TWI489214B - A photohardenable resin composition, a dry film and a cured product thereof, and a printed wiring board having a hardened film formed using the same - Google Patents

Description

Photocurable resin composition, dry film and cured product thereof, and printed wiring board having the hardened film formed using the same

The present invention relates to a photocurable resin composition which can be developed by an aqueous alkali solution, in particular, a photocurable resin composition for photo-curing by ultraviolet exposure or laser exposure, a dry film thereof and a cured product thereof. And a printed wiring board having the hardened film formed using the above.

Recently, some of the printed wiring boards for the people's livelihood and the solder masks of almost all industrial printed wiring boards are formed by high-precision and high-density from the viewpoint of high-precision and high-density, and are used to form images by heat and light. A liquid-like development type solder resist which is at least one of the final hardening (this hardening).

Among them, in view of environmental problems, the use of an aqueous alkali solution as a developing liquid for image forming liquid is mainly used, and it is used in a large amount in the manufacture of printed wiring boards.

In the conventional alkali-developing type resist welding, a carboxyl group-containing resin, in particular, an epoxy acrylate-modified resin is generally used.

For example, Patent Document 1 reports on a novolak type. A solder resist composition formed by reacting an epoxy compound with an unsaturated monobasic acid to form a photosensitive anhydride, a photopolymerization initiator, a diluent, and an epoxy compound.

Further, Patent Document 2 discloses that an epoxy resin obtained by reacting epichlorohydrin with a reaction product of salicylaldehyde and a monohydric phenol is added to (meth)acrylic acid, and further, a photosensitive carboxylic acid or an anhydride thereof is reacted. A solder resist composition formed of a resin, a photopolymerization initiator, an organic solvent, or the like.

Further, Patent Document 3 discloses a polyurethane compound obtained by reacting an epoxy acrylate compound having an ethylenically unsaturated group and two or more hydroxyl groups with a diisocyanate compound and a diol compound having a carboxyl group. A photopolymerizable monomer having an ethylenically unsaturated group, a photopolymerization initiator, an epoxy compound, and a photosensitive resin composition containing a ceria filler having an average particle diameter of 3 to 300 nm.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. S61-243869 (Patent Application)

[Patent Document 2] Japanese Laid-Open Patent Publication No. Hei-3-250012 (Patent Application)

[Patent Document 3] Japanese Laid-Open Patent Publication No. 2011-013622 (Scope of Patent Application)

However, conventional alkali-developing type photoresist inks have durability, particularly chemical resistance (for example, alkali resistance) and water resistance, compared with thermosetting type and solvent-developing solder resist inks. There is still room for improvement in terms of heat resistance and adhesion to the substrate.

These are considered to be due to the influence of the hydrophilic group-containing component in the main component which can be used for alkali imaging. In other words, the hydrophilic group-containing component is in a state of being easily impregnated with a chemical liquid, water, water vapor or the like. Therefore, the chemical resistance of the resist or the adhesion between the resist film and copper tends to decrease.

Moreover, in the conventional alkali-developing type of photoresist ink, the cooling shrinkage after hardening shrinkage and hardening is large, especially in high-temperature surface mounting in lead-free solder, cracking or warpage of the coating film occurs, and wafer mounting is performed. Sometimes it has an adverse effect. In particular, when the above-mentioned solder resist ink is filled with a filler, cracking of the coating film occurs regardless of the type or particle diameter. Especially in the case of high filling, the occurrence of cracking of the coating film is remarkable.

In the future, printed wiring boards, because the most important thing is that the interposer substrate becomes thinner or coreless, it is considered that the PKG solder mask must have excellent resolution.

However, an object of the present invention is to provide a photocurable resin composition which is excellent in resolution, excellent in cold heat and chemical resistance and HAST resistance of a cured product, and which is small in warpage and which can be developed by an aqueous alkali solution. A photocurable dry film, a cured product, and a printed wiring board including the same.

The above object was found to be achieved by a photocurable resin composition which can be imaged by an aqueous alkali solution, which comprises (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) an average particle diameter of 300 nm. The photocurable resin composition of the spherical cerium oxide filler is characterized in that the (C) spherical cerium oxide filler having an average particle diameter of 300 nm or less is the total amount of the photocurable resin composition. The blending amount is 60% by mass or more.

In the photocurable resin composition of the present invention, the (A) alkali-soluble resin is preferably a carboxyl group-containing resin having no (A-1) photosensitive group.

In the photocurable resin composition of the present invention, the (A) alkali-soluble resin further preferably contains a carboxyl group-containing resin having a photosensitive group (A-2).

The photocurable resin composition of the present invention further preferably contains (D) an epoxy resin.

In the photocurable resin composition of the present invention, the epoxy resin (D) is preferably an epoxy resin having a (D-1) naphthalene structure.

Further, in the photocurable resin composition of the present invention, a carboxyl group-containing resin having no (A-1) photosensitive group is reacted by reacting a polybasic acid anhydride with a polyol resin in which a polyphenol compound is modified with an alkylene oxide. The resulting carboxyl group-containing resin is preferred.

The photocurable resin composition of the present invention is as described above (A-2) Photosensitive carboxyl group-containing resin, which is obtained by reacting (meth)acrylic acid with a polyol resin modified with an alkylene oxide, and further reacting a polybasic acid anhydride with a carboxyl group-containing resin good.

Further, the above object of the present invention is to provide a photocurable dry film obtained by applying and drying a photocurable resin composition of the present invention to a carrier film, or to wet the photocurable resin composition or dry film. It is solved by a cured wiring obtained by photohardening or applied to a carrier film or a printed wiring board having the cured product.

According to the present invention, it is possible to provide a photocurable resin which is excellent in cold heat and chemical resistance and HAST resistance of a dry film or a cured product, has a low incidence of warpage of a cured product, and further exhibits excellent resolution by an aqueous alkali solution. A composition, a photocurable dry film obtained thereby, a cured product, and a printed wiring board including the same.

In particular, in the present invention, the cerium oxide filler having an average particle diameter of 300 nm and the cerium oxide filler are spherical, and the cracking of the cured product is suppressed, and the resolution is improved and the warpage property is lowered. Moreover, the photocurable resin composition of the present invention can be cured even with a small exposure amount, and is excellent in energy use efficiency.

The photocurable resin composition of the present invention can be imaged by an aqueous alkali solution by an aqueous alkali solution. (A) an alkali-soluble resin, (B) a photopolymerization initiator, and (C) a spherical cerium oxide filler having an average particle diameter of 300 nm or less, which is characterized by a total amount of the photocurable resin composition. The compounding amount of the spherical ceria filler having an average particle diameter of 300 nm or less is 60% by mass or more.

Each component will be described below.

[ingredient (A): alkali soluble resin]

The present invention uses an alkali soluble resin. As the alkali-soluble resin, a carboxyl group-containing resin or a phenol resin is preferably used. In particular, the use of a carboxyl group-containing resin is preferred from the viewpoint of development.

The carboxyl group-containing resin can be used for various carboxyl group-containing resins which have a carboxyl group in the molecule, do not have an ethylenically unsaturated double bond (non-photosensitive), or have such (photosensitive) conventionally known.

In particular, a non-photosensitive carboxyl group-containing resin having an ethylenically unsaturated double bond in a molecule is preferred from the viewpoints of improvement in flexibility, reduction in warpage (low warpage), and improvement in crack resistance.

Specific examples of the non-photosensitive carboxyl group-containing resin include the following compounds (any of an oligomer and a polymer).

(1) A diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a carboxyl group such as dimethylolpropionic acid or dimethylolbutanoic acid a diol compound, a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, a bisphenol A-based alkylene oxide addition diol, a phenolic hydroxyl group, and an alcoholic property A carboxyl group-containing urethane resin obtained by addition polymerization of a diol compound such as a hydroxy compound.

(2) A urethane resin containing a carboxyl group obtained by addition polymerization of a diisocyanate and a diol compound containing a carboxyl group.

(3) copolymerizing with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate or isobutylene by an unsaturated carboxylic acid such as (meth)acrylic acid A carboxyl-containing resin is obtained.

(4) reacting a dicarboxylic acid such as adipic acid, citric acid or hexahydrophthalic acid with a bifunctional epoxy resin or a bifunctional oxygen cyclobutane resin, and adding a hydroxyl group to form phthalic anhydride or tetrahydrophthalic anhydride. A carboxyl group-containing polyester resin of a dibasic acid anhydride such as hexahydrophthalic anhydride.

(5) A carboxyl group-containing resin obtained by ring-opening an epoxy resin or an oxycyclobutane resin to react a polybasic acid anhydride with a hydroxyl group formed.

(6) A compound having a plurality of phenolic hydroxyl groups in one molecule, that is, a reaction product of a polyol resin obtained by reacting a polyphenol compound with an alkylene oxide such as ethylene oxide or propylene oxide; A carboxyl group-containing resin obtained by reacting a polybasic acid anhydride.

In the present specification, the term "(meth)acrylate" means acrylate, methacrylate, and a mixture of these.

As a non-photosensitive carboxyl group-containing resin, which is never contained In view of chlorine, it is preferred to use the above (1), (2), and (6). Among them, the above (6) having an aromatic ring, excellent thermal and chemical resistance and PCT resistance, and low warpage, and having a good balance of all characteristics is preferable.

