KR20160051705A - Curable resin composition, dry film and cured product thereof, and printed wiring board using same - Google Patents

Abstract

The present invention provides a curable resin composition having excellent electrical characteristics, flexibility, and low bending properties, and prevents the generation of cracks and appearance errors. The curable resin composition comprises: (A) a carboxyl group-contained resin; (B) a photopolymerization initiator; and (C) an organic filler in which a surface is coated by silica. The organic filler in which a surface is coated by silica in the (C) is preferably a urethane resin in which a surface is coated by silica.

Description

TECHNICAL FIELD The present invention relates to a curable resin composition, a dry film and a cured product thereof, and a printed circuit board using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition,

The present invention relates to a curable resin composition, a dry film and a cured product thereof, and a printed wiring board using the same.

2. Description of the Related Art It is known to compound an organic filler in a curable resin composition for obtaining a coating film (cured film), which is one of constituent elements of a printed wiring board and a flexible wiring board (hereinafter abbreviated as FPC) For example, when a phosphorus-containing compound capable of imparting flame retardancy to soften a coating film and an epoxy resin having excellent heat resistance are incorporated in the curable resin composition, cracks are generated in the cured film during cutting of the wiring board, It may become easier to do. In order to suppress the occurrence of cracks in the cured coating film, for example, Patent Document 1 discloses an alkali developing type photocurable and thermosetting resin composition containing polyurethane fine particles. Further, in order to suppress the occurrence of cracks in the cured coating by highly blending an inorganic filler for the purpose of imparting excellent functional properties, Patent Document 2 discloses a curable resin composition containing an organic filler having a specific modulus of elasticity and an average particle diameter .

Japanese Patent Laid-Open No. 2002-293882 (Claims) Japanese Patent Application Laid-Open No. 2009-102623 (Claims)

However, in the case of using an organic filler, occurrence of defective appearance that the organic filler is crushed in the manufacturing process of the printed wiring board or the FPC, that is, the pressing process, the gloss is generated at the abutted portion of the press machine, . In addition, there has been a demand for improving the compatibility of the organic filler with the resin component and the electrical properties of the cured coating. On the other hand, in the thin FPC, there is a problem that the FPC may be warped due to the influence of the coating formed by curing the curable resin composition.

Accordingly, an object of the present invention is to provide a curable resin composition which is excellent in electric characteristics, flexibility, low warpage, and in which generation of cracks and occurrence of appearance defects are suppressed.

The inventors of the present invention have made intensive investigations in order to solve the above problems, and as a result, they found that the above problems can be solved by using an organic filler whose surface is coated with silica, and have completed the present invention.

That is, the curable resin composition of the present invention is characterized by containing (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, and (C) an organic filler whose surface is coated with silica.

It is preferable that the curable resin composition of the present invention is an urethane resin in which the surface of the above (C) surface-covered organic filler is coated with silica.

The curable resin composition of the present invention is a curable resin composition wherein the carboxyl group-containing resin (A) is a group consisting of a bisphenol A structure, a bisphenol F structure, a biphenol structure, a biphenol novolak structure, a biscensilene structure, a biphenyl novolac structure, and a urethane structure Is a carboxyl group-containing resin having at least one partial structure selected from the group consisting of

The curable resin composition of the present invention preferably further contains (D) a flame retardant.

The flame retardant (D) is preferably a phosphorus-containing compound.

It is preferable that the phosphorus-containing compound is a phenoxyphosphazene oligomer or a phosphinic acid metal salt.

The curable resin composition of the present invention preferably further contains (E) an epoxy resin having a biphenyl novolak structure.

The curable resin composition of the present invention is preferably used for forming a solder resist.

The curable resin composition of the present invention is preferably black.

The dry film of the present invention is characterized in that any one of the above-mentioned curable resin compositions is applied to a film and dried.

The cured coating of the present invention is characterized in that at least one of the above-mentioned curable resin composition or the above-mentioned dry film is thermally cured or photo-cured.

The printed wiring board of the present invention is characterized by comprising the cured coating.

According to the present invention, it becomes possible to provide a curable resin composition which is excellent in electrical characteristics, flexibility and low warpage, and is capable of suppressing the generation of cracks and appearance defects.

The curable resin composition of the present invention is characterized in that the resin composition containing (A) the carboxyl group-containing resin and (B) the photopolymerization initiator contains (C) an organic filler whose surface is coated with silica.

By incorporating an organic filler whose surface is coated with silica, it is possible to suppress the occurrence of cracks in the cured coating while preventing occurrence of appearance defects during the pressing process. In addition, it has been found that the organic filler coated with silica is excellent in insulation reliability because of its good compatibility with the resin component.

It has also been found that a curable resin composition having excellent flame retardancy can be obtained by further blending an epoxy resin having a biphenyl novolac structure (E) with a phosphorus-containing compound as the flame retardant (D) in the curable resin composition of the present invention .

It has also been found that a curable resin composition having excellent hiding properties can be obtained by making the curable resin composition of the present invention black. In particular, it was found that by containing a black colorant and a colorant other than black, a curable resin composition excellent in hiding property can be obtained even though resolution is improved by making it black.

Hereinafter, each component will be described in detail.

[(A) Resin containing a carboxyl group]

As the carboxyl group-containing resin (A), a resin containing a known carboxyl group can be used. The resin composition can be made alkali-developable by the presence of a carboxyl group. It is preferable that the curable resin composition of the present invention has an ethylenically unsaturated bond in the molecule in addition to the carboxyl group in view of the photocurable property and the resistance to development, May be used as a component. When the resin of the component (A) does not have an ethylenically unsaturated bond, it is necessary to use a compound (photopolymerizable monomer) having at least one ethylenic unsaturated group in the molecule in order to render the composition photocurable. As the ethylenically unsaturated double bond, those derived from acrylic acid or methacrylic acid or derivatives thereof are preferable.

