combination of 2 or more types. (D) The blending amount of the inorganic filler is preferably 80 to 450 parts by mass, more preferably 100 to 200 parts by mass relative to 100 parts by mass of the solid content of the (A) alkali-soluble resin. When it is 80 parts by mass or more, heat resistance is excellent. When it is 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. By adding a thermosetting component, it is expected that the heat resistance will be further improved. A thermosetting component can be used individually by 1 type or in combination of 2 or more types. As the thermosetting component, any conventional ones can be used. For example, amine resins such as melamine resins, benzoguanamine resins, melamine derivatives, benzoguanamine derivatives, isocyanate compounds, blocked isocyanate compounds, cyclic carbonate compounds, epoxy compounds, oxetane compounds, etc. can be used Conventional thermosetting components such as episulfide resin, bismaleimide, and carbodiimide resin. 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 with a single epoxy group, that is, a multifunctional epoxy compound, a compound with multiple oxetanyl groups in the molecule, that is, a multifunctional oxetane compound, a compound with multiple sulfide groups in the molecule, That is, episulfide resin and so on.

As the polyfunctional epoxy compound, exemplified are epoxidized vegetable oil; bisphenol A type epoxy resin; hydroquinone type epoxy resin; bisphenol type epoxy resin; thioether type epoxy resin; brominated epoxy resin; novolac Type epoxy resin; bisphenol novolac type epoxy resin; bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin; glycidylamine type epoxy resin; hydantoin type epoxy resin; alicyclic Formula epoxy resin; trihydroxyphenylmethane type epoxy resin; bixylenol type or diphenol type epoxy resin or a mixture of these; bisphenol S type epoxy resin; bisphenol A novolac type epoxy resin ; Tetrahydroxyphenylethane type epoxy resin; Heterocyclic epoxy resin; Diglycidyl phthalate resin; Tetraglycidyl xylene yl ethane resin; Epoxy resin containing naphthyl groups; Dicyclopentadiene skeleton epoxy resin; glycidyl methacrylate copolymerized epoxy resin; cyclohexyl maleimide and glycidyl methacrylate copolymerized epoxy resin; epoxy modified Polybutadiene rubber derivatives; CTBN modified epoxy resin, but not limited to these. These epoxy resins can be used individually by 1 type or in combination of 2 or more types. Among them, particularly preferred are novolak type epoxy resin, bisphenol type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin, biphenol novolak type epoxy resin, and naphthalene type epoxy resin. Or a mixture of these.

Examples of oxetane compounds 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-oxetanyl) methyl acrylate, methacrylic acid (3-methyl- Multifunctional oxetanes such as 3-oxetanyl) methyl ester, (3-ethyl-3-oxetanyl) methyl methacrylate or these oligomers or copolymers In addition, examples include oxetanol and novolac resins, poly(p-hydroxystyrene), cardo bisphenols, calixarenes, calix resorcinarenes, or Ether compounds with hydroxyl-containing resins such as silsesquioxane, etc. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth)acrylate is also exemplified.

Examples of compounds having a plurality of cyclic sulfide groups in the molecule include bisphenol A type episulfide resins and the like. Furthermore, an episulfide resin in which the oxygen atom of the epoxy group of the novolak type epoxy resin is substituted with a sulfur atom by the same synthesis method can also be used. The blending amount of the thermosetting component having plural cyclic (thio) ether groups in these molecules is 1 equivalent relative to the alkali soluble group such as the carboxyl group or phenolic hydroxyl group of (A) alkali-soluble resin, cyclic (sulfur) ) The ether group is preferably 0.6 to 2.5 equivalents, more preferably 0.8 to 2.0 equivalents.

Examples of amine-based resins such as melamine derivatives and benzoguanamine derivatives include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycol urea compounds, methylol urea compounds, and the like.

As the isocyanate compound, a polyisocyanate compound can be blended. Examples of polyisocyanate compounds include 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, naphthalene-1,5-diisocyanate, o-xylene diisocyanate, Aromatic polyisocyanates such as m-xylene diisocyanate and 2,4-toluene dimer; tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate Aliphatic polyisocyanates such as isocyanate, 4,4-methylene bis(cyclohexyl isocyanate) and isophorone diisocyanate; alicyclic polyisocyanates such as bicycloheptane triisocyanate; and the addition of the isocyanate compounds exemplified above Body, biuret body and isocyanurate body.

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, for example, the above-mentioned polyisocyanate compound and the like are exemplified. Examples of isocyanate blocking agents include, for example, phenol-based blocking agents; internal amine-based blocking agents; active methylene-based blocking agents; alcohol-based blocking agents; oxime-based blocking agents; thiol-based blocking agents; Amide-based blocking agent; imine-based blocking agent; amine-based blocking agent; imidazole-based blocking agent; imine-based blocking agent, etc.

The thermosetting component may be used singly or in combination of two or more kinds. The blending amount of the thermosetting component is preferably 20 to 60 parts by mass, more preferably 30 to 50 parts by mass relative to 100 parts by mass of the solid content of the (A) alkali-soluble resin. At 20 parts by mass or more, heat resistance is excellent. In the case of 60 parts by mass or less, storage stability is improved.