Further, in the resin composition of the present invention, a photosensitive carboxyl group-containing resin as an alkali-soluble resin is preferably added. Specific examples of the photosensitive carboxyl group-containing resin include the following compounds (any of an oligomer and a polymer). Further, the ethylenically unsaturated double bond in the carboxyl group-containing resin is preferably derived from acrylic acid or methacrylic acid or such derivatives.

(7) A diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, and a carboxyl group such as dimethylolpropionic acid or dimethylolbutanoic acid A diol compound, a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide addition diol, and a phenol A photosensitive urethane resin containing a carboxyl group obtained by addition polymerization of a diol compound such as a hydroxyl group or an alcoholic hydroxyl group.

(8) Diisocyanate, with bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bixylenol epoxy resin, a (meth) acrylate of a bifunctional epoxy resin such as a phenol type epoxy resin or a partially acid anhydride modified product thereof, and a carboxyl group-containing photosensitive uric acid obtained by addition polymerization reaction with a diol compound containing a carboxyl group Ethyl resin.

(9) In the resin synthesis of (7) or (8) above, a hydroxyalkyl (meth) acrylate or the like is added to have one hydroxyl group in the molecule. And a compound of one or more (meth) acrylonitrile groups is a terminal (meth) acrylated photosensitive urethane resin containing a carboxyl group.

(10) In the resin synthesis of (8) or (9) above, a molar reaction product of isophorone diisocyanate and pentaerythritol triacrylate is added to the molecule having one isocyanate group and 1 The compound of the above (meth) propylene fluorenyl group is a terminal (meth) acrylated photosensitive urethane resin containing a carboxyl group.

(11) A photosensitive resin containing a carboxyl group in which (meth)acrylic acid is reacted with a bifunctional or higher polyfunctional (solid) epoxy resin, and a hydroxyl group present in a side chain is added to a dibasic acid anhydride.

(12) reacting (meth)acrylic acid with a polyfunctional epoxy resin which oxidizes a hydroxyl group of a bifunctional (solid) epoxy resin and further epichlorohydrin, and forms a photosensitive group containing a carboxyl group of a dihydroxy acid anhydride Resin.

(13) reacting a dicarboxylic acid such as adipic acid, decanoic acid or hexahydrophthalic acid with a bifunctional oxygen cyclobutane resin to form a hydroxy group of phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride. A carboxyl group-containing polyester photosensitive resin of a dibasic acid anhydride.

(14) A reaction product of a polyol resin obtained by reacting an alkylene oxide such as ethylene oxide or propylene oxide with a compound having a plurality of phenolic hydroxyl groups in one molecule, that is, a polyphenol compound, A photosensitive resin containing a carboxyl group obtained by reacting a monocarboxylic acid containing an unsaturated group such as acrylic acid, and further reacting a polybasic acid anhydride with the obtained reaction product.

(15) making a monocarboxylic acid containing an unsaturated group with 1 molecule The reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups with a cyclic carbonate compound such as ethyl carbonate or propylene carbonate, and reacting the polybasic acid anhydride with the obtained reaction product to obtain a carboxyl group-containing photosensitive property Resin.

(16) A photosensitive resin containing a carboxyl group formed by further adding a resin having the above (7) to (15) to a compound having one epoxy group and one or more (meth) acrylonitrile groups in one molecule .

These photosensitive carboxyl group-containing resins may be used in addition to those described in (7) to (16), and the types may be used singly or in combination of plural kinds. In particular, a resin having an aromatic ring among the carboxyl group-containing resins is excellent not only in excellent resolution but also excellent in PCT or crack resistance.

Among them, the carboxyl group-containing resin (14) and (15), which are synthesized from a phenol compound as a starting material, are chlorine-free, and have excellent insulating properties such as HAST resistance and PCT resistance, and the toughness in the present invention. It is also excellent, and as a result, the crack resistance is also excellent, so that it can be suitably used.

The above-mentioned carboxyl group-containing resin can be said to be the following regardless of sensitivity or non-photosensitivity.

That is, because of the skeleton. The side chain of the polymer has a large number of carboxyl groups, so it can be imaged with a dilute aqueous alkali solution.

Further, the acid value of the carboxyl group-containing resin is suitably in the range of 40 to 200 mgKOH/g, more preferably in the range of 45 to 120 mgKOH/g.

If the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, the base Development becomes difficult, on the other hand, if it exceeds 200 mgKOH/g, it will advance. Since the exposure of the exposed portion is caused by the liquid imaging liquid, the line width becomes thinner than necessary, or the exposed portion and the unexposed portion are dissolved and peeled off in a developing solution without distinction, and the normal resist pattern is drawn. The difficulty is not good.

Further, the weight average molecular weight of the carboxyl group-containing resin varies depending on the resin skeleton, and is generally from 2,000 to 150,000, more preferably from 5,000 to 100,000. If the weight average molecular weight is less than 2,000, there is a problem that the non-stick property is deteriorated, and the development resistance of the coating film after exposure cannot be obtained, and the resolution is greatly deteriorated. On the other hand, when the weight average molecular weight exceeds 150,000, there is a problem that the developability is remarkably deteriorated.

The amount (solid content) of the carboxyl group-containing resin is suitably from 10 to 60% by mass, preferably from 20 to 50% by mass, based on the photocurable resin composition. When the amount of the carboxyl group-containing resin is less than 10% by mass, there is a problem that the film strength is lowered, which is not preferable. On the other hand, when the amount is more than 60% by mass, the viscosity of the photocurable resin composition is high, or the coatability to the carrier film is lowered, which is not preferable.

In addition, when a photosensitive carboxyl group-containing resin and a non-photosensitive carboxyl group-containing resin are used, the content ratio (photosensitive carboxyl group-containing resin: carboxyl group-containing resin having no photosensitivity) is based on the mass of the solid component (1). :9)~(9:1), preferably (2:8)~(8:2), more preferably (5:5)~(7:3). In this range, it is possible to obtain a cured product of a resin composition which is excellent in both resolution and low warpage, and a printed wiring board having the same, in particular, while avoiding an increase in exposure amount.

Photosensitive carboxyl-containing resin and non-photosensitive carboxyl-containing tree The fat may be used alone or in combination of two or more. Among the carboxyl group-containing resins, in particular, the resin having an aromatic ring is preferred because it has a high refractive index and excellent resolution, and further has excellent dissolvability, PCT resistance, and crack resistance in a novolac structure. .

As the phenol resin, a compound having a phenolic hydroxyl group, for example, a compound having a biphenyl skeleton, a phenyl group skeleton, or a skeleton thereof, or a compound containing a phenolic hydroxyl group such as phenol or o-cresol may be used. 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, methyl hydroquinone, 2,6-dimethyl hydroquinone, trimethyl hydroquinone, gallic phenol A phenol resin having various skeletons synthesized by phloroglucin or the like.

For example, a phenol novolak resin, an alkylphenol novolak resin, a bisphenol A novolak resin, a dicyclopentadiene type phenol resin, a Xylok type phenol resin, a terpene modified phenol resin, a polyvinyl phenol, a bisphenol can be used. F, a bisphenol S type phenol resin, a poly-p-hydroxystyrene, a condensate of naphthol and an aldehyde, a condensate of a dihydroxy naphthalene and an aldehyde, and the like are conventionally used.

These may be used alone or in combination of two or more.

The commercially available product of the phenol resin is exemplified by HF1H60 (manufactured by Mingwa Kasei Co., Ltd.) PHENOLITE TD-2090, PHENOLITE TD-2131 (manufactured by Dainippon Printing Co., Ltd.), BESMOL CZ-256-A (manufactured by DIC Corporation), and Shonol BRG-555. Shonol BRG-556 (manufactured by Showa Denko KK), CGR-951 (manufactured by Maruzen Oil Co., Ltd.), or CST70, CST90, S-1P, S-2P (manufactured by Maruzen Oil Co., Ltd.) of polyvinyl phenol. this The phenol resin may be used singly or in combination of two or more kinds.

In the present invention, as the alkali-soluble resin, any of a carboxyl group-containing resin and a phenol resin, or a mixture thereof may be used.

Further, in the photocurable resin composition of the present invention, a material containing no ethylenically unsaturated group is used as the alkali-soluble resin (component A), and it is necessary to use one or more molecules, preferably 2, in the molecule. One or more compounds having an ethylenically unsaturated group, that is, a photopolymerizable monomer. The photopolymerizable monomer is photocured by irradiation with an active energy ray, and contributes to dissolution of an alkali-soluble resin by an alkali-soluble resin. Further, in the case of using a carboxyl group-containing resin, a photopolymerizable monomer may be used in combination for the purpose of further promoting photocuring.

In either case, one type or a plurality of types of photopolymerizable monomers described later may be used.

[ingredient (B): photopolymerization initiator]

In order to form the resin composition of the present invention into a photocurable resin composition, a photopolymerization initiator is formulated. The photopolymerization initiator is selected from the group consisting of an oxime ester photopolymerization initiator having an oxime ester group, an α-aminoacetophenone photopolymerization initiator, and a fluorenylphosphine oxide photopolymerization initiator. One or more kinds of photopolymerization initiators in the group are preferred.

As the oxime ester photopolymerization initiator, commercially available products are CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF JAPAN Co., Ltd., N-1919 manufactured by ADEKA Co., Ltd., ADEKA ARKLS NCI-831, and the like. Also, it can be suitably used in the molecule with 2 Specific examples of the photopolymerization initiator of the oxime ester group include an oxime ester compound having a carbazole structure represented by the following general formula.