Specific examples of the carboxyl group-containing resin that can be used in the curable resin composition of the present invention include the following compounds (any of oligomers and polymers) listed below.

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

(2) a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate and an aromatic diisocyanate, a dialcohol compound containing a carboxyl group such as dimethylolpropionic acid and dimethylolbutanoic acid, and a polycarbonate polyol, a polyether polyol Containing urethane resin obtained by a mid-portion reaction of a diol compound such as a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group .

(3) a process for producing a polyisocyanate compound by reacting a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate with a polycarbonate-based polyol, a polyether-based polyol, A-type alkylene oxide adduct diol, a terminal carboxyl group-containing urethane resin formed by reacting an acid anhydride with a terminal of a urethane resin by a heavy-chain reaction of a diol compound such as a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(4) a bifunctional epoxy resin such as a bisphenol A type epoxy resin, a hydrogenated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a beacilene type epoxy resin and a biphenol type epoxy resin (Meth) acrylate or a partial acid anhydride thereof, a carboxyl group-containing dialcohol compound and a diol compound.

(5) In the synthesis of the resin of the above (2) or (4), a compound having one hydroxyl group and at least one (meth) acryloyl group in the molecule such as hydroxyalkyl (meth) Meth) acrylated carboxyl group-containing urethane resin.

(6) In the synthesis of the resin of the above (2) or (4), it is preferable to use a mixture of isophorone diisocyanate and pentaerythritol triacrylate, such as equimolar reactants, having one isocyanate group and at least one (meth) acryloyl group in the molecule (Meth) acrylate obtained by adding a compound to a carboxyl group-containing urethane resin.

(7) reacting a polyfunctional (solid) epoxy resin as described below with (meth) acrylic acid, adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride to the hydroxyl groups present in the side chain Photosensitive carboxyl group-containing resin.

(8) A photosensitive carboxyl group-containing resin obtained by reacting a polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of a bifunctional (epoxy) epoxy resin with epichlorohydrin, and reacting (meth) acrylic acid with the resulting hydroxyl group added with a dibasic acid anhydride.

(9) A carboxyl group-containing polyester resin in which a dicarboxylic acid is reacted with a multifunctional oxetane resin as described below, and dibasic acid anhydride is added to the resulting primary hydroxyl group.

(10) A process for producing a polyoxyalkylene compound, which comprises reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in a molecule with an alkylene oxide such as ethylene oxide or propylene oxide with a monocarboxylic acid containing an unsaturated group, A carboxyl group-containing photosensitive resin obtained by reacting an anhydride.

(11) A process for producing a reaction product comprising reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in a molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate, with a monocarboxylic acid containing an unsaturated group, A carboxyl group-containing photosensitive resin.

(12) A process for producing an epoxy compound having a plurality of epoxy groups in a molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and a compound having an unsaturated (meth) Containing monocarboxylic acid, and reacting the alcoholic hydroxyl group of the obtained reaction product with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic acid anhydride, pyromellitic acid anhydride or adipic acid, Photosensitive resin.

(13) The resin composition as described in any one of (1) to (12) above, wherein one epoxy group in the molecule such as glycidyl (meth) acrylate and? -Methyl glycidyl (meth) A compound having a diol group is further added to the photosensitive resin composition.

Since the carboxyl group-containing resin as described above has a large number of carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.

The acid value of the carboxyl group-containing resin is preferably in the range of 20 to 200 mg KOH / g, and more preferably in the range of 40 to 150 mg KOH / g. When the acid value of the carboxyl group-containing resin is 20 mgKOH / g or more, the adhesion of the coating film becomes good, and the alkali development becomes good. On the other hand, in the case where the acid value is 200 mgKOH / g or less, dissolution of the exposed portion by the developer can be suppressed, so that the line is thinned more than necessary or the dissolution and peeling in the developer without distinction between the exposed portion and the non- Thus, the resist pattern can be satisfactorily drawn.

The weight average molecular weight of the carboxyl group-containing resin used in the present invention varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is 2,000 or more, the tackfree performance is good, the humidity resistance of the coated film after exposure is good, the film reduction during development can be suppressed, and the decrease in resolution can be suppressed. On the other hand, when the weight average molecular weight is 150,000 or less, developability is good and storage stability is excellent.

Among the above-mentioned carboxyl group-containing resins, the polyfunctional epoxy resin used for the synthesis of the resin is preferably a bisphenol A structure, a bisphenol F structure, a biphenol structure, a biphenol novolac structure, a biscensilene structure, a biphenyl novolac structure, and a urethane structure , Or a hydrogenated compound thereof, is preferred from the viewpoints of low flexural and flexural resistance of the obtained cured product.

Of the carboxyl group-containing resins having a urethane structure, carboxyl group-containing urethane resins obtained by using a diisocyanate having an isocyanate group (including a diisocyanate) not having an isocyanate group directly bonded to a benzene ring are free from yellowing, And is low in ultraviolet ray absorption. Therefore, when the composition is an alkali developable composition, it has a good resolution and is preferable.

In the present specification, (meth) acrylate is a generic term for acrylate, methacrylate, and mixtures thereof, and the same applies to other similar expressions.

The amount of the carboxyl group-containing resin (A) is preferably 5 to 60 mass%, more preferably 10 to 60 mass%, more preferably 20 to 60 mass%, and particularly preferably 30 To 50% by mass. When it is from 5 to 60% by mass, the coating film strength is good, the viscosity of the composition is appropriate, and the coatability and the like can be improved.

[(B) Photopolymerization initiator]

As the photopolymerization initiator (B), known photopolymerization initiators can be used. For example, oxime ester-based photopolymerization initiators having an oxime ester group,? -Aminoacetophenone-based photopolymerization initiators and acylphosphine oxide- Is preferably used as the photopolymerization initiator.