(Compound with ethylenically unsaturated group) 　　 The photocurable resin composition of the present invention may contain a reactive diluent which is different from (A) alkali-soluble resin, specifically, it has an ethylenically unsaturated group Compound. As the compound having an ethylenically unsaturated group, conventionally used photopolymerizable oligomers of photocurable monomers, photopolymerizable vinyl monomers, and the like can be used.

Examples of the photopolymerizable oligomer include unsaturated polyester-based oligomers and (meth)acrylate-based oligomers. Examples of (meth)acrylate oligomers include phenol novolac epoxy (meth)acrylate, cresol novolac epoxy (meth)acrylate, and bisphenol-type epoxy (meth)acrylic acid. Epoxy (meth)acrylate, urethane (meth)acrylate, epoxy urethane (meth)acrylate, polyester (meth)acrylate, polyether ( (Meth)acrylate, polybutadiene modified (meth)acrylate, etc.

As the photopolymerizable vinyl monomer system, known and used, for example, styrene derivatives such as styrene, chlorostyrene, and α-methylstyrene; vinyl acetate, vinyl butyrate, or vinyl benzoate can be cited. Vinyl esters such as vinyl isobutyl ether, vinyl-n-butyl ether, vinyl-tertiary butyl ether, vinyl-n-pentyl ether, vinyl isoamyl ether, vinyl-n-butyl ether Stearyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether and other vinyl ethers; acrylamide, methacrylamide, N -Hydroxymethacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethacrylamide, N-ethoxymethacrylamide, N-butoxymethacrylamide (Meth)acrylamides such as amines; allyl compounds such as triallyl isocyanurate, diallyl phthalate, diallyl isophthalate, etc.; (meth)acrylic acid 2-Ethylhexyl ester, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, phenoxy (meth)acrylate (Meth)acrylic acid esters such as ethyl ester; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, pentaerythritol tri(meth)acrylate, and hydroxyalkyl (meth)acrylates ; Alkoxyalkylene glycol mono(meth)acrylates such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; ethylene glycol di(meth)acrylate, Butylene glycol di(meth)acrylates, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylic acid Ester, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. alkylene polyol poly(meth)acrylate; diethylene glycol di(meth)acrylate, triethylenedi Polyoxyalkylene glycol poly(meth)acrylates such as alcohol di(meth)acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane tri(meth)acrylate, etc.; Poly(meth)acrylates such as neopentyl glycol hydroxypivalate di(meth)acrylate; isocyanurates such as [(meth)acryloxyethyl] isocyanurate Ester type poly(meth)acrylates, etc. These can be used alone or in combination of two or more according to the required characteristics.

The compound having an ethylenically unsaturated group can be used singly or in combination of two or more kinds. The blending 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 relative to 100 parts by mass of the solid content of the (A) alkali-soluble resin. When it is 3 parts by mass or more, it contributes to high sensitivity. When it is 25 parts by mass or less, the resolution is good.

(Thermosetting catalyst) "The photocurable resin composition of the present invention may contain a thermosetting catalyst. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole and other imidazole derivatives; dicyandiamide, benzyldimethylamine, 4-(dimethyl Amine)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc. Compounds, hydrazine compounds such as dihydrazine adipate and dihydrazine sebacate; phosphorus compounds such as triphenylphosphine, etc. Moreover, guanamine, acetguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloxyethyl-S-triazine, 2-vinyl-2, 4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine. Isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine. S-triazine derivatives such as isocyanuric acid adducts are preferably used in combination with compounds that can also function as adhesion imparting agents and thermosetting catalysts. Moreover, as long as it can be used as a thermosetting catalyst, it may also be an organic filler.

The thermosetting catalyst preferably has an average particle diameter (D50) of 1 μm or less and a maximum particle diameter (D100) of 6 μm or less. In particular, the average particle diameter is preferably 800 nm or less, more preferably 600 nm or less. The maximum particle size is preferably 5 μm or less, more preferably 4 μm or less. The smaller the average particle size and the maximum particle size, the better the gold plating resistance. Here, the average particle size is the value of D50 measured by the laser diffraction method. An example of a measuring device for the laser diffraction method is Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd.

As the thermosetting catalyst, an organic filler having an amine group is preferred, and specifically, at least one of melamine and dicyanodiamide (DICY) is preferred.

The thermosetting catalyst can be used singly or in combination of two or more. The blending amount of the thermosetting catalyst is preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass relative to 100 parts by mass of the solid content of the (A) alkali-soluble resin. When it is 0.5 parts by mass or more, heat resistance is excellent. When it is 10 parts by mass or less, storage stability is improved.

(Organic solvent) "The photocurable resin composition of the present invention may contain an organic solvent for the purpose of preparation of the composition or adjustment of viscosity when applied to a substrate or carrier film. As organic solvents, ketones such as methyl ethyl ketone and cyclohexanone can be used; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol Alcohol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether and other glycols Ethers; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether ethyl Esters such as acid esters, dipropylene glycol monomethyl ether acetate, propylene carbonate, etc.; aliphatic hydrocarbons such as octane and decane; petroleum ether, naphtha, naphtha and other petroleum solvents, etc. Know the commonly used organic solvents. These organic solvents can be used individually by 1 type or in combination of 2 or more types.