In the formula, X represents 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, and an alkyl group having 1 to 8 carbon atoms). An oxy group, an amine group, an alkylamino group having a carbon number of 1 to 8 or a dialkylamino group, a naphthyl group (an alkyl group having 1 to 17 carbon atoms, and an alkyl group having 1 to 8 carbon atoms) An oxy group, an amine group, an alkylamino group having a carbon number of 1 to 8 or a dialkylamino group, and Y and Z respectively represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, and a carbon number of 1 ~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, amine group, alkyl group having an alkyl group having 1 to 8 carbon atoms) a substituted amino group or a dialkylamine group, a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amine group, an alkyl group having an alkyl group having 1 to 8 carbon atoms) Alkenyl or dialkylamino group substituted, fluorenyl, pyridyl, benzofuranyl, benzothienyl, Ar represents an alkylene group having a carbon number of 1 to 10, a vinyl group, a phenyl group, and a stretching group. Biphenyl, pyridine, stilbene, thiophene, thiol, thienyl, furanyl, 2,5-pyrrole-diyl, 4,4'-stilbene-diyl, 4,2 '-styrene-two Base, n is an integer of 0 or 1.

In particular, in the above 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, and Ar is preferably a phenylene group, a naphthyl group, a thiophene group or a thienyl group.

The amount of the oxime ester-based photopolymerization initiator is preferably from 0.01 to 5 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (solid content). When the amount is less than 0.01 parts by mass, the photocurability of the resin composition is insufficient, and the coating film is peeled off, and the coating properties such as chemical resistance are lowered. On the other hand, when it exceeds 5 parts by mass, the light absorption on the surface of the solder resist coating film becomes intense, and the deep hardenability tends to be lowered. More preferably 0.5 to 3 parts by mass.

As the α-aminoacetophenone photopolymerization initiator, specifically, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylacetone-1, 2-benzyl group can be exemplified. -2-dimethylamino-1-(4-morpholinylphenyl)-butan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)- 1-[4-(4-morpholinyl)phenyl]-1-butanone, N,N-dimethylaminoacetophenone, and the like. Commercially available products include Irgacure 907, Irgacure 369, Irgacure 379, etc., manufactured by BASF JAPAN.

As the fluorenylphosphine oxide-based photopolymerization initiator, specifically, 2,4,6-trimethylbenzylphosphonium diphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)-benzene Phosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentylphosphine oxide, and the like. Commercially available products include Lucirin TPO, Irgacure 819, and the like manufactured by BASF JAPAN.

The amount of the α-aminoacetophenone photopolymerization initiator and the mercaptophosphine oxide photopolymerization initiator is relative to the carboxyl group-containing resin (solid content) 100 parts by mass is preferably 0.1 to 30 parts by mass. When the amount is less than 0.1 part by mass, the photocurability of the resin composition is insufficient, and the coating film is peeled off, and the coating properties such as chemical resistance are lowered. On the other hand, when it exceeds 30 parts by mass, the effect of reducing the outgassing cannot be obtained, and the light absorption on the surface of the solder resist coating film becomes intense, and the deep hardenability tends to be lowered. More preferably 0.5 to 15 parts by mass.

The resin composition of the present invention is preferably an oxime ester photopolymerization initiator. By using an oxime ester photopolymerization initiator, not only a small amount of sufficient sensitivity can be obtained, but also the volatilization of the photopolymerization initiator in the thermal step after thermal curing and after the mounting is less, so that the hard coating film can be suppressed. Shrinkage, which can significantly reduce warpage.

Further, a fluorenylphosphine oxide-based photopolymerization initiator is also preferred. By the use of fluorenylphosphine oxide, the deep hardenability in the photoreaction is enhanced, and the phosphorus concentration in the hardened coating film can be effectively obtained by incorporating the phosphorus-containing compound component from the initiator into the hardened material network by light irradiation cracking. Lifting can further improve the flame retardancy.

In the resin composition of the present invention, it is effective to use either an oxime-based photopolymerization initiator or a fluorenylphosphine oxide-based photopolymerization initiator, but the balance and processing of the linear shape and opening of the above-mentioned resist In view of the improvement of the precision, the oxime ester photopolymerization initiator and the fluorenylphosphine oxide-based photopolymerization initiator are preferably used in combination with low warpage, flexibility, and flame retardancy.

Further, Irgacure 389 and Irgacure 784 manufactured by BASF JAPAN Co., Ltd. may be suitably used as the photopolymerization initiator.

In addition to the above photopolymerization initiator, a photoinitiating aid or a sensitizer may be used in the present invention.

[Photopolymerization starter and sensitizer]

Further, as a photoinitiating aid and a sensitizing agent which can be suitably used in the resin composition of the present invention, a benzoin compound, an acetophenone compound, an anthraquinone compound, a thioxanthone compound, a ketal compound, and the like can be exemplified. A benzophenone compound, a tertiary amine compound, and a xanthone compound.

Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and the like.

The acetophenone compound is specifically exemplified by, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1 - Dichloroacetophenone and the like.

Specific examples of the hydrazine compound include 2-methyl hydrazine, 2-ethyl hydrazine, 2-t-butyl hydrazine, 1-chloroindole and the like.

The thioxanthone compound, specifically, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthene Ketones, etc.

Specific examples of the ketal compound include acetophenone dimethyl ketal, benzyl dimethyl ketal and the like.

The benzophenone compound is specifically exemplified by, for example, benzophenone, 4-benzylguanidino-diphenyl sulfide, 4-benzylindolyl-4'-methyldiphenyl sulfide, 4-benzylindenyl-4 '-Ethyl diphenyl sulfide, 4-benzylindolyl-4'-propyl diphenyl sulfide, and the like.

The tertiary amine compound may, for example, be, for example, an ethanolamine compound or a compound having a dialkylaminobenzene structure, for example, 4,4'-dimethylaminobenzophenone (available from Japan Soda Co., Ltd.) in a commercial product. Nissocure MABP), 4,4'-diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.), dialkylaminobenzophenone, 7-(diethylamino)- a dialkylamino group such as 4-methyl-2H-1-benzopipene-2-one (7-(diethylamino)-4-methylcoumarin) contains a coumarin compound, 4 - dimethylamino benzoic acid ethyl ester (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylamino benzoic acid ethyl ester (Quantacure DMB manufactured by Intenational Bio-synthesis Co., Ltd.), 4-dimethylamine Chiral acid (n-butoxy) ethyl ester (Quantacure BEA, manufactured by Intenational Bio-synthesis Co., Ltd.), p-dimethylamino benzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4 2-Ethylaminobenzoic acid 2-ethylhexyl ester (Esolol 507, manufactured by Van Dyk Co., Ltd.), 4,4'-diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.), and the like.

Further, the tertiary amine compound is preferably a compound having a dialkylaminobenzene structure, wherein the dialkylaminobenzophenone compound and the dialkylamine group having a maximum absorption wavelength in the range of 350 to 450 nm are used. The coumarin compound and the ketocoumarin are particularly excellent.

As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is less preferable in toxicity. A dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm in an ultraviolet region, so that coloring is small, and of course, a colorless and transparent photosensitive composition can be provided, and a coloring pigment can be provided to reflect the coloring pigment itself. The color of the solder mask. special Further, 7-(diethylamino)-4-methyl-2H-1-benzopipene-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

The amount of the tertiary amine compound to be added is preferably 0.1 to 20 parts by mass based on 100 parts by mass (solid content) of the carboxyl group-containing resin.

When the amount of the tertiary amine compound is less than 0.1 part by mass, a sufficient sensitizing effect may not be obtained. On the other hand, when it exceeds 20 parts by mass, the light absorption on the surface of the dry solder resist coating film by the tertiary amine compound becomes intense, and the deep hardenability tends to be lowered. More preferably, it is 0.1 to 10 parts by mass.

Among the above photoinitiating aids and sensitizers, a thioxanthone compound and a tertiary amine compound are preferred. In particular, the thioxanthone compound is preferred from the viewpoint of deep curing property of the resin composition. Among them, thioxanthone containing 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone, etc. The compound is preferred.

The amount of the thioxanthone compound to be added is preferably 20 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin (solid content). When the amount of the thioxanthone compound is more than 20 parts by mass, the thick film hardenability is lowered and the cost of the product is increased. More preferably, it is 10 mass parts or less.

These photoinitiating aids and sensitizers may be used singly or in combination of two or more.

The above photopolymerization initiator, photoinitiator, and sensitizer The total amount of the photosensitive resin composition for a printed wiring board which can be used for the alkali-developing is preferably 35 parts by mass or less based on 100 parts by mass of the carboxyl group-containing resin. When it exceeds 35 mass parts, the deep hardenability of the resin composition by such light absorption tends to fall.

Further, since the photopolymerization initiator, the photoinitiator, and the sensitizer absorb a specific wavelength, the sensitivity may be lowered depending on the case, and the ultraviolet absorber functions as an ultraviolet absorber. However, these are not intended for the purpose of merely increasing the sensitivity of the composition. It is necessary to absorb light of a specific wavelength, and it is possible to improve the photoreactivity of the surface, and to change the line shape and the opening of the resist in a vertical, tapered, and anti-conical shape, and to improve the processing precision of the line width or the opening diameter.

[Component C: spherical cerium oxide filler having an average particle diameter of 300 nm or less]

In the resin composition of the present invention, a spherical cerium oxide filler having an average particle diameter of 300 nm or less (hereinafter also referred to as spherical nano cerium oxide) is used. It is preferably 200 nm or less, and the lower limit is preferably 3 nm or more. The average particle diameter is determined by a laser diffraction method.