Examples of the oxime ester-based photopolymerization initiator include commercially available products such as CGI-325, Irgacure OXE01, Irgacure OXE02, AD-1919 and NCI-831 manufactured by BASF Japan Co., have. Further, a photopolymerization initiator system having two oxime ester groups in the molecule can be preferably used, and specific examples thereof include oxime ester compounds having a carbazole structure represented by the following general formula.

(Wherein 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, an alkoxy group having 1 to 8 carbon atoms, An alkyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an amino group, an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group having 1 to 8 carbon atoms) Y and Z each represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen group, a phenyl group, a phenyl group (an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 8 carbon atoms, An alkyl group having 1 to 8 carbon atoms or a dialkylamino group), a naphthyl group (an alkyl group having 1 to 17 carbon atoms, an alkyl group having 1 to 8 carbon atoms, An alkyl group having 1 to 8 carbon atoms, or an alkylamino group having 1 to 8 carbon atoms or a dialkylamino group), anthryl group, pyridyl group, benzofuryl group or benzothienyl group, Ar is a bond, To 10 carbon atoms, such as alkylene, vinylene, phenylene, biphenylene, pyridylene, naphthylene, thiophene, anthrylene, thienylene, furylene, 2,5- -Diyl, 4,2'-styrene-diyl, and n is 0 or an integer of 1)

In particular, it is preferable that X and Y are each a methyl group or an ethyl group, Z is a methyl group or a phenyl group, n is 0, Ar is a bond, or phenylene, naphthylene, thiophene or thienylene.

As preferable carbazole oxime ester compounds, there may be mentioned compounds which can be represented by the following general formula.

(Wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms or a phenyl group which may be substituted with a nitro group, a halogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² represents an alkyl group having 1 to 4 carbon atoms , An alkoxy group having 1 to 4 carbon atoms, or a phenyl group optionally substituted with an alkyl group or an alkoxy group having 1 to 4 carbon atoms, R ³ may be connected with an oxygen atom or a sulfur atom, An alkyl group of 1 to 20 carbon atoms which may be substituted, or a benzyl group which may be substituted with an alkoxy group of 1 to 4 carbon atoms, R ⁴ represents an acyl group represented by a nitro group or XC (= O) - , X represents an aryl group, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula, which may be substituted with an alkyl group having 1 to 4 carbon atoms.

)

)

In addition, Japanese Patent Application Laid-Open Nos. 2004-359639, 2005-097141, 2005-220097, 2006-160634, 2008-094770 A carbazole oxime ester compound described in Japanese Patent Application Laid-Open No. 2008-509967, Japanese Patent Publication No. 2009-040762, and Japanese Patent Laid-Open No. 2011-80036.

The blending amount of such oxime ester-based photopolymerization initiator is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A). When the amount is 0.01 part by mass or more, the photocurability is good and the coating film properties such as chemical resistance are improved. On the other hand, when the amount is 5 parts by mass or less, the light absorption at the surface of the coating film becomes good and the deep portion curing property is improved. More preferably 0.5 to 3 parts by mass.

Specific examples of the? -aminoacetophenone-based photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1,2-benzyl- -1- [4- (4-morpholinyl) phenyl] -1- [2- (dimethylamino) -Butanone, N, N-dimethylaminoacetophenone, and the like. Commercially available products include Irgacure 907, Irgacure 369 and Irgacure 379 manufactured by BASF Japan.

Specific examples of the acylphosphine oxide-based photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6- Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like. Commercially available products include Lucirin TPO manufactured by BASF Japan, Irgacure 819 manufactured by BASF Japan, and the like.

It is preferable that the blending amount of the? -Aminoacetophenone-based photopolymerization initiator and the acylphosphine oxide-based photopolymerization initiator is 0.01 to 15 parts by mass relative to 100 parts by mass of the carboxyl group-containing resin (A). When the amount is 0.01 parts by mass or more, the photocurability is good and deterioration of coating film properties such as chemical resistance can be suppressed. On the other hand, when the amount is less than 15 parts by mass, outgas is reduced and the light absorption on the surface of the coating film becomes better and the deep portion curing property is improved. More preferably 0.5 to 10 parts by mass.

In addition to the photopolymerization initiator, photoinitiators and sensitizers may be used. Examples of the photopolymerization initiator, photoinitiator and sensitizer that can be preferably used in the photosensitive resin composition include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, Xanthene compounds and the like.

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

Specific examples of the acetophenone compound include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone. have.

Specific examples of the anthraquinone compound include 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone, and 1-chloro anthraquinone.

Specific examples of the thioxanthone compound include 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone. .

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

Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenylsulfide, 4-benzoyl-4'-methyldiphenylsulfide, 4-benzoyl- -4'-propyldiphenyl sulfide, and the like.

Specific examples of the tertiary amine compound include ethanolamine compounds and compounds having a dialkylaminobenzene structure such as 4,4'-dimethylaminobenzophenone (Nissokyure MABP manufactured by Nippon Soda Co., Ltd.), 4, (Diethylamino) -4-methyl-2H-1-benzopyran-2-one (7-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Dimethylaminobenzoate (Kayacure EPA, manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (manufactured by International Bio-Synthesis Co., Ltd.) (Quantacure DMB), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthesis Inc.), p-dimethylaminobenzoic acid isoamylethylester (Kayacure manufactured by Nippon Kayaku Co., DMBI), 4-dimethylaminobenzoic acid 2-ethylhexyl There may be mentioned solrol (Esolol) 507) or the like (Van Dyk), manufactured.

Of these, thioxanthone compounds and tertiary amine compounds are preferred. Particularly, it is preferable that a thioxanthone compound is contained in view of the deep curing property. Among them, it is preferable to include thioxanthone compounds such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone .

The amount of such a thioxanthone compound is preferably 20 parts by mass or less based on 100 parts by mass of the carboxyl-containing resin (A). When the compounding amount of the thioxanthone compound is 20 parts by mass or less, the thick film curing property is good and the cost of the product is reduced. More preferably 10 parts by mass or less.