(Other optional components) 　　 The photocurable resin composition of the present invention may also incorporate other curing components or other additives conventionally used in the field of electronic materials. Examples of other curing components include isocyanate resins, active ester resins, maleimide compounds, and alicyclic olefin polymers. Examples of other additives include thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, anti-aging agents, and antibacterial agents. Anti-mold agent, defoaming agent, leveling agent, tackifier, adhesion imparting agent, thixotropy imparting agent, light start aid, sensitizer, thermoplastic resin, organic filler, mold release agent, surface treatment agent , Dispersants, dispersing aids, surface modifiers, stabilizers, phosphors, etc.

The photocurable resin composition of the present invention can be used as a dry film or as a liquid. When used as a liquid, it may be single-liquid or two-liquid or more.

The light-curable resin composition of the present invention has an absorbance at a wavelength of 365 nm, preferably 0.3 to 0.85 per 15 μm of the dry coating film thickness.

Next, the dry film of the present invention has a resin layer obtained by coating and drying the photocurable resin composition of the present invention on a carrier film. When forming a dry film, first, dilute the photocurable resin composition of the present invention with the above-mentioned organic solvent to adjust the viscosity to an appropriate viscosity. , Rubber roll coater, reverse roll coater, conveyor roll coater, gravure coater, spray coater, etc., coat uniform thickness on the carrier film. Subsequently, the coated 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 the film thickness after drying is generally 3 to 150 μm, preferably the range of 5 to 60 μm is appropriately selected.

As the carrier film, a plastic film is used. For example, polyester film such as polyethylene terephthalate (PET), polyimide film, polyimide imide film, polypropylene film, and polystyrene film can be used. And other plastic films. The thickness of the carrier film is not particularly limited, but it is generally selected appropriately within the range of 10 to 150 μm. More preferably, it is in the range of 15 to 130 μm.

After forming a film of the photocurable resin composition of the present invention on a carrier film, a peelable cover film is preferably laminated on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. As the peelable cover film, for example, polyethylene film, polytetrafluoroethylene film, polypropylene film, surface-treated paper, etc. can be used. As a cover film, what is necessary is just to have adhesive force less than a resin layer and a carrier film when peeling a cover film.

Furthermore, in the present invention, the photocurable resin composition of the present invention may be coated on the above-mentioned cover film and dried to form a resin layer, and a carrier film may be laminated on the surface thereof. That is, in the present invention, when a dry film is produced, any one of a carrier film and a cover film can be used as the film to which the photocurable resin composition of the present invention is applied.

The printed circuit 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. As a manufacturing method of the printed circuit board of the present invention, for example, the photocurable resin composition of the present invention is adjusted to a viscosity suitable for the coating method using the above-mentioned organic solvent, and the substrate is applied by dip coating or flow coating. After coating by method, roll coating method, bar coating method, screen printing method, curtain coating method, etc., the organic solvent contained in the composition is volatilized and dried (temporary drying) at a temperature of 60~100°C. Form a non-tacky resin layer. Furthermore, in the case of a dry film, after the resin layer is brought into contact with the substrate by a laminator or the like, the resin layer can be formed on the substrate by peeling off the carrier film.

As the above-mentioned substrate, for example, a printed circuit board or a flexible printed circuit board in which a circuit is formed with copper, etc., can be used. Paper phenol, paper epoxy resin, glass cloth epoxy resin, glass polyimide, glass cloth/ Non-woven epoxy resin, glass cloth/paper epoxy resin, synthetic fiber epoxy resin, fluororesin. Polyethylene. Polyphenylene ether, polyphenylene oxide. Cyanate ester and other high-frequency circuits with copper-clad laminates and other materials, copper-clad laminates of all grades (FR-4, etc.), as well as metal substrates, polyimide film, PET film, polyethylene naphthalate Diester (PEN) film, glass substrate, ceramic substrate, wafer board, etc.

The volatilization drying performed after coating the photocurable resin composition of the present invention can use a hot air circulating drying furnace, IR furnace, heating plate, forced oven, etc. The method of convective contact and the method of blowing on the support with the nozzle) are carried out.

After the resin layer is formed on the printed circuit board, it is selectively exposed with active energy rays through a mask formed with a specific pattern, and the unexposed part is developed by a dilute alkali aqueous solution (for example, 0.3 to 3% by mass sodium carbonate aqueous solution), and Form the pattern of the hardened object. Furthermore, the cured product is irradiated with active energy rays and then heated and cured (for example, 100~220°C) or heated and cured after being irradiated with active energy rays, or only heated and cured, and the curing is finally completed (formal curing), and various properties such as adhesion and hardness are formed. Excellent hardened film. In addition, when the photocurable resin composition of the present invention contains a photobase generator, it is preferably heated after exposure and before development. As the heating condition after exposure and before development, it is preferably, for example, heating at 60 to 150°C for 1 to 60 minute.