Further, it is preferred that the spherical nano cerium oxide used in the present invention is treated with a decane coupling agent on the surface to be used. This is to prevent precipitation or aggregation after dispersion in the liquid, and as a result, the storage stability is excellent. Moreover, it can also be stably put in without agglutination when the composition is prepared. Further, the wettability of the resin and the filler of the obtained cured product can be improved.

The organic group contained in the above decane coupling agent may, for example, be a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, an amine group, a urea group, a chloropropyl group, a fluorenyl group, or a poly Thioether, isocyanic acid Ester group and the like.

The commercial product of the above decane coupling agent may, for example, be KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM. -503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBE-9103, KBM-9103, KBM-573, KBM-575 , KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007 (all of which are trade names; manufactured by Shin-Etsu Chemical Co., Ltd.). These may be used alone or in combination of two or more.

The spherical nano-cerium dioxide of the present invention may be used alone or in combination of two or more. It may be used in combination with other kinds of fillers as will be described later.

In the present invention, the resolution of the resin composition can be greatly improved by using spherical nano-cerium oxide.

The spherical nano cerium oxide component in the photocurable resin composition is a starting point for scattering light, and this light scattering exerts a great influence on the resolution. It is estimated from the theory of Rayleigh scattering, Mie scattering, etc. that the light scattering phenomenon depends on the particle diameter of the nano cerium oxide particles. This is because in the equation of Mie scattering, the larger the size parameter of the scatterer, the stronger the scattering intensity of the light. Further, if the size parameter becomes small enough with respect to the wavelength of light, the scattering intensity becomes small.

Therefore, the size of the spherical nano-cerium oxide is smaller than the wavelength of light used for exposure, and light scattering can be suppressed, and a photocurable resin composition excellent in resolution of the present invention can be obtained.

Further, the spherical nano-cerium oxide of the present invention has good dispersibility in a resin, and is spherical in shape, and the occurrence of cracks in the cured film is favorably reduced. Further, it is expected that even if the filling is high, the occurrence of warpage can be reduced, and the bending resistance can be improved.

Examples of other fillers which can be used in combination with spherical nano-cerium oxide are spherical cerium oxide fillers having an average particle diameter of more than 300 nm, or other conventional inorganic or organic fillers, especially alumina, barium sulfate, talc, and Noyenburg bauxite particles. Further, as the filler which can impart flame retardancy, aluminum hydroxide, magnesium hydroxide, diaspore or the like can be used.

Further, the spherical nano-cerium oxide used in the present invention is not limited to a true spherical shape as long as it is spherical. As a suitable component (C), for example, a sphericity of 0.8 or more as measured below can be exemplified.

The sphericity is determined as follows. The photograph was taken by SEM, and the area and the circumference of the observed particles were calculated as values calculated by (sphericity) = {4π × (area) ÷ (circumference) 2}. Specifically, the average value of 100 particles was measured using an image processing device.

The method for producing the spherical cerium oxide particles is not particularly limited, and a method known to a collaborator can be applied. For example, it can be produced by burning a tantalum powder by a VMC (Vap-erized Metal Combustion) method. In the VMC method, a chemical flame is formed by a burner in an atmosphere containing oxygen, and a metal powder constituting a part of the target oxide particles is put into an amount sufficient to form a dust cloud to the chemical flame, so that deflagration occurs to obtain oxide particles. method.

Spherical nano-cerium oxide in the resin composition of the present invention The blending amount is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 70% by mass to 85% by mass or less based on the total composition (the alkali-available resin is converted as a solid content). When the amount of the spherical nano-cerium oxide is less than 60% by mass, the viscosity of the curable resin composition is lowered, and the printability is lowered or the hardenability of the cured product is reduced, which is not preferable.

The other type of filler may be added to the spherical cerium oxide filler (component C) of the present invention in an amount of 50% by mass or more, preferably 80% by mass or more, based on the total amount of the filler.

The amount of nano cerium oxide can be understood by measuring the amount of residue after combustion. Specifically, it can be measured by setting TG-DTA (manufactured by Hitachi High-Tech Co., Ltd.) having a combustion condition of 800 to 1000 °C.

Further, NANOCRYL (trade name) XP 0396, XP 0596, XP 0733 manufactured by Hanse-Chemie Co., Ltd., in which nano cerium oxide is dispersed in a compound having one or more ethylenically unsaturated groups or a polyfunctional epoxy resin, can be used. XP 0746, XP 0765, XP 0768, XP 0953, XP 0954, XP 1045 (all are product grade names), or you can also use NANOPOX (trade name) XP 0516, XP 0525, XP 0314 manufactured by Hanse-Chemie. For the product grade name). In this case, the amount of nano cerium oxide and the total amount of other kinds of fillers are the same as above.

[Photopolymerizable monomer]

The photocurable resin composition of the present invention may contain a photoreactive monomer which is conventionally used. The photopolymerizable monomer has one or more ethylene in the molecule. A compound of a sexually unsaturated group. The photoreactive monomer is a photocuring agent which contributes to the carboxyl group-containing resin caused by the irradiation of the active energy ray.

The compound used for the photopolymerizable monomer may, for example, be a conventionally known polyester (meth) acrylate, polyether (meth) acrylate, ethyl urethane (meth) acrylate, or carbonic acid. Ester (meth) acrylate, epoxy (meth) acrylate, and the like. Specifically, a hydroxyalkyl acrylate such as 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate; ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol or the like can be exemplified; Diacrylates of diols; acrylamides such as N,N-dimethyl decylamine, N-methylol acrylamide, N,N-dimethylaminopropyl acrylamide; N , amino-alkyl acrylates such as N-dimethylaminoethyl acrylate and N,N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, and pentaerythritol a polyvalent alcohol such as dipentaerythritol or cis-hydroxyethyl trimer isocyanate or such an ethylene oxide adduct, a propylene oxide adduct, or an ε-caprolactone adduct, etc. Polybasic acrylates; phenoxy acrylates, bisphenol A diacrylates, and oxirane ethylene oxide adducts thereof or methacrylate adducts such as propylene oxide adducts; a polyacrylate of a glycidyl ether such as a glycidyl ether, a glycerol triepoxypropyl ether, a trimethylolpropane triepoxypropyl ether or a triepoxypropyl trimer isocyanate; In the above, a polyol such as a polyether polyol, a polycarbonate diol, a hydroxyl-terminated polybutadiene, or a polyester polyol is directly acrylated, or a diisocyanate is acrylated with a urethane. Acrylates and melamine acrylates, and at least any one of the methacrylates corresponding to the above acrylates.

Among them, by using a photopolymerizable monomer having an aromatic ring, it is preferable from the viewpoint of reduction in warpage.

Further, an epoxy acrylate resin which reacts acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate and isophorone may be used. A semi-carbamate ethyl ester compound of a diisocyanate such as a diisocyanate, an epoxy urethane acrylate compound reacted with a hydroxyl group of the epoxy acrylate resin, or the like is used as a photoreactive monomer. Such an epoxy acrylate-based resin can improve photocurability without lowering the dryness of the touch.

The amount of the photopolymerizable monomer is 5 to 100 parts by mass, more preferably 5 to 70 parts by mass, per 100 parts by mass (solid content) of the photosensitive carboxyl group-containing resin and the photosensitive resin-containing resin. The ratio.

When the amount is less than 5 parts by mass, the photocurability is lowered, and the alkali image after irradiation with the active energy ray is difficult to form, which is not preferable. On the other hand, when it exceeds 100 parts by mass, the solubility in the aqueous alkali solution is lowered and the coating film becomes brittle, which is not preferable.

[thermosetting component]

The photocurable resin composition of the present invention can be thermally cured in addition to photohardening.

By further thermally curing the resin composition after light curing, the properties of the cured product such as heat resistance and insulation reliability can be improved.

As a thermosetting component, an isocyanate compound can be used. , blocked isocyanate compound, amine based resin, maleimide compound, benzoxazine resin, carbodiimide resin, cyclic carbonate compound, epoxy compound, polyfunctional oxycyclobutane compound, episulfide A thermosetting resin which is conventionally used for resins and the like.

In the present invention, it is preferred to use an epoxy resin (D) in particular.

As the epoxy resin, a conventionally known polyfunctional epoxy resin having at least two epoxy groups in one molecule can be used. The epoxy resin may be in the form of a liquid or a solid or semi-solid.