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable. Among them, a dialkylaminobenzophenone compound, a dialkylamino group-containing coumarin compound having a maximum absorption wavelength in the range of 350 to 450 nm, Is particularly preferable.

As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because it has low toxicity. Since the dialkylamino group-containing coumarin compound has a maximum absorption wavelength of 350 to 410 nm in the ultraviolet ray region, it is possible to provide a colored cured coating which has little coloration and reflects the color of the coloring pigment itself using a colorless pigment as well as a colorless transparent cured coating It becomes possible. Particularly, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable in that it exhibits an excellent increase / decrease effect on laser light having a wavelength of 400 to 410 nm.

The amount of such a tertiary amine compound is preferably 0.1 to 20 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A). When the compounding amount of the tertiary amine compound is 0.1 part by mass or more, a sufficient increase or decrease effect can be obtained. On the other hand, when the amount is 20 parts by mass or less, the light absorption at the surface of the coating film by the tertiary amine compound is reduced, and the deep portion curing property is improved. More preferably 0.1 to 10 parts by mass.

These photopolymerization initiators, photoinitiator, and sensitizer may be used alone or in admixture of two or more.

It is preferable that the total amount of the photopolymerization initiator, photoinitiator and sensitizer is 35 parts by mass or less based on 100 parts by mass of the carboxyl-containing resin (A). When the amount is 35 parts by mass or less, the lowering of the deep portion curing property due to the light absorption can be suppressed.

In addition, the above-mentioned photopolymerization initiator, photoinitiator, and sensitizer absorb specific wavelengths, and in some cases, the sensitivity is lowered and may function as an ultraviolet absorber. However, they are not used for the purpose of improving the sensitivity of the composition. It is possible to increase the photoreactivity of the surface by absorbing light of a specific wavelength as needed and to change the line shape and the opening of the resist to vertical, tapered, and reverse tapered shapes, and improve the processing accuracy of the line width and the opening diameter have.

[(C) Organic filler whose surface is coated with silica]

The organic filler in which the (C) surface is coated with silica is fine particles containing a polymer and can be used as long as the surface is covered with silica. The method of silica coating is not particularly limited. The thickness of the silica coating may be such that the presence of silicon (Si) can be confirmed by energy dispersive X-ray analysis (EDX). The average particle diameter of the organic filler is not particularly limited and may be any particle diameter that can be used as a filler. The average particle diameter is preferably from 0.1 to 30 μm, more preferably from 0.1 to 10 μm, as an average particle diameter obtained from the particle size distribution measurement result of the volume average measured by the laser diffraction particle size distribution measuring apparatus.

The amount of the organic filler in which the surface of (C) is coated with silica is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.

Examples of the polymer constituting the organic filler include a polyester polymer, a polyurethane polymer, a polyester urethane polymer, a polyamide polymer, a polyester amide polymer, an acrylic polymer, a cellulosic polymer, a polylactic acid polymer, A clock polymer, and the like. It may also be a hydroxyl group-containing elastomer or other elastomer. For example, a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyester amide elastomer, an acrylic elastomer, an olefin elastomer, an epoxy-containing polybutadiene elastomer, . A resin obtained by modifying an epoxy group of some or all of epoxy resins having various skeletons with both terminal carboxylic acid modified butadiene-acrylonitrile rubbers can also be used. These polymers may be used singly or as a mixture of two or more kinds. Of these polymers, polyurethane polymers are preferable, and urethane resins are more preferable.

In the curable resin composition of the present invention, a filler other than the organic filler in which the (C) surface of the (C) surface is coated with silica may be compounded, if necessary, in order to increase the physical strength and the like of the resulting cured product. As such a filler, an inorganic filler for known purpose can be used, and barium sulfate, spherical silica and talc are particularly preferably used. For the purpose of imparting flame retardancy, aluminum hydroxide, magnesium hydroxide, hydrotalcites, and boehmite can also be used. In addition, a compound having at least one ethylenic unsaturated group, or NANOCRYL (trade name) XP 0396, XP 0596, XP 0733, manufactured by Hanse-Chemie Co., Ltd. in which nanosilica is dispersed in the polyfunctional epoxy resin, XP 0516, XP 0525, XP 0314 (All product class name) NANOPOX (product name) manufactured by NANHANS-CAMISA Co., ) Can also be used. These may be used singly or in combination of two or more.

The amount of the filler is preferably 500 parts by mass or less, more preferably 0.1 to 300 parts by mass, particularly preferably 0.1 to 150 parts by mass, based on 100 parts by mass of the carboxyl-containing resin (A). When the compounding amount of the filler is 500 parts by mass or less, the viscosity of the curable resin composition does not become excessively high, the printability is good, and the cured product becomes hard to be decomposed.

((D) flame retardant)

In the curable resin composition of the present invention, it is preferable to use a conventionally known flame retardant for the purpose of improving the flame retardancy of the resulting cured product. From the viewpoint of the environment, a halogen-free flame retardant is preferable. As the flame retardant, for example, aluminum hydroxide, magnesium hydroxide, hydrotalcites and boehmite which are inorganic fillers imparting flame retardancy to the phosphorus-containing compound or the curable resin composition may be blended. Among the flame retardants, phosphorus-containing compounds are preferred. The flame retardant may be used alone, or two or more flame retardants may be used in combination.

The phosphorus-containing compound includes those known as organophosphorus flame retardants. Among such organophosphorus flame retardants, preferred are phosphoric acid esters and condensed phosphoric acid esters, phosphorus-containing (meth) acrylates, phosphorus-containing compounds having phenolic hydroxyl groups, cyclic phosphazene compounds, phosphazene oligomers, phosphinic acid metal salts, And a compound represented by the formula (I).