As the exposure machine used for the above-mentioned active energy ray irradiation, if it is equipped with a high-pressure mercury lamp, ultra-high pressure mercury lamp, metal halide lamp, mercury arc lamp, etc., the device irradiates ultraviolet rays in the range of 350 to 450 nm, and direct drawing can also be used. Device (for example, a direct laser imaging device that directly draws an image with a laser using CAD data from a computer). As the light source or laser light source of the direct drawing machine, the maximum wavelength should be in the range of 350~450nm. The amount of exposure used for image formation varies with film thickness, etc., but is generally 10~1000 mJ/cm ² , preferably in the range of 20~800 mJ/cm ^2.

As the above-mentioned developing method, dipping, rinsing, spraying, brushing, etc. can be used. As the developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, etc. can be used. Alkaline aqueous solutions of ammonia, amines, etc.

The photocurable resin composition of the present invention can be better used to form a hardened film on a printed circuit board, better used to form a permanent coating film, and better used to form a solder resist and an interlayer insulating film , Cover layer and use. Furthermore, according to the photocurable resin composition of the present invention, a cured product with excellent appearance and surface smoothness can be obtained even if it is a thin film. Because of its excellent sensitivity and resolution, it can be used well in demanding films with high reliability. Formation of flexible printed circuit boards, such as package substrates, especially permanent coatings (especially solder resists) for FC-BGA.

In particular, the photocurable resin composition of the present invention can be preferably used to form a thin film, preferably a cured film having a thickness of 3-40 μm, more preferably 5-30 μm. [Example]

Examples and comparative examples are shown below to specifically illustrate the present invention, but the present invention is not limited to the following examples. In addition, the following "parts" and "%" are all based on quality unless otherwise specified.

(Synthesis of Alkali-soluble Resin A-1) In an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device, and a stirring device, a novolak type cresol resin (trade name "SHONOL CRG951", Showa Denko Corporation) Prepared, OH equivalent: 119.4) 119.4 parts, 1.19 parts of potassium hydroxide and 119.4 parts of toluene, replace nitrogen in the system while stirring, and heat up. Secondly, 63.8 parts of propylene oxide was slowly added dropwise, and ^{reacted at 125-132°C and 0-4.8 kg/cm 2} for 16 hours. Subsequently, it was cooled to room temperature, and 1.56 parts of 89% phosphoric acid was added and mixed in the reaction solution to neutralize potassium hydroxide to obtain a novolac type with 62.1% non-volatile content and 182.2 mgKOH/g (307.9g/eq.) hydroxyl value. Propylene oxide reaction solution of cresol resin. The phenolic hydroxyl group has an average addition of 1.08 mol per 1 equivalent of propylene oxide. The resulting novolak-type cresol resin propylene oxide reaction solution 293.0 parts, 43.2 parts acrylic acid, 11.53 parts methanesulfonic acid, 0.18 parts methyl hydroquinone, and 252.9 parts toluene are fed into the reaction equipped with a mixer, a thermometer and an air blowing tube Air was blown into the vessel at a rate of 10ml/min, and the reaction was carried out at 110°C for 12 hours while stirring. The water produced by the reaction is used as an azeotropic mixture with toluene, and 12.6 parts of water is distilled out. After cooling to room temperature, the resulting reaction solution was neutralized with 35.35 parts of a 15% sodium hydroxide aqueous solution, and then washed with water. Subsequently, the toluene was replaced with 118.1 parts of diethylene glycol monoethyl ether acetate in an evaporator and distilled off to obtain a novolac type acrylate resin solution. Next, 332.5 parts of the obtained novolac type acrylate resin solution and 1.22 parts of triphenylphosphine are fed into a reactor equipped with a stirrer, a thermometer and an air blowing tube, and air is blown in at a speed of 10ml/min, and slowly added while stirring 60.8 parts of tetrahydrophthalic anhydride, react at 95~101°C for 6 hours, take it out after cooling. In this way, a solution of photosensitive carboxyl group-containing resin A-1 with a solid content of 65% and an acid value of the solid content of 87.7 mgKOH/g was obtained. Hereinafter, the solution of this carboxyl group-containing photosensitive resin is referred to as resin solution A-1.