Examples of the epoxy resin include, for example, jER828, jER834, jER1001, and jER1004 manufactured by Mitsubishi Chemical Corporation, Epiclon 840, Epiclon 850, Epiclon 1050, Epiclon 2055 manufactured by DIC Corporation, and Epotohto YD-011 and YD-013 manufactured by Dongdu Chemical Co., Ltd. , YD-127, YD-128, DER317, DER331, DER661, DER664 manufactured by The Dow Chemical Company, SUMI-EPOXY ESA-011, ESA-014, ELA-115, ELA-made by Sumitomo Chemical Industries Co., Ltd. 128. AER330, AER331, AER661, AER664, etc. (all are trade names) of bisphenol A type epoxy resin manufactured by Asahi Kasei Industrial Co., Ltd.; jERYL903 manufactured by Mitsubishi Chemical Corporation, Epiclon 152 and Epiclon 165 manufactured by DIC Corporation Epotohto YDB-400, YDB-500, manufactured by Dongdu Chemical Co., Ltd., DER542 manufactured by Dow Chemical Co., Ltd., SUMI-EPOXY ESB-400 manufactured by Sumitomo Chemical Industries Co., Ltd., ESB-700, AER711, AER manufactured by Asahi Kasei Kogyo Co., Ltd. Brominated epoxy resin such as 714 (both trade names); jER152, jER154 manufactured by Mitsubishi Chemical Corporation, DEN431, DEN438, and DIC manufactured by Dow Chemical Co., Ltd. Epiclon N-730, Epiclon N-770, Epiclon N-865, Epotohto YDCN-701, YDCN-704 manufactured by Dongdu Chemical Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S manufactured by Nippon Kayaku Co., Ltd. , RE-306, NC-3000, SUMI-EPOXY ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Industries, AERECN-235, ECN-299, manufactured by Asahi Kasei Kogyo Co., Ltd., YDCN-700, manufactured by Nippon Steel Chemical Co., Ltd. -2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704 YDCN-704A, DIC company Epiclon N-680, N-690, N-695 A novolac type epoxy resin such as a product name; Epiclon 830 manufactured by DIC Corporation, jER807 manufactured by Mitsubishi Chemical Corporation, Epotohto YDF-170, YDF-175, YDF-2004 manufactured by Dongdu Chemical Co., Ltd. (all products) Name) bisphenol F type epoxy resin; hydrogenated bisphenol A type epoxy resin such as Epotohto ST-2004, ST-2007, ST-3000 (trade name) manufactured by Dongdu Chemical Co., Ltd.; jER604 manufactured by Mitsubishi Chemical Corporation Epotohto YH-434 manufactured by Dongdu Chemical Co., Ltd., SUMI-EPOXY ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (all of which are trade names), epoxy propylamine epoxy resin; Grease; alicyclic epoxy resin of CELOXIDE 2021 (all trade name) manufactured by Daicel Chemical Industry Co., Ltd.; YL-933 manufactured by Mitsubishi Chemical Corporation, TEN manufactured by Dow Chemical Co., Ltd., EPPN-501, EPPN-502, etc. (all are trade names) trishydroxyphenylmethane type epoxy resin; dimethyl-6056, YX-4000, YL-6121 (all trade name) manufactured by Mitsubishi Chemical Corporation, such as bi-xylenol type or biphenol Type epoxy resin or a mixture of these; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ADEKA Corporation, DIC Corporation Bisphenol S type epoxy resin such as EXA-1514 (trade name) manufactured by Seiko Co., Ltd.; bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; jERYL-931 manufactured by Mitsubishi Chemical Corporation Tetrahydroxyphenylethane type epoxy resin (all of which are trade names); Reciprocating ring epoxy resin of TEPIC (both trade name) manufactured by Nissan Chemical Industries Co., Ltd.; BLEMMER DGT manufactured by Nippon Oil Co., Ltd. Epoxypropyl phthalate resin; tetra-glycidyl dimethyl phenol ethane resin such as ZX-1063 manufactured by Dongdu Chemical Co., Ltd.; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032 manufactured by DIC Corporation Epoxy resin containing naphthyl group such as EXA-4750 or EXA-4700; epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC Corporation; CP-50S and CP manufactured by Nippon Oil Co., Ltd. -50M epoxy methacrylate copolymerized epoxy resin; further copolymerized epoxy resin of cyclohexylmaleimide and epoxypropyl methacrylate; CTBN modified epoxy resin ( For example, YR-102, YR-450, etc. manufactured by Dongdu Chemical Co., Ltd., etc., but are not limited thereto.

These epoxy resins may be used alone or in combination of two or more.

In the present invention, among the epoxy resins, an epoxy resin (component D-1) having a naphthalene structure is particularly preferable. By using an epoxy resin having a naphthalene structure, the low warpage and flame retardancy of the cured product are enhanced.

Specific examples of the commercially available materials include ESN-190, ESN-360 (manufactured by Nippon Steel Chemical Co., Ltd.), and HP-4032, EXA-4750, and EXA-4700 (manufactured by DIC Corporation).

These hardening resins can be used alone or in combination 2 More than one kind. By using an epoxy resin having a naphthalene structure, the softness of the cured coating film is improved, and the linear expansion coefficient is further reduced.

The amount of the thermosetting component is 5 parts by mass to 50 parts by mass, preferably 10 to 30 parts by mass, per 100 parts by mass (solid content) of the photosensitive carboxyl group-containing resin and the photosensitive resin-containing resin. The ratio.

Further, the photocurable resin composition of the present invention can be formed by using a colorant, a specific copolymer, a binder polymer, an elastomer, an adhesion promoter, an antioxidant, an additive such as an ultraviolet absorber, and an organic solvent. . The ingredients of these are described below.

[Colorant]

In the curable resin composition of the present invention, a coloring agent can be formulated.

As the coloring agent, a conventionally known coloring agent such as red, blue, green, or yellow may be used, and any of a pigment, a dye, and a coloring matter may be used. Specifically, for example, the following colorimetric index (C.I.; The Society of Dyers and Colourists) number is included. However, halogen-free coloring agents are preferred from the viewpoint of reducing environmental load and affecting the human body.

Red colorant:

Examples of the red coloring agent include monoazo, bisazo, azo lake, benzimidazolone, anthracene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. For example, the following can be specifically exemplified.

Monoazo system: Pigment Red 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114,146,147 , 151, 170, 184, 187, 188, 193, 210, 245, 253, 258, 266, 267, 268, 269.

Bisazo: Pigment Red 37, 38, 41.

Monoazo lake system: Pigment Red 48:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,52:2,53:1,53 :2,57:1,58:4,63:1,63:2,64:1,68.

Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208.

The system is: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224.

Diketopyrrolopyrrole: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272.

Condensed azo system: Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242.

Department: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207.

Quinacridone system: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:

Examples of the blue colorant include indigo and lanthanide, and the pigment is classified as a pigment. Specifically, Pigment Blue 15, Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3 , Pigment Blue 15:4, Pigment Blue 15:6, Pigment Blue 16, Pigment Blue 60.

As the dye system, Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent can be used. Blue 70 and so on. In addition to the above, a metal-substituted or unsubstituted indigo compound can also be used.

Green colorant:

As the green colorant, there are also indigo, lanthanide, and lanthanide. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like can be used. In addition to the above, a phthalocyanine compound which may be substituted with or without a metal may be used.

Yellow colorant:

Examples of the yellow coloring agent include a monoazo type, a bisazo type, a condensed azo type, a benzimidazolone type, an isoindolinone type, and an anthraquinone type. Specific examples thereof include the following.

Lanthanum: Solvent Yellow 163, Pigment Yellow 24, Pigment Yellow 108, Pigment Yellow 193, Pigment Yellow 147, Pigment Yellow 199, Pigment Yellow 202.

Isoindolinone series: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185.

Condensed azo system: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180.

Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181.

Monoazo system: Pigment Yellow 1,2,3,4,5,6,9,10,12,61,62,62:1,65,73,74,75,97,100,104,105,111 , 116, 167, 168, 169, 182, 183.

Diazo system: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198.

In addition, for the purpose of adjusting the color tone, a coloring agent such as purple, orange, brown or black may be added.

Specific examples include Pigment Violet 19, 23, 29, 32, 36, 38, 42, Solvent Violet 13, 36, CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16 , CI Pigment Orange 17, CI Pigment Orange 24, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49, CI Pigment Orange 51 , CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73, CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Black 1, CI Pigment Black 7, and the like.

The blending ratio of the coloring agent is preferably 0 to 10 parts by mass, preferably 0 to 10 parts by mass, based on 100 parts by mass (solid content) of the photosensitive carboxyl group-containing resin and the photosensitive resin-containing resin. It is used in a ratio of 0.1 to 5 parts by mass.

[Binder Polymer]

In the resin composition of the present invention, a conventionally known binder polymer can be used for the purpose of improving the flexibility and dryness of the resulting cured product.

As the binder polymer, a cellulose-based, polyester-based or phenoxy resin-based polymer can be preferably used.

Cellulose polymer is made from acetic acid produced by EASTMAN Acid cellulose (CAB), cellulose acetate propionate (CAP) series, polyester polymer is VYLON series manufactured by Toyobo Co., Ltd., phenoxy resin polymer is bisphenol A, bisphenol F and hydrogenated compounds thereof. The phenoxy resin is preferred.

The amount of the binder polymer added is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, based on 100 parts by mass of the total of the photosensitive carboxyl group-containing resin and the photosensitive resin-containing resin. It is 5 to 30 parts by mass. When the amount of the binder polymer is more than 50 parts by mass, the alkalinity of the curable resin composition is poor, and the working life for enabling development becomes short, which is not preferable.

[Y-X-Y type block copolymer]

The photocurable resin composition of the present invention may be used in combination with a block copolymer. The block copolymer generally means two or more polymer units having different properties, and is a copolymer in which a chain structure is formed by covalent bonding.

The YXY-type block copolymer is used in combination with a spherical cerium oxide filler having an average particle diameter of 300 nm or less to suppress cracking in the cured product obtained from the photocurable resin composition of the present invention. The sex is improved and the warpage is reduced.

The block copolymer used in the present invention is represented by the following formula (I)

Y-X-Y (I)

(wherein Y is a glass transition point Tg of 0 ° C or more, preferably 50 ° C or more of polymer units, and X is a glass transition point Tg of less than 0 ° C, preferably The block copolymer represented by the polymer unit of -20 ° C or lower is preferable, and further preferably solid at 20 ° C or higher and 30 ° C or lower.