(Wherein R ⁵ , R ⁶ and R ⁷ each independently represent a substituent other than a halogen atom)

In the general formula (I), R ⁵ and R ⁶ are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ⁷ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may be substituted with a cyano group Dihydroxyphenyl group or a 3,5-di-t-butyl-4-hydroxyphenyl group, but is not limited thereto.

Examples of commercially available products of the phosphorus-containing compounds represented by the above general formula (I) include HCA, SANKO-220, M-ESTER and HCA-HQ (all trade names of Sanko).

The phosphorus-containing (meth) acrylate is preferably a compound having a phosphorus element and having a plurality of (meth) acryloyl groups in the molecule. Specifically, R ⁵ and R ⁶ in the general formula (I) Atom, and R < ⁷ > is a (meth) acrylate derivative. Generally, it can be synthesized by Michael addition reaction of 9,10-dihydro-9-oxa-10-phosphapenanthrene-10-oxide with a polyfunctional (meth) acrylate monomer for known purpose.

Examples of the (meth) acrylate monomers include diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; Polyhydric alcohols such as hexanediol, trimethylol propane, pentaerythritol, dipentaerythritol and tris-hydroxyethylisocyanurate, or ethylene oxide adducts, propylene oxide adducts or caprolactone adducts thereof Polyfunctional acrylates; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; And polyhydric acrylates of glycidyl ethers such as urethane acrylates, glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate of the polyhydric alcohols ; And melamine acrylate, and at least one of the respective methacrylates corresponding to the acrylate.

The phosphorus-containing compound having a phenolic hydroxyl group has high hydrophobicity and heat resistance, does not deteriorate in electrical characteristics due to hydrolysis, and has high solder heat resistance. When the epoxy resin in the thermosetting resin is used as a preferred combination, since the epoxy resin is introduced into the network in reaction with the epoxy group, there is an advantage that the resin does not bleed out after curing. Among the phosphorus-containing compounds having a phenolic hydroxyl group, those represented by the general formula (I) in which R ⁷ is a phenyl group substituted with a hydroxyl group are mentioned. Commercially available products include HCA-HQ manufactured by Sanko Corporation.

The phosphorus-containing compound, which is an oligomer or a polymer, has an advantage that the decrease in the bending property is small due to the influence of the alkyl chain and the molecular weight is large, so that there is no bleeding out after curing. Commercial products include M-Ester-HP manufactured by Sanko Co., Ltd. and Byron 337 manufactured by Toyobo Co., Ltd.

As the phosphazene oligomer, a phenoxyphosphazene compound is effective, and a substituted or unsubstituted phenoxyphosphazene oligomer or a cyclic compound of a trimer, a tetramer, or a pentamer, and a liquid or a solid powder can be used. have. Examples of commercially available products include FP-100, FP-300, and FP-390 manufactured by Fushimi Fine Chemical Co., Among them, phenoxyphosphazene oligomers substituted with an alkyl group or a polar group such as a hydroxyl group or a cyano group have high solubility in a carboxyl group-containing resin, and even when added in a large amount, there is no problem such as recrystallization.

Also, as other phosphazene oligomers, at least one (meth) acrylate group in a molecule obtained by reacting an acrylate compound with at least one of phosphorus-containing dicarboxylic acid and anhydride thereof represented by the following general formula (II) ≪ / RTI >

Examples of the hydrocarbon group having 1 to 6 carbon atoms represented by R ⁸ and R ⁹ in the general formula (II) include an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, a cycloalkyl group , And a phenyl group. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, Examples of the alkenyl group having 1 to 6 carbon atoms, such as an allyl group, include a vinyl group, an allyl group, a 3-butenyl group, an isobutenyl group, a 4-pentenyl group and a 5-hexenyl group. The hydrocarbon group having 1 to 6 carbon atoms may be branched or substituted.

Examples of the phosphorus-containing dicarboxylic acid or its anhydride include compounds obtained by reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide with itaconic acid and anhydrides thereof have.

As the acrylate compound, an acrylate compound having a functional group capable of reacting with the carboxyl group or the carboxylic acid anhydride of the dicarboxylic acid or an anhydride thereof is preferable. The acrylate moiety can be added by such a reaction. Such an acrylate compound may be a monofunctional acrylate containing one (meth) acrylate group in the molecule or a polyfunctional acrylate containing two or more (meth) acrylate groups in the molecule. Examples of the functional group include an epoxy group, a hydroxyl group and an amino group. Examples of the acrylate compound having an epoxy group include glycidyl (meth) acrylate and 2-methyl-2,3-epoxypropyl (meth) acrylate. Examples of the acrylate compound having a hydroxyl group include 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate. Examples of the acrylate compound having an amino group include diethylaminoethyl acrylate and the like. Of these functional groups, an epoxy group and a hydroxyl group are more preferable.

The reaction method to be added with the functional group may be a known reaction method.

Examples of the phosphazene oligomer include mono- or bifunctional phosphazene oligomers obtained by reacting a phosphorus-containing dicarboxylic acid represented by the general formula (II) synthesized as in the above example with glycidyl methacrylate, And bifunctional phosphazene oligomers obtained by reacting phosphorus-containing dicarboxylic acid with hydroxy (meth) acrylate and, if necessary, dialcohol.

The amount of the acrylate compound to be added to the phosphorus-containing dicarboxylic acid or anhydride thereof represented by the general formula (II) is not particularly limited, but the phosphorus concentration of the phosphazene oligomer may be in the range of 2% to 7% To prepare an acrylate compound.

By using the phosphorus-containing dicarboxylic acid or its anhydride represented by the above-mentioned general formula (II), it is possible to obtain a phosphazene oligomer easily acrylated at both terminals. By using the terminal acrylated phosphazene oligomer thus obtained, a flame retardant curable resin composition excellent in flexibility and low warpage and capable of obtaining a flame retardant film free from bleeding out at high temperature pressing can be obtained have.