(Synthesis of alkali-soluble resin A-2) In a flask equipped with a thermometer and a stirrer, feed 456 parts of bisphenol A, 228 parts of water, and 649 parts of 37% formaldehyde. Keep the temperature below 40°C, and add 25% hydroxide. 228 parts of sodium aqueous solution were reacted at 50°C for 10 hours after the addition was completed. After the reaction, it was cooled to 40°C and neutralized to pH 4 with 37.5% phosphoric acid aqueous solution while keeping the temperature below 40°C. Then stand still to separate the water layer. After separation, add 300 parts of methyl isobutyl ketone and dissolve it uniformly, then wash with 500 parts of distilled water 3 times, and remove water, solvents, etc. under reduced pressure at a temperature below 50°C. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1230 parts of a methanol solution of the polymethylol compound. After a part of the obtained methanol solution of polymethylol compound was dried in a vacuum dryer at room temperature, the solid content was 55.2%. Into a flask equipped with a cooling tube and a stirrer, 500 parts of methanol solution of the obtained polymethylol compound and 440 parts of 2,6-xylenol were fed and dissolved uniformly at 50°C. After uniformly dissolving, the methanol is removed at a temperature below 50°C under reduced pressure. Then, 8 parts of oxalic acid was added and reacted at 100°C for 10 hours. After the reaction, the distillate was removed at 180° C. and 50 mmHg under reduced pressure to obtain 550 parts of novolak resin A. In an autoclave equipped with a thermometer, a nitrogen introduction device, an alkylene oxide introduction device and a stirring device, 130 parts of novolak resin A, 2.6 parts of 50% sodium hydroxide aqueous solution, toluene/methyl isobutyl ketone (mass ratio = 2/1) 100 parts, replace the system with nitrogen while stirring, then heat and increase the temperature, and slowly introduce 60 parts of propylene oxide ^{at 150°C and 8 kg/cm 2 to react.} After the reaction continued for about 4 hours until the gauge pressure reached 0.0 kg/cm ² , it was cooled to room temperature. Add and mix 3.3 parts of 36% hydrochloric acid aqueous solution to this reaction solution to neutralize sodium hydroxide. The neutralization reaction product was diluted with toluene, washed with water 3 times, and the solvent was removed with an evaporator to obtain a propylene oxide adduct of novolak resin A with a hydroxyl value of 189 g/eq. This phenolic hydroxyl group adds 1 mole on average per 1 equivalent of propylene oxide. 189 parts of propylene oxide adduct, 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 fed into the obtained novolak resin A of propylene oxide adduct. Equipped with a mixer, a thermometer, and an air blowing tube In the reactor, the temperature was raised to 115°C while blowing in the air while stirring, the water produced by the reaction was distilled out as an azeotropic mixture with toluene, and the reaction was continued for 4 hours, and then cooled to room temperature. The resulting reaction solution was washed with a 5% NaCl aqueous solution, and after the toluene was removed by distillation under reduced pressure, diethylene glycol monoethyl ether acetate was added to obtain an acrylic resin solution with a solid content of 67%. Next, in a 4-necked flask with a stirrer and a reflux cooler, 322 parts of the resulting acrylic resin solution, 0.1 part of hydroquinone monomethyl ether, and 0.3 part of triphenylphosphine were fed into the 4-necked flask. The mixture was heated at 110°C and four 60 parts of hydrogen phthalic anhydride was reacted for 4 hours, and after cooling, it was taken out. The thus obtained photosensitive carboxyl group-containing resin solution has a solid content of 70% and a solid acid value of 81 mgKOH/g. Hereinafter, the solution of this carboxyl group-containing photosensitive resin is referred to as resin solution A-2.

(Synthesis of alkali-soluble resin A-3) 600g of p-diethylene glycol monoethyl ether acetate is fed into o-cresol novolac type epoxy resin [manufactured by DIC, EPICLON N-695, softening point 95°C, epoxy equivalent 214, average number of functional groups 7.6] 1070 g (glycidyl number (total number of aromatic rings): 5.0 mol), 360 g (5.0 mol) of acrylic acid, and 1.5 g of hydroquinone, heated and stirred at 100°C to uniformly dissolve.　　 Next, 4.3 g of triphenylphosphine was fed, and after heating and reacting at 110° C. for 2 hours, the temperature was raised to 120° C. and the reaction was carried out for 12 hours. Into the resulting reaction liquid, 415 g of aromatic hydrocarbons (SOLVESSO 150) and 456.0 g (3.0 mol) of tetrahydrophthalic anhydride were fed, reacted at 110°C for 4 hours, and cooled to obtain a photosensitive resin containing carboxyl groups. Solution. The solid content of the resin solution thus obtained was 65%, and the acid value of the solid content was 89 mgKOH/g. Hereinafter, this solution of the carboxyl group-containing photosensitive resin is referred to as resin solution A-3.

(Preparation of blue colorant paste C-1, C-2, RC-1) (C-1) 　　 12 parts by mass of phthalocyanine blue, 5 parts by mass of CAP (cellulose acetate propionate) resin, 83 parts by mass of DPM (dipropylene glycol monomethyl ether) were mixed and dispersed with a bead mill for 3 hours to obtain a blue colorant slurry C-1. The average particle size of the obtained phthalocyanine blue was measured by using Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd., and measuring the sample after diluting the blue colorant slurry with MIBK (methyl isobutyl ketone) to measure the appropriate concentration. The measurement result of the sample is the value measured by the laser diffraction method and the D50 value is 220nm, and the D100 value is 600nm. (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 is measured by using Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd., and measuring the sample diluted with MIBK to measure the appropriate concentration. The measurement result of this sample is the value measured by the laser diffraction method and the D50 value is 280nm, and the D100 value is 600nm. (RC-1) 　　 The 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 is measured by using Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd., and measuring the sample diluted with MIBK to measure the appropriate concentration. The measurement result of this sample is the value measured by the laser diffraction method, and the D50 value is 400 nm, and the D100 value is 1 μm.