Thus, it is considered that a block copolymer which is compatible with the matrix at both ends and in which the central block is incompatible with the matrix is likely to exhibit a specific structure in the matrix.

The polymer unit Y is preferably polymethyl methacrylate (PMMA), polystyrene (PS) or the like, and the polymer unit X is poly n-butyl acrylate (PBA), polybutadiene (PB), or the like. Preferably. Further, when a styrene unit, a hydroxyl group-containing unit, a carboxyl group-containing unit, an epoxy group-containing unit, an N-substituted acrylamide unit, or the like is introduced into one part of the polymer unit Y, it is excellent in compatibility with the carboxyl group-containing resin described above. The hydrophilic unit can further improve the compatibility.

For example, the method described in Japanese Patent Application No. 2005-515281 and No. 2007-516326 is exemplified.

Specifically, in the formula (I), Y is polystyrene, polyepoxypropyl methacrylate, or N-substituted polyacrylamide, polymethyl (meth) acrylate or a carboxylic acid modified product thereof. Or a hydrophilic group-modified substance, and X is preferably poly-n-butyl (meth) acrylate or polybutadiene.

As a commercial item of the Y-X-Y type block copolymer, an acrylic triblock copolymer produced by living polymerization manufactured by Arkema Co., Ltd. can be exemplified. As a specific example, a MAM type represented by polymethyl methacrylate-polybutyl acrylate-polymethyl methacrylate can be exemplified (for example) For example, M51, M52, M53, M22, etc., MAM A type modified by carboxylic acid (for example, SM4032XM10 or the like, or MAM N type modified by hydrophilic group (for example, 52N, 22N, etc.).

Further, the block copolymer has a mass average molecular weight (Mw) of 20,000 or more and 400,000 or less, and preferably 30,000 to 300,000. The molecular weight distribution (Mw/Mn) is preferably 3 or less.

If the mass average molecular weight is less than 20,000, the effect of toughness and flexibility is not obtained, and the viscosity is also poor. On the other hand, when the mass average molecular weight exceeds 400,000, the viscosity of the curable resin composition becomes high, and printability, developability, and the like are remarkably deteriorated.

The amount of the above-mentioned block copolymer is preferably from 1 to 50 parts by mass, more preferably from 5 to 35 parts by mass, per 100 parts by mass (solid content) of the carboxyl group-containing resin (A).

When the amount is less than 1 part by mass, the effect is not expected, and when it is 50 parts by mass or more, the development of the photocurable resin composition or the coating property may be deteriorated, which is not preferable.

[elastomer]

The resin composition of the present invention can be formulated with an elastomer for the purpose of imparting flexibility to the obtained cured product, improving the brittleness of the cured product, and the like.

The elastomer may, for example, be a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide amine elastomer, a polyester amide amine elastomer, or acrylic acid. It is an elastomer or an olefin elastomer.

Further, a resin obtained by modifying a part or all of the epoxy groups of the epoxy resins having various skeletons with a carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used.

Further, an epoxy-containing polybutadiene-based elastomer, an acrylic-containing polybutadiene-based elastomer, a hydroxyl group-containing polybutadiene-based elastomer, a hydroxyl group-containing isoprene-based elastomer, or the like may be used.

The elastomer may be used singly or in combination of two or more.

[Adhesion promoter]

In the resin composition of the present invention, a adhesion promoter for improving the adhesion between the layers or the adhesion between the photosensitive resin layer and the substrate can be used.

As the adhesion promoter, for example, benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholinyl group can be exemplified. Methyl-1-phenyl-triazole-2-thione, 5-amino-3-morpholinylmethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, Triazole, tetrazole, benzotriazole, carboxybenzotriazole, amine-containing benzotriazole, decane coupling agent, and the like.

[Antioxidants]

Most of the polymer materials are oxidatively degraded in a chain when the oxidation starts, and the function of the polymer material is lowered. In the resin composition of the present invention, at least one of (1) a radical scavenger which invalidates the generated radical, and (2) a peroxide which is produced may be added. An antioxidant that decomposes into a harmless substance and a peroxide decomposing agent that does not generate new radicals.

Specific examples of the radical scavenger include hydroquinone, 4-tert-butyl catechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, and 2,6-di-t-butyl. Base-p-cresol, 2,2-methylene-bis-(4-methyl-6-t-butylphenol), 1,1,3-parade (2-methyl-4-hydroxy-5) -t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-cis (3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1, a phenolic system such as 3,5-gin (3',5'di-t-butyl-4-hydroxybenzyl)-S-triazine-2,4,6-(1H,3H,5H)trione, An anthraquinone compound such as p-methoxyphenol or benzoquinone, an amine compound such as bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate or phenothiazine.

The radical scavenger may be a commercially available one, for example, Adekastab AO-30, Adekastab AO-330, Adekastab AO-20, Adekastab LA-77, Adekastab LA-57, Adekastab LA-67, Adekastab LA-68, Adekastab LA-87 (above is manufactured by Asahi Kasei Co., Ltd., trade name), IRGANOX1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (above, BASF JAPAN, trade name )Wait.

As the specific antioxidant, a phosphorus compound such as triphenylphosphite, neopentyl tetrakisalyl thiopropionate, dilauryl thiodipropionate, or the like, may be exemplified as the antioxidant which acts as a peroxide decomposing agent. A sulfur-based compound such as distearyl 3,3'-thiodipropionate.

The peroxide decomposing agent may be a commercially available one. For example, Adekastab TPP (product name manufactured by Asahi Kasei Co., Ltd.), Mark AO-412S (manufactured by Adeka Argus Chemical Co., Ltd., trade name), Sumilizer TPS (manufactured by Sumitomo Chemical Co., Ltd., trade name) may be mentioned. )Wait.

The antioxidant may be used alone or in combination of two or more.

[UV absorber]

Polymer materials absorb light and therefore decompose. Since the resin composition of the present invention is used for the stabilization of ultraviolet rays, an ultraviolet absorber can be used in addition to the antioxidant.

Examples of the ultraviolet absorber include a benzophenone derivative, a benzoate derivative, a benzotriazole derivative, a triazine derivative, a benzothiazole derivative, a cinnamic acid ester derivative, and an amine anisate derivative. , dibenzyl benzyl methane derivatives and the like.

Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxy-benzophenone 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-n-octyl Oxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, etc., as specific examples of the benzoate derivative, may be exemplified 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di-t-butyl As a specific example of the benzotriazole derivative, a 4-hydroxybenzoate and a hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate can be exemplified as 2-( 2'-hydroxy- 5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl -5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole , 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy-3',5'-di-t-pentylphenyl)benzotriazole, etc. Specific examples of the triazine derivative include hydroxyphenyltriazine, bisethylhexyloxyphenol methoxyphenyltriazine, and the like.

As the ultraviolet absorber, a commercially available one can be exemplified, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (The above is a BASF JAPAN company, trade name).

The ultraviolet absorber may be used alone or in combination of two or more. By using in combination with an antioxidant, the molded article obtained from the curable resin composition of the present invention can be stabilized.

[Other additives]

Further, in the resin composition of the present invention, an additive such as a thermal polymerization inhibitor, a tackifier, an antifoaming agent, a leveling agent, a decane coupling agent, or a rust inhibitor may be used.

Among them, as a thermal polymerization inhibiting agent, hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, gallic phenol, phenothiazine, or the like can be used. As the tackifier, fine powder of cerium oxide, organic bentonite, montmorillonite, or the like can be used, and at least one of a defoaming agent and a leveling agent can be used, and a polyfluorene-based system, a fluorine-based system, a polymer-based system, or the like can be used. As the decane coupling agent, an imidazole type, a thiazole type, a triazole type, or the like can be used. Adjustable additives.

In order to prevent non-autonomous thermal polymerization of the resin composition or polymerization over time, a thermal polymerization inhibitor may be used.

As a thermal polymerization inhibiting agent, for example, 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butyl catechol, gallic phenol, 2-hydroxydiphenyl can be exemplified. Methyl ketone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-4- Cresol, 2,2'-methylenebis(4-methyl-6-t-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and Organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelating compound of nitroso compound and Al, and the like.

[Organic solvents]

Further, in the present invention, an organic solvent can be used. The organic solvent can be used in the synthesis of the carboxyl group-containing resin, the components A to C, the component D, E, F, and the necessary additives, and the photosensitive resin composition obtained by coating on the substrate or the carrier film. When used, it is used to adjust the viscosity.

Examples of the organic solvent include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, and stones. Oil solvent, etc.

More specifically, ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, ceramide, methyl cyanisol, and butyl race can be exemplified.珞Su, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, etc. Alcohol ethers, esters of ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol butyl ether acetate, etc., ethanol An alcohol such as propanol, ethylene glycol or propylene glycol, an aliphatic hydrocarbon such as octane or decane, or a petroleum solvent such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha or solvent naphtha.

Such an organic solvent may be used singly or as a mixture of two or more.

The curable resin composition of the present invention may be in the form of a dry film comprising a carrier film (support) and a layer formed of a curable resin composition formed on the carrier film.

In the case of dry film formation, the curable resin composition of the present invention is diluted with an organic solvent to adjust to a suitable viscosity, and is used in a corner wheel coater, a knife coater, a lip coater, a bar coater, and a squeeze coat. Cloth machine, reverse coater, transfer roll coater, gravure coater, spray coater equal to carrier film The upper thickness is uniformly applied, and usually, the film is obtained by drying at a temperature of 50 to 130 ° C for 1 to 30 minutes. The coating film thickness is not particularly limited, and generally, the film thickness after drying is suitably selected in the range of 10 to 150 μm, preferably 20 to 60 μm.