The phosphazene oligomer is preferably a bifunctional phosphorus-containing acrylate from the viewpoints of flexibility and low bendability. When the phosphazene oligomer is bifunctional, the heat resistance becomes good and the lowering of the flexibility can be suppressed.

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

Further, by using the phosphinic acid metal salt, the flame retardancy can be improved without impairing the flexibility of the cured coating. By using the phosphinic acid metal salt having excellent heat resistance, it is possible to suppress bleeding out of the flame retardant in thermal press at the time of mounting.

Specific examples of the phosphinic acid constituting the phosphinic acid metal salt include phosphinic acid, dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methanedi (methylphosphinic acid) (Dimethylphosphinic acid), methylphenylphosphinic acid, phenylphosphinic acid, diphenylphosphinic acid, and mixtures thereof.

Examples of the metal component constituting the phosphinate include calcium, magnesium, aluminum, zinc, bismuth, manganese, sodium and potassium. Preferably, it is calcium, magnesium, aluminum, or zinc.

Commercially available products of phosphinic acid metal salts include Exolit OP 930 and Exolit OP 935 manufactured by Clariant.

The phosphorus-containing compound may be used singly or in combination of two or more. The compounding amount of the phosphorus-containing compound is 5 to 150 parts by mass, preferably 10 to 80 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A). When the amount is 150 parts by mass or less, the cured film obtained has good bending properties and the like.

The aluminum hydroxide may be untreated or may be a surface treated with a silane coupling agent having a vinyl group or an epoxy group at the end, stearic acid, oleic acid, phosphoric acid ester, or the like. Commercially available products of aluminum hydroxide include Higilit H42M, Higilit H42S, Higilit H42T, Higilit H42ST-V, B1403, B1403ST and B1403T manufactured by Nippon Keiki Kogyo Co., Ltd., manufactured by Showa Denko K.

The magnesium hydroxide may be a natural product or a synthetic product, or may be an untreated surface, a surface treated with a silane coupling agent having a vinyl group or an epoxy group at the end, stearic acid, oleic acid, phosphoric acid ester or the like. Examples of commercially available products of magnesium hydroxide include Kisuma 5A, Kisma 5B, Kisma 5E, Kisma 5J, Kisma 5P, Kisuma 5L, Magnifin H5, Magnifin H7 , Magninfin H10, and the like.

The amount of the inorganic filler imparting flame retardancy such as aluminum hydroxide and magnesium hydroxide is preferably 500 parts by mass or less, more preferably 0.1 to 300 parts by mass, particularly preferably 100 parts by mass or less, based on 100 parts by mass of the carboxyl-containing resin (A) Is 0.1 to 150 parts by mass. When the compounding amount of the filler is 500 parts by mass or less, the viscosity of the curable resin composition does not become excessively high, the printability is good, and the cured product becomes hard to be decomposed.

((E) an epoxy resin having a biphenyl novolak structure)

In the present invention, the flame retardancy can be improved by containing an epoxy resin having a biphenyl novolak structure (E). As the epoxy resin having a biphenyl novolak structure (E), various conventionally known epoxy compounds having a biphenyl novolac structure and an epoxy group in the molecule can be used. Commercially available products include, for example, NC-3000-L, NC-3000, NC-3000-H and NC-3100 manufactured by Nippon Kayaku Co., The epoxy resin having the biphenyl novolak structure (E) may be used singly or in combination of two or more.

The blending amount of the epoxy resin having the biphenyl novolak structure (E) is preferably 5 to 100 parts by mass, more preferably 10 to 70 parts by mass, based on 100 parts by mass of the carboxyl group-containing resin (A) . When the amount is 5 parts by mass or more, sufficient flame retardancy can be imparted. On the other hand, when the amount is 100 parts by mass or less, low bending property and flexibility are improved.

Further, in order to further improve the heat resistance of the curable resin composition of the present invention, other thermosetting components other than the epoxy resin having the biphenyl novolak structure (E) may be used in combination. As the thermosetting component, known isocyanate compounds, block isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds and episulfide resins A thermosetting resin for public use can be used. Among them, a preferable thermosetting component is a thermosetting component having at least one of a plurality of cyclic ether groups and cyclic thioether groups in one molecule (hereinafter abbreviated as cyclic (thio) ether groups). These thermosetting components having a cyclic (thio) ether group are commercially available, and various properties can be given depending on the structure thereof.

The thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is a compound having in the molecule a plurality of cyclic ether groups or cyclic thioether groups of 3, 4 or 5-membered rings, or two or more kinds of groups, Namely, a compound having a plurality of epoxy groups, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having a plurality of thioether groups in the molecule, .

Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, epiclon 840 manufactured by DIC, Epiclon 850, Epiclon 1050, Epiclon 2055, DER317, DER331, DER661, DER664 manufactured by Dow Chemical Co., Sumi-epoxy ESA-011 and ESA-014 manufactured by Sumitomo Chemical Kagaku Kogyo Co., Bisphenol A type epoxy resin such as AER330, AER331, AER661, AER664 (all trade names) manufactured by Asahi Chemical Industry Co., Ltd., ELA-115, ELA-128; JERYL903 manufactured by Mitsubishi Chemical Corporation, Epiclon 152 manufactured by DIC Corporation, Epiclon 165, Epototo YDB-400, YDB-500 manufactured by Toko Kasei Co., DER542 manufactured by Dow Chemical Co., Brominated epoxy resin of Sumi-epoxy ESB-400, ESB-700, AER711 and AER714 manufactured by Asahi Chemical Industry Co., Ltd. (all trade names); JER152, jER154 manufactured by Mitsubishi Chemical Corporation, DEN431, DEN438 manufactured by Dow Chemical Company, Epiclon N-730 manufactured by DIC, Epiclon N-770, Epiclon N-865, EOCN-1025, EOCN-1020, EOCN-104S, RE-306 manufactured by Nippon Kayaku Co., Ltd., SUMI EPOXY ESCN-195X and ESCN-220 manufactured by Sumitomo Chemical Co., , Novolak type epoxy resins such as AERECN-235 and ECN-299 (all trade names) manufactured by Asahi Kasei; Bisphenol F type epoxy resin such as Epiclon 830 manufactured by DIC Corporation, jER 807 manufactured by Mitsubishi Kagaku Co., Ltd., Epototo YDF-170, YDF-175 and YDF-2004 manufactured by Tokto Kasei Co., Hydrogenated bisphenol A type epoxy resins such as Epototo ST-2004, ST-2007 and ST-3000 (trade name) manufactured by Tokuga Seisakusho; A glycidylamine type epoxy resin such as jER604 manufactured by Mitsubishi Kagaku Co., Ltd., Epitoto YH-434 manufactured by Toko Kasei Co., Ltd. and SUMI EPOX ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (all trade names) Hidanto dolphin epoxy resin; Alicyclic epoxy resins such as Celloxide 2021 and CY179 (all trade names) manufactured by Daicel Chemical Industries, Ltd.; A trihydroxyphenylmethane type epoxy resin such as YL-933 manufactured by Mitsubishi Chemical Corporation, T.E.N., EPPN-501, and EPPN-502 manufactured by Dow Chemical Co. (all trade names); Biscylenol-type or biphenol-type epoxy resins such as YL-6056, YX-4000 and YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation; Bisphenol S type epoxy resins such as EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Adeka Co., and EXA-1514 (trade name) manufactured by DIC Corporation; A bisphenol A novolak type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Corporation; Tetraphenylol ethane type epoxy resin such as jERYL-931 (all trade names) manufactured by Mitsubishi Chemical Corporation; A heterocyclic epoxy resin of TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); Diglycidyl phthalate resins such as Niche-like manufactured Bremer DGT; Tetraglycidylcylenoyl ethane resins such as ZX-1063 manufactured by Toko Chemical Co., Ltd.; Epoxy resin containing naphthalene group such as ESN-190, ESN-360 manufactured by Shin-Etsu Chemical Co., Ltd., HP-4032, EXA-4750 and EXA-4700 manufactured by DIC Corporation; Epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; flexible tough epoxy resin of EXA-4816, EXA-4822, EXA-4850 series; Glycidyl methacrylate copolymer-based epoxy resins such as Nicot-like manufactured CP-50S and CP-50M; And copolymerized epoxy resins of cyclohexylmaleimide and glycidyl methacrylate, but are not limited thereto. These epoxy resins may be used alone or in combination of two or more.

When another epoxy resin is used in addition to an epoxy resin having a biphenyl novolac structure, a bifunctional epoxy resin is preferable from the viewpoints of flexibility and low bending property, and a bifunctional epoxy resin is a powder epoxy resin, .

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [ Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, , Poly (p-hydroxystyrene), cardo type bisphenols, calixarene, calix resorcinarene, or a mixture of oxalic alcohol and novolak resin, poly And ether compounds of a resin having a hydroxyl group such as sesquioxane. Other examples include copolymers of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate.

Examples of the episulfide resin having a plurality of cyclic (thio) ether groups in the molecule include YL7000 (bisphenol A type episulfide resin) manufactured by Mitsubishi Chemical Corporation and YSLV-120TE manufactured by Dotogasei Co., An episulfide resin in which an oxygen atom of the epoxy group of the novolac epoxy resin is substituted with a sulfur atom can also be used by using a similar synthesis method.

The blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.3 to 2.5 equivalents, more preferably 0.5 to 2.0 equivalents based on 1 equivalent of the carboxyl group of the carboxyl group-containing resin (A) Range. When the compounding amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is 0.3 equivalent or more, the carboxyl group is hardly left in the cured coating, and heat resistance, alkali resistance, electrical insulation and the like are good. On the other hand, when the amount is 2.5 equivalents or less, a low molecular weight cyclic (thio) ether group hardly remains in the dry film, and the strength and the like of the cured film are good.

When a thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is used, it is preferable to contain a thermosetting catalyst. Examples of such thermosetting catalysts include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, Imidazole derivatives such as sol, 1-cyanoethyl-2-phenylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all the products of imidazole-based compounds) manufactured by Shikoku Chemicals, Inc., U-CAT ) 3503N, U-CAT3502T (all of the block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102 and U-CAT5002 (both bicyclic amidine compounds and salts thereof). But is not limited thereto. It is not limited to these, and any kind may be used as far as it accelerates the reaction between a thermal curing catalyst of an epoxy resin or an oxetane compound or a carboxyl group with at least one of an epoxy group and an oxetanyl group, It may be used. Further, it is also possible to use at least one selected from the group consisting of guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid Or an S-triazine derivative such as an adduct may be used. Preferably, a compound that also functions as such an adhesion-imparting agent is used in combination with the above-mentioned thermosetting catalyst.

The blending amount of these thermosetting catalysts is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass based on 100 parts by mass of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule in terms of solid content.

Examples of the amino resin include amino resins such as melamine derivatives and benzoguanamine derivatives. For example, methylolmelamine compounds, methylolbenzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. The alkoxymethylated melamine compound, the alkoxymethylated benzoguanamine compound, the alkoxymethylated glycoluril compound, and the alkoxymethylated urea compound may be used in combination with the respective methylolmelamine compounds, methylolbenzoguanamine compounds, methylolglycoluril compounds, and methylol urea compounds Methylol group into an alkoxymethyl group. The kind of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group. Particularly, a melamine derivative having a formalin concentration of 0.2% or less is desirable for human body and environment.