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

(Preparation of Silica Paste D-1) Preparation of (D-1) 70 parts by mass of spherical silica (SFP-20M manufactured by Denka) and 25 parts by mass of PMA (propylene glycol monomethyl ether acetate) as a solvent Parts and 5 parts by mass of a dispersant (BYK-111 manufactured by BYK, Japan), uniformly dispersed with a bead mill for 2 hours to obtain silica slurry D-1. The average particle size of the spherical silica obtained is measured by using Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. on a sample diluted with MIBK to measure the appropriate concentration. The measurement result of this sample is the value measured by the laser diffraction method, and the D50 value is 0.7 μm, and the D100 value is 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. (alumina surface treatment barium sulfate)) as a solvent PMA (propylene glycol monomethyl) Ether acetate) 25 parts by mass and 5 parts by mass of a dispersant (BYK-111 manufactured by BYK) were uniformly dispersed for 2 hours with a bead mill to obtain barium sulfate slurry D-2. The average particle size of the obtained barium sulfate is measured by using Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd., and measuring a sample diluted with MIBK to measure the appropriate concentration. The measurement result of this sample is the value measured by the laser diffraction method, and the D50 value is 0.30 μm, and the D100 value is 1.0 μm.

(Preparation of Silica Paste RD-1) Preparation of (RD-1) 70 parts by mass of spherical silica (FB-5D manufactured by Denka) and 25 parts by mass of PMA (propylene glycol monomethyl ether acetate) as a solvent Parts and 5 parts by mass of a dispersant (BYK-111 manufactured by BYK, Japan), uniformly dispersed with a bead mill for 2 hours to obtain silica slurry D-1. The average particle size of the spherical silica obtained is measured by using Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd. on a sample diluted with MIBK to measure the appropriate concentration. The measurement result of this sample is the value measured by the laser diffraction method and the D50 value is 5.0 μm, and the D100 value is 12.5 μm.

(Preparation of Melamine Dispersion Product 1) 　　55 parts by mass of melamine and 45 parts by mass of carbitol acetate were mixed and dispersed by a bead mill for 2 hours to obtain a melamine dispersion product 1. The average particle size and maximum particle size of the obtained melamine dispersion 1 were measured using Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd., and measured on a sample diluted with MIBK to measure an appropriate concentration. The measurement result of this sample is the value measured by the laser diffraction method and the D50 value is 600nm, and the D100 value is 5.0μm.

(Preparation of Melamine Dispersion Product 2) 　　 55 parts by mass of melamine and 45 parts by mass of carbitol acetate were mixed and dispersed by a bead mill for 4 hours to obtain a melamine dispersion product 2. The average particle size and the maximum particle size of the obtained melamine dispersion are measured using Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd., and measured on a sample diluted with MIBK to measure the appropriate concentration. The measurement result of this sample is the value measured by the laser diffraction method, and the D50 value is 400 nm, and the D100 value is 4.0 μm.

(Preparation of dicyanodiamide (DICY) dispersion 1) 　　 70 parts by mass of dicyanodiamide and 30 parts by mass of carbitol acetate were mixed and dispersed by a bead mill for 2 hours to obtain a DICY dispersion 1. The average particle diameter and the maximum particle diameter of the obtained DICY dispersion 1 were measured using Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd., and measured on a sample diluted with MIBK to measure an appropriate concentration. The measurement result of this sample is the value measured by the laser diffraction method, and the D50 value is 800 nm, and the D100 value is 6.0 μm.

(Preparation of Dicyanodiamide (DICY) Dispersion 2)

70 parts by mass of dicyanodiamide and 30 parts by mass of carbitol acetate were mixed and dispersed with a bead mill for 4 hours to obtain DICY dispersion product 2. The average particle diameter and the maximum particle diameter of the obtained DICY dispersion 1 were measured using Microtrac MT3300EXII manufactured by Nikkiso Co., Ltd., and measured on a sample diluted with MIBK to measure an appropriate concentration. The measurement result of this sample is the value measured by the laser diffraction method, and the D50 value is 400 nm, and the D100 value is 4.0 μm.

[Examples 1 to 14 and Comparative Examples 1 and 2]

According to the points shown in the following Tables 1 to 3, the various ingredients are blended in the proportions (parts by mass) shown in Tables 1 to 4, and after pre-mixing with a mixer, they are kneaded with a bead mill to prepare a photocurable resin composition. In addition, the blending amount in the table indicates the solid content (non-volatile content).

(Production of dry film)

The photocurable resin composition prepared above was coated on a PET film using an applicator so that the film thickness of the resin layer after drying became a specific film thickness, and dried at 80°C for 30 minutes to obtain a dry film.

(Absorbance)

According to the method described in the above (Production of Dry Film), a dry film with a resin layer thickness of 15 μm after drying was produced. A dry film with a thickness of 15 μm of the above resin layer was laminated on a glass substrate, and the PET film was peeled off. Subsequently, the absorbance was measured using a spectrophotometer V-670.