As the carrier film, a plastic film can be used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyimide film, a polypropylene film, or a polystyrene film can be used. good. The thickness of the carrier film is not particularly limited, and is generally suitably selected in the range of 10 to 150 μm.

After the resin composition of the present invention is formed on a carrier film, it is preferable to laminate the surface of the film to prevent peeling of the film surface.

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. Considering the peeling of the cover film, the adhesion of the film to the cover film becomes smaller than the adhesion of the film to the carrier film.

The resin composition of the present invention is adjusted to a viscosity suitable for a coating method by, for example, an organic solvent, by a dip coating method, a flow coating method, a roll coating method, a bar coating method, a screen printing method, a curtain coating method, or the like. The method is applied to a substrate, and the organic solvent contained in the composition is volatilized and dried (preliminary drying) at a temperature of about 60 to 100 ° C to form a non-tacky coating film. Further, when the coating composition is applied onto a carrier film and dried as a dry film for film winding, the photocurable resin composition layer is laminated on the substrate in contact with the substrate by a bonding machine or the like. After the material is removed, it can be shaped by peeling off the carrier film. Into the resin insulation layer.

As the substrate, in addition to a printed wiring board or a flexible printed wiring board in which a circuit is formed in advance, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/non-woven fabric can also be used as an example. Epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluororesin. Polyethylene. Polyphenylene ether. A high-voltage circuit such as a cyanate ester resin or the like, a copper-laminated plate of all grades (FR-4, etc.), a polyimide film, a PET film, a glass substrate, a ceramic substrate, and a crystal. Round plate, etc.

The volatilization drying after the application of the photocurable resin composition of the present invention can be carried out by using a hot air circulation type drying furnace, an IR furnace, a hot plate, a convection oven or the like (using a heat source having a method of heating air by steam) The method of countercurrent contact of hot air in the dryer and the manner in which the support is sprayed by the nozzle are performed.

In the present invention, the solvent of the photocurable resin composition or the dry film is volatilized and dried, and the coating film thus obtained is exposed to light (irradiation of active energy rays), and the exposed portion (illuminated by the active energy ray) Partially) hardened.

For example, for a photocurable resin composition or a dry film after drying, exposure by an active energy ray can be performed by a contact or non-contact method by forming a mask having a pattern. Further, for the photocurable resin composition or the dry film, the exposed portion can be photohardened by direct pattern exposure by a laser direct exposure machine.

In any of the above methods, the unexposed portion can be imaged by a dilute aqueous alkali solution (for example, 0.3 to 3 wt% aqueous sodium carbonate solution) to form a resist. Graphic type.

The exposure machine for the active energy ray irradiation may be a device that is equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short-arc lamp, and the like, and is irradiated with ultraviolet rays in the range of 350 to 450 nm.

Further, the direct drawing device can be used (for example, a laser direct imaging device that directly draws an image by laser by CAD data from a computer). As a laser light source for a direct-drawing machine, any one of a gas laser and a solid laser can be used as long as laser light having a maximum wavelength of 350 to 410 nm is used.

The amount of exposure for forming an image varies depending on the film thickness or the like, but is generally set to be in the range of 20 to 800 mJ/cm ² , preferably 20 to 600 mJ/cm ² .

As the developing method, a dip method, a shower method, a spray method, a brush method, or the like can be used as the developing solution, and potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, or sodium citrate can be used. An aqueous solution of an alkali such as ammonia or an amine.

Further, in the case where the flame-retardant resin composition of the present invention contains a thermosetting component, it can be thermally cured by heating at a temperature of, for example, about 140 to 180 ° C, and the carboxyl group of the carboxyl group-containing resin reacts with the thermosetting component. A cured coating film having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties is formed.

The invention is further illustrated in detail by the following examples. Further, the present invention is not limited to the following embodiments. In the examples, the "parts" and "%" of the materials used in the materials are qualitative unless otherwise stated. The amount is the benchmark.

The photocurable resin composition of the present invention is suitable as a permanent film of a printed wiring board, and is more suitable as a solder resist or an interlayer insulating material.

[Examples] [Examples 1 to 9 and Comparative Examples 1 to 4]

Each of the materials was prepared in accordance with the composition described in Table 1 below, and prepared by mixing with a stirrer, followed by kneading with a three-roll mill to prepare a thermosetting resin composition.

Further, a photosensitive carboxyl group-containing resin solution, a photosensitive carboxyl group-containing resin solution, and cerium oxide (slurry) were produced in the following order.

[Synthesis of photosensitive carboxyl group-containing resin solution A-2]

A phenol novolak type cresol resin (Shonol (registered trademark) CRG951, OH equivalent: 119.4) 119.4 g was placed in an autoclave equipped with a thermometer, a nitrogen gas introducing device, an alkylene oxide introducing device, and a stirring device. 1.19 g of potassium hydroxide and 119.4 g of toluene were substituted with nitrogen gas while stirring, and the temperature was raised by heating.

Next, 63.8 g of propylene oxide was gradually dropped by the above alkylene oxide introducing device, and reacted at 125 to 132 ° C and 0 to 4.8 kg/cm ² for 16 hours. Thereafter, the mixture was cooled to room temperature, and 1.56 g of 89% phosphoric acid was added and neutralized with potassium hydroxide to obtain propylene oxide of a novolac type cresol resin having a nonvolatile content of 62.1% and a hydroxyl group of 182.2 g/eq. Reaction solution. This is an average of 1.08 mole addition of alkylene oxide per one equivalent of phenolic hydroxyl groups.

293.0 g of an alkylene oxide reaction solution of the obtained novolac type cresol resin, 43.2 g of acrylic acid, 11.53 g of methanesulfonic acid, 0.18 g of methyl hydroquinone, and 252.9 g of toluene were placed in a mixer, a thermometer, and an air blowing tube. In the reactor, air was blown at a rate of 10 ml/min, and reacted at 110 ° C for 12 hours while stirring. The water formed by the reaction was distilled as azeotrope with toluene to distill off 12.6 g of water.

Thereafter, the resulting reaction solution was cooled to room temperature, neutralized with 35.35 g of a 15% aqueous sodium hydroxide solution, and then washed with water. Then, the toluene side was distilled off with 118.1 g of diethylene glycol monoethyl ether acetate as an evaporator to obtain a novolac type acrylate resin solution. Further, 332.5 g of the obtained novolak-type acrylate resin solution and 1.22 g of triphenylphosphine were placed in a reactor equipped with a stirrer, a thermometer, and an air blowing tube, and air was blown at a rate of 10 ml/min while stirring. 60.8 g of tetrahydrophthalic anhydride was slowly added and reacted at 95 to 101 ° C for 6 hours.

Thus, a resin solution of a carboxyl group-containing photosensitive resin having a solid content of 88 mg KOH/g and a nonvolatile content of 71% was obtained. Hereinafter, this is referred to as varnish A-2.

[Synthesis of non-photosensitive carboxyl group-containing resin solution A-1]

It is equipped with a thermometer, a nitrogen gas introduction device, and an alkylene oxide introduction device. In the autoclave of the mixing device, a novolak type cresol resin (manufactured by Showa Denko Co., Ltd., Shonol (registered trademark) CRG951, OH equivalent: 119.4), 119.4 g, potassium hydroxide 1.19 g, and toluene (119.4 g) were added while stirring. The inside of the system was replaced with nitrogen, and the temperature was raised by heating.

Next, 63.8 g of propylene oxide was slowly dropped, and reacted at 125 to 132 ° C and 0 to 4.8 kg / cm ² for 16 hours. Thereafter, the mixture was cooled to room temperature, and 0.56 g of 89% phosphoric acid was added to the reaction solution to neutralize potassium hydroxide to obtain an epoxy of a novolac type cresol resin having a nonvolatile content of 62.1% and a hydroxyl value of 182.2 g/eq. Propane reaction solution. This is an average of 1.08 mole addition of alkylene oxide per one equivalent of phenolic hydroxyl groups.

Further, 293 g of the above product and 1.22 g of triphenylphosphine were placed in a reactor equipped with a stirrer, a thermometer, and an air blowing tube, air was blown at a rate of 10 ml/min, and tetrahydrophthalic anhydride was gradually added with stirring (molecular weight 152) 152 g, reacted at 95 to 101 ° C for 6 hours.

Thus, a resin solution of a carboxyl group-containing resin having an acid value of 100 mg KOH (56)/g of a solid matter and 75% of a nonvolatile content was obtained. Hereinafter, this is referred to as varnish A-1.

[Modulation of spherical cerium oxide slurry]

500 g of normal spherical cerium oxide, 495 g of diethylene glycol monoethyl ether acetate (carbitol acetate) as a solvent, and 5 g of a vinyl decane coupling agent as a decane coupling agent were mixed and stirred to be a bead mill. The machine was subjected to dispersion treatment using 0.5 μm zirconia beads. This was repeated three times and filtered through a 3 μm filter to prepare an average particle diameter of 150 nm, 200 nm, 300 nm, and 450 nm. Each of the 770 nm cerium oxide slurry.