(Concealment)

According to the method described in the above (Production of Dry Film), a dry film with the thickness of the resin layer after drying of 18 μm, 23 μm, and 28 μm was produced. Next, each dry film is laminated on a printed circuit board with a Cu thickness of 6 μm and a comb pattern of L/S=15/20. For this, the HMW680GW (metal halide lamp, scattered light) manufactured by ORC is used for full exposure with an optimal exposure amount: 800mJ. After the PET film was peeled off, the cumulative exposure amount was further adjusted to 1000 mJ and irradiated with ultraviolet rays, and then heated at 160° C. for 1 hour to be cured.

With regard to the obtained printed circuit board with a cured film, the concealment of the circuit was evaluated visually.

◎: Using a dry film with a resin layer thickness of 18μm after drying, it is good when the thickness of the cured film is 10μm on copper

○: Using a dry film with a resin layer thickness of 23μm after drying, it is good when the thickness of the cured film is 15μm on copper

△: Using a dry film with a resin layer thickness of 28μm after drying, it is good when the thickness of the cured film is 20μm on copper

×: Use a dry film with a thickness of 8μm in the resin layer after drying, and it is not good when the thickness of the cured film is 10μm on copper.

(Appearance) 　　 According to the method described in the above (Production of Dry Film), a dry film with a resin layer thickness of 15 μm after drying was produced. Next, a dry film with a thickness of 15 μm of the above-mentioned resin layer is laminated on a substrate with a 35 μm copper foil that has undergone CZ treatment. For this, the HMW680GW (metal halide lamp, scattered light) manufactured by ORC is used for full exposure with an optimal exposure amount: 800mJ. After the PET film was peeled off, the cumulative exposure amount was further adjusted to 1000 mJ and irradiated with ultraviolet rays, and then heated at 160° C. for 1 hour to be cured.　　 Regarding the obtained printed circuit board with a cured film, the presence or absence of particles on the cured film was confirmed with an optical microscope at 500 times.　　◎: no particles with a particle size of 5μm or less 　　○: no particles with a particle size of 10μm or less 　　△: less than 15 particles with a particle size of 10μm or less 　　×: more than 15 particles with a particle size of 10μm or less

(Surface smoothness) 　　 According to the method described in the above (Production of Dry Film), a dry film with a resin layer thickness of 15 μm after drying was produced. On the surface of the dry film with a film thickness of 15 μm of the resin layer, visually observe 10 places in an area of 8 cm in width x 20 cm in length to confirm that there is no sticking, and confirm that the film thickness crosses with a micrometer.　　◎: No sticking, unevenness difference ±1μm 　　○: No sticking, unevenness difference ±2μm 　　△: No sticking, unevenness difference ±3μm 　　×: No sticking

(Sensitivity) 　　 According to the method described in the above (Production of Dry Film), a dry film with a resin layer thickness of 15 μm after drying was produced. On a substrate with a 35μm copper foil treated by CZ, the above resin layer is laminated with a dry film with a thickness of 15μm, using a projection exposure machine UFX-2223M-APU01 that cuts off the longer wavelength than the i-line, and exposes it by Stouffer 41 segments of step tablet are exposed. The PET film was peeled off, and the amount of exposure when the gloss sensitivity was 8 steps or more when developed with 1.0 wt% sodium carbonate aqueous solution for 60 seconds was measured.　　◎: less than 200mJ 　　○: more than 200mJ less than 350mJ 　　△: more than 350mJ less than 500mJ 　　×: more than 500mJ

(Resolution) 　　 According to the method described in the above (Production of Dry Film), a dry film with a resin layer thickness of 15 μm after drying was produced. On a substrate with 35μm copper foil treated by CZ, laminate the above resin layer with a 15μm dry film, and use a projection exposure machine UFX-2223M-APU01 that cuts off the longer wavelength than the i-line to have openings Exposure in a graphical way. Peel off the PET film and develop with 1.0wt% sodium carbonate aqueous solution to confirm the smallest opening diameter that can be formed.　　◎: good opening diameter of 50μm 　　○: good opening diameter of 80μm 　　△: good opening diameter of 100μm 　　×: no good opening diameter of 100μm