*1: 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide (Lucirin TPO: manufactured by BASF JAPAN)

*2: Ethylketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-indazol-3-yl]-, 1,1-(O-acetamidine) (Irgacure) OXE 02: BASF JAPAN company)

*3: (stock) Admatechs spherical cerium oxide slurry

*4: C.I.Pigment Blue 15:3

*5: C.I.Pigment Yellow147

*6: 2-mercaptobenzothiazole

*7: Diethylene glycol monoethyl ether acetate

*8: Naphthalene type epoxy resin (ESN-355: manufactured by Nippon Steel Chemical Co., Ltd.)

*9: Bisphenol type epoxy resin (YSLV-80XY: manufactured by Dongdu Chemical Co., Ltd.)

*10: dipentaerythritol pentaacrylate

*11: Tricyclodecane dimethanol diacrylate

*12: FUSELEX WX (made by Ronson)

Using the photocurable resin composition (varnish) produced in Examples 1 to 9 and Comparative Examples 1 to 4, samples for evaluation were prepared by the following procedures.

<1-1. Production of the most suitable exposure amount evaluation sample>

A circuit pattern substrate having a copper thickness of 18 μm was subjected to surface roughening treatment using a copper surface roughening agent (MECetchbond (registered trademark) CZ-8100 manufactured by MEC Co., Ltd.), and then washed with water and dried.

Next, the photocurable resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4 were applied by a screen printing method to the entire substrate, and dried in a hot air circulating drying oven at 80 ° C for 30 minutes. The film thickness of the dried resin composition was 20 μm. This was used as the sample for the most suitable exposure measurement evaluation.

<1-2. The most suitable exposure measurement>

The exposure of each sample for evaluation was performed in a state in which a step wedge (Kodak No. 2) was placed between the exposure apparatus and the evaluation sample by using an exposure apparatus equipped with a high-pressure mercury lamp. Further, the step wedge is a film having a concentration gradient, and the exposure amount is a exposure having a gradient of 21 stages in each sample by subjecting the sample to the exposure device with one exposure.

The sample for evaluation after exposure was subjected to development at 30 ° C for 90 seconds using a 0.2 MPa, 1 wt% aqueous sodium carbonate solution. In the step wedge piece, the resin is not cured until the eighth stage of the film concentration is concentrated (the light transmission amount is small), and the amount of light of the exposure device is adjusted so that the development can be removed. The amount of light used for hardening of the resin was evaluated by the following criteria.

○: The exposure amount is less than 300mJ/cm ²

△: The exposure amount is 300 mJ/cm ² or more, and less than 500 mJ/cm ²

×: The exposure amount is 500 mJ/cm ² or more

<2-1. Production of samples for evaluation of resistance to cold and heat

A solution obtained by appropriately diluting the photocurable resin compositions of Examples 1-9 and Comparative Examples 1-4 with methyl ethyl ketone was applied to a PET carrier film (Toray Co., Ltd., FB). -50: 16 μm), dried at 80 ° C for 30 minutes. The film thickness of the dry film after drying was 20 μm.

The obtained dry film was bonded to a circuit pattern substrate having a copper thickness of 18 μm so that the curable resin layer was in contact with the substrate, and the laminate was bonded using a vacuum laminator. On the substrate, the PET carrier film was peeled off by exposing the solder resist pattern to the most suitable exposure amount using the exposure apparatus equipped with the high-pressure mercury short-arc lamp.

The development was carried out for 60 seconds under the conditions of a spray pressure of 0.2 MPa with a 1% by mass aqueous solution of sodium carbonate at 30 ° C to obtain a solder resist pattern. This substrate was irradiated with ultraviolet rays under the conditions of an integrated exposure amount of 1000 mJ/cm ² in a UV conveyor belt furnace, and then cured by heating at 160 ° C for 60 minutes. The obtained printed wiring board was used as the following sample for evaluation of the cold and cold resistance.

<2-2. Evaluation of cold and heat rigor tolerance>

Using a hot and cold sputum tester (manufactured by ETAC Co., Ltd.), the sample for evaluation of the thermal and thermal resistance was kept at -55 ° C for 30 minutes, and then the temperature was raised to 125 ° C, and this was maintained for 30 minutes. This was performed as a cycle of 500 cycles of resistance test.

After the test, the shape of the cured product after the treatment was visually observed to evaluate the occurrence of the crack. The judgment criteria are as follows.

○: The cracking rate is less than 20%

△: The crack occurrence rate is 30% or more and less than 50%.

×: The crack occurrence rate is 50% or more

<3-1. Production of sample for resolution evaluation>

A sample for evaluation of resolution was prepared in the same manner as in the production of samples for evaluation of cold and heat tolerance. However, in this test, in place of the defect and the absence of ○, pattern exposure was performed so that the dry film was provided with an opening of 80 μm. Use this as a sample for the following resolution evaluation.

<3-2. Resolution Evaluation>

The opening having an opening diameter of 80 μm was observed by SEM (scanning electron microscope) and evaluated based on the following criteria.

○: Cu at the bottom of the opening is a good shape that can be confirmed

×: Cu at the bottom of the opening is unconfirmable

<4-1. Production of sample for warpage evaluation>

The photocurable resin compositions of Examples 1 to 9 and Comparative Examples 1 to 4 were applied to a 35 μm copper foil. This was taken as the following sample for warpage evaluation.

<4-2. Warpage evaluation>

The sample for warpage evaluation was hardened under the same conditions as in 2-1 to form a cured product. The cured product was cut out in a 50 mm × 50 mm square with a copper foil, and the warpage of the four corners was measured to obtain an average value, which was evaluated based on the following criteria.

○: Those whose warpage is less than 10 mm.

△: The warpage is 10 mm or more and less than 15 mm.

×: The warpage is 15 mm or more.

<5-1. Preparation of sample for HAST tolerance evaluation>

A sample for HAST resistance evaluation was prepared in the same manner as the sample for the evaluation of the cold and heat tolerance test. However, in this test, instead of applying a circuit pattern substrate having an electrolytic gold plated copper thickness of 18 μm, a dry film was applied onto a BT substrate on which a comb-shaped electrode (line/gap = 15 μm / 15 μm) was formed. This was taken as a sample for the following HAST tolerance evaluation.

<5-2.HAST tolerance evaluation>

The sample for HAST resistance evaluation was placed in a high-temperature and high-humidity bath at 130 ° C and a humidity of 85%, and the charging voltage was 5.5 V for 168 hours, and the in-tank HAST test was performed.

The insulation resistance value in the tank after 168 hours was measured to evaluate the HAST resistance. The judgment criteria are as follows.

○: more than 10 ⁸ Ω △: 10 ⁶ ~ 10 ⁸ Ω

×: less than 10 ⁶ Ω or short circuit

In the resin compositions of Examples 1 to 15 and Comparative Examples 1 to 4, the amount of cerium oxide (residue amount) was measured using a temperature of TG/DTA6200 manufactured by Hitachi High-Tech Co., Ltd. at 800 to 1000 °C.

The results of the above tests are shown in Table 2 below.

As a result of the above-mentioned respective tests, the photocurable resin composition of the present invention showed satisfactory results in all of the exposure amount, the resolution, the warpage, the cold heat resistance and the HAST resistance.

On the other hand, in the comparative example, the nano cerium oxide having a particle diameter of 300 nm or less is not used, or the cured product is less than 60% by mass based on the total amount of the photocurable resin composition. There is no improvement in the balance of good characteristics as in the present invention.

The present invention is not limited to the configurations and examples of the embodiments described above, and various modifications are possible within the scope of the invention.

Claims (9)

A photocurable resin composition which can be imaged by an aqueous alkali solution, which comprises (A-1) a carboxyl group-containing resin having no photosensitive group, (B) a photopolymerization initiator, and (C) an average particle diameter The photocurable resin composition of the spherical cerium oxide filler of 300 nm or less is characterized in that the (C) spherical cerium oxide having an average particle diameter of 300 nm or less is the total amount of the photocurable resin composition. The blending amount of the filler is 60% by mass or more. The photocurable resin composition which can be imaged by an aqueous alkali solution according to claim 1, further comprising (A-2) a carboxyl group-containing resin having a photosensitive group. A photocurable resin composition which can be imaged by an aqueous alkali solution according to claim 1 or 2, wherein the (A-1) carboxyl group-containing resin having no photosensitive group is obtained by using a polybasic acid anhydride and a polyphenol A carboxyl group-containing resin obtained by reacting a compound with an alkylene oxide-modified polyol resin. A photocurable resin composition which can be imaged by an aqueous alkali solution, wherein the (A-2) carboxyl group-containing resin having a photosensitive group is obtained by using (meth)acrylic acid and polyphenol The compound is reacted with an alkylene oxide-modified polyol resin, and further a carboxyl group-containing resin obtained by reacting a polybasic acid anhydride. The photocurable resin composition of claim 1 or 2, further comprising (D) an epoxy resin. The photocurable resin composition according to claim 5, wherein the (D) epoxy resin is (D-1) an epoxy resin having a naphthalene structure. A photocurable dry film obtained by coating and drying a photocurable resin composition according to any one of claims 1 to 6 on a carrier film. A cured product obtained by photocuring a photocurable resin composition according to any one of claims 1 to 6 or a photocurable dry film, wherein the photocurable dry film is composed of the photocurable resin The material is coated and dried on the film. A printed wiring board characterized by having a cured film obtained by applying the photocurable resin composition according to any one of claims 1 to 6 or drying the photocurable resin composition to a film. The photocurable dry film is applied to a substrate, and a film of the photocurable resin composition is provided, and the film is photohardened by irradiation of an active energy ray, and then thermally cured.