*8：日本BASF公司製IRGACURE TPO( 2,4,6-三甲基苯甲醯基-二苯基-氧化膦) 　　*9：日本BASF公司製IRGACURE 907(2-甲基-1-(4-甲基硫苯基)-2-嗎啉丙烷-1-酮) 　　*10：日本化藥公司製KAYACURE DETX-S(2,4-二乙基噻噸酮) 　　*11：上述調製之藍色著色劑(酞青藍，平均粒徑220nm，無表面處理)漿料C-1 　　*12：上述調製之藍色著色劑(酞青藍，平均粒徑280nm，無表面處理)漿料C-2 　　*13：上述調製之藍色著色劑(酞青藍，平均粒徑400nm，無表面處理)漿料RC-1 　　*14：上述調製之黃色著色劑(Cromophtal Yellow，平均粒徑150nm，無表面處理)漿料 　　*15：上述調製之氧化矽(SPF-30M，平均粒徑0.7μm，有表面處理)漿料D-1 　　*16：上述調製之鋇(B-30，平均粒徑0.3μm，有表面處理)漿料D-2 　　*17：上述調製之氧化矽(FB-5D，平均粒徑5.0μm，有表面處理)漿料RD-1 　　*18：日本化藥公司製DPHA(二季戊四醇六丙烯酸酯) 　　*19：市售品(平均粒徑：5μm，最大粒徑：20μm) 　　*20：市售品(平均粒徑：3μm，最大粒徑：15μm) 　　*21：日本BYK公司製BYK-361N(調平劑) 　　*22：表中之摻合量表示漿料中之固成分合計。藍色著色劑/漿料中之固成分=12/17 　　*23：表中之摻合量表示漿料中之固成分合計。黃色著色劑/漿料中之固成分=10/15 　　*24：表中之摻合量表示漿料中之固成分合計。無機填充劑/漿料中之固成分=70/75*1: Solution A-1 of the above-synthesized alkali-soluble resin *2: Solution A-2 of the above-synthesized alkali-soluble resin *3: Solution A-3 of the above-synthesized alkali-soluble resin *4: EPICLON N manufactured by DIC -870 (bisphenol A novolac epoxy resin); dissolved in CA (carbitol acetate); non-volatile content 75% *5: EPICLON N-730A (phenol novolac epoxy resin) manufactured by DIC *6: IRGACURE OXE02 (Ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(O- Acetyl oxime)) *7:

*8: IRGACURE TPO (2,4,6-trimethylbenzyl-diphenyl-phosphine oxide) manufactured by BASF Japan *9: IRGACURE 907 (2-methyl-1-(4) manufactured by BASF Japan -Methylthiophenyl)-2-morpholinepropan-1-one) *10: KAYACURE DETX-S (2,4-diethylthioxanthone) manufactured by Nippon Kayaku Co., Ltd. *11: Blue prepared above Colorant (phthalocyan blue, average particle size 220nm, no surface treatment) slurry C-1 *12: Blue colorant (phthalocyan blue, average particle size 280nm, no surface treatment) slurry C-2 prepared above *13: Blue colorant prepared above (phthalocyanine blue, average particle size 400nm, no surface treatment) slurry RC-1 *14: Yellow colorant prepared above (Cromophtal Yellow, average particle size 150nm, no surface treatment ) Slurry *15: The above-prepared silica (SPF-30M, average particle size 0.7μm, with surface treatment) Slurry D-1 *16: The above-prepared barium (B-30, average particle size 0.3μm, with Surface treatment) slurry D-2 *17: The above-prepared silica (FB-5D, average particle size 5.0μm, with surface treatment) slurry RD-1 *18: DPHA (dipentaerythritol hexaacrylic acid) manufactured by Nippon Kayaku Co., Ltd. Ester) *19: Commercial product (average particle size: 5μm, maximum particle size: 20μm) *20: Commercial product (average particle size: 3μm, maximum particle size: 15μm) *21: BYK-361N manufactured by BYK Japan (Leveling agent) *22: The blending amount in the table represents the total solid content in the slurry. Blue colorant/solid content in slurry=12/17 *23: The blending amount in the table represents the total solid content in the slurry. Yellow colorant/solid content in the slurry=10/15 *24: The blending amount in the table represents the total solid content in the slurry. Inorganic filler/solid content in slurry=70/75

*25：上述調製之三聚氰胺分散品1(平均粒徑：600nm，最大粒徑：5.0μm) 　　*26：上述調製之三聚氰胺分散品2(平均粒徑：400nm，最大粒徑：4.0μm) 　　*27：上述調製之DICY分散品1(平均粒徑：800nm，最大粒徑：6.0μm) 　　*28：上述調製之DICY分散品2(平均粒徑：400nm，最大粒徑：4.0μm)

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

From the results in the above table, it can be seen that the photocurable resin composition of the present invention can form a cured product with excellent appearance and surface smoothness, as well as excellent sensitivity and resolution.

Claims (6)

A photocurable resin composition containing (A) alkali-soluble resin, (B) photopolymerization initiator, (C) blue colorant, and (D) inorganic filler for alkali-developable photocurable resin The composition is characterized in that the average particle diameter of the aforementioned (C) blue coloring agent is 300 nm or less, and the blending amount of the aforementioned (C) blue coloring agent is 0.20 relative to the total solid content of the photocurable resin composition ~0.40% by mass, the average particle size of the aforementioned (D) inorganic filler is 1.0μm or less. The photocurable resin composition according to claim 1, wherein, as a thermosetting catalyst, an organic filler having an amine group having an average particle diameter of 1 μm or less and a maximum particle diameter of 6 μm or less is further contained. The photocurable resin composition of claim 1, wherein, as the aforementioned (B) photopolymerization initiator, an oxime ester-based photopolymerization initiator is contained, and based on the total amount of the photopolymerization initiator, the aforementioned oxime ester-based photopolymerization initiator The blending amount of the polymerization initiator is 8% by mass or more in terms of solid content. A dry film characterized by having a resin layer obtained from the photocurable resin composition of claim 1. A cured product characterized by curing the photocurable resin composition of any one of claims 1 to 3 or the resin layer of a dry film as claimed in claim 4 have to. A printed wiring board characterized by having a cured product as claimed in claim 5.