Commercially available products of the amino resin include, for example, Cymel 300, Copper 301, Copper 303, Copper 370, Copper 325, Copper 327, Copper 701, Copper Copper 266, Copper Copper 267, Copper Copper 238, Copper Copper 1141, Copper Copper Copper 202, 750, copper Mx-032, copper Mx-270, copper Mx-280 (manufactured by Mitsui Cyanamid Co., Ltd.) , Mx-290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM , Copper Mw-750LM (manufactured by Sanwa Chemical Co., Ltd.), and the like.

As the isocyanate compound, a polyisocyanate compound having a plurality of isocyanate groups in the molecule can be used. As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate or alicyclic polyisocyanate is used. Specific examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m - xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylene bis (cyclohexyl isocyanate) and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. Examples of the isocyanate compound adduct, buretate and isocyanurate include the isocyanate compounds mentioned above.

The blocked isocyanate group contained in the block isocyanate compound is a group in which an isocyanate group is protected by a reaction with a blocking agent and is temporarily inactivated. When heated to a predetermined temperature, the block agent dissociates to produce an isocyanate group.

As the block isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate block agent is used. Examples of the isocyanate compound capable of reacting with the block agent include isocyanurate type, buret type, and adduct type. Examples of the isocyanate compound used for synthesizing the block isocyanate compound include an aromatic polyisocyanate, an aliphatic polyisocyanate or an alicyclic polyisocyanate. Specific examples of the aromatic polyisocyanate, the aliphatic polyisocyanate and the alicyclic polyisocyanate include the compounds exemplified above.

Examples of the isocyanate block agent include phenolic block agents such as phenol, cresol, xylenol, chlorophenol, and ethylphenol; lactam-based blocking agents such as ε-caprolactam, δ-pareolactam, γ-butyrolactam and β-propiolactam; Active methylene blockers such as ethyl acetoacetate and acetylacetone; But are not limited to, methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, Alcohol-based blocking agents such as butyl acetate, diacetone alcohol, methyl lactate and ethyl lactate; Oxime-based blocking agents such as formaldehyde scavengers, acetal aldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, and cyclohexane oxime; Mercaptan-based blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methyl thiophenol and ethyl thiophenol; Acid amide type block agents such as acetic acid amide, benzamide and the like; Imide block agents such as succinic acid imide and maleic acid imide; Amine-based blocking agents such as xylidine, aniline, butylamine, and dibutylamine; Imidazole-based blocking agents such as imidazole and 2-ethylimidazole; Imine blockers such as methylene imine and propylene imine, and the like.

The block isocyanate compound may be a commercially available one, for example, Sumidor BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117 B-830, B-830 (trade name, manufactured by Nippon Polyurethane Industry Co., Ltd.), Desmotam 2170, Desmoterm 2265 (manufactured by Sumitomo Bayer Urethane Co., TPA-B80E, 17B-60PX, and E402-B80T (manufactured by Asahi Chemical Industry Co., Ltd., trade name; product of Mitsui Takeda Chemical Co., Ltd.), B- Trade name). Further, SMILDIR BL-3175 and BL-4265 are obtained by using methyl ethyl oxime as a block agent.

The blending amount of the polyisocyanate compound or the block isocyanate compound is preferably 1 to 100 parts by mass, more preferably 2 to 70 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A) in terms of solid content. When the blending amount is 1 part by mass or more, sufficient toughness of the coating film is obtained. On the other hand, when the amount is 100 parts by mass or less, the storage stability is good.

In the curable resin composition of the present invention, an urethane formation catalyst may be added to accelerate the curing reaction of the hydroxyl group, the carboxyl group and the isocyanate group. As the urethanization catalyst, it is preferable to use at least one urethane-forming catalyst selected from the group consisting of tin catalyst, metal chloride, metal acetylacetonate salt, metal sulfate, amine compound and amine salt.

Examples of the tin catalyst include organic tin compounds such as stannous octoate and dibutyltin dilaurate, and inorganic tin compounds.

Examples of the metal chloride include chloride of a metal selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al. Examples of the metal chloride include divalent cobalt chloride, .

The metal acetylacetonate salt is an acetylacetonate salt of a metal selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu and Al and is, for example, cobalt acetylacetonate, nickel acetylacetonate, Nate and so on.

Examples of the metal sulfate include sulfate of a metal selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu and Al, and copper sulfate, for example.

Examples of the amine compound include triethylenediamine, N, N, N ', N'-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) , N ", N" -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholonodiethylether, N-methylimidazole, dimethylamino Pyridine, triazine, N'- (2-hydroxyethyl) -N, N, N'-trimethyl- bis (2- aminoethyl) ether, N, N-dimethylhexanolamine, N, (2-hydroxyethyl) -N, N ', N ", N" -tetramethyldiethylenes such as N, N, N, N'-trimethyl-N '- (2-hydroxyethyl) -N, N' (N, N-dimethylaminopropyl) amine, bis (N, N-dimethylaminopropyl) isopropane Aminoquinuclidine, 4-aminoquinuclidine, 2-quinuclidinol, 3-quinuclidinol, 4-quinuclidinol, 1- (2'-hydroxy Propyl imidazole, 1- (2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imidazole, 1- Imidazole, 1- (2'-hydroxypropyl) -2-methylimidazole, 1- (3'-aminopropyl) imidazole, 1- , N, N-dimethylaminopropyl-N '- (2-hydroxyethyl) imidazole, 1- (3'- (2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ', N'-bis (2-hydroxypropyl) amine, (2-hydroxyethyl) amine, N, N-dimethylaminoethyl-N ', N'-bis (2-hydroxypropyl) amine, melamine and At least one of benzoguanamine, Can.

Examples of the amine salt include organic acid salt-based amine salts such as DBU (1,8-diazabicyclo [5.4.0] undecene-7).

The blending amount of the urethanization catalyst is preferably 0.01 to 20 parts by mass, more preferably 0.5 to 10.0 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A) in terms of solid content.

(coloring agent)

The curable resin composition of the present invention may contain a colorant. As the colorant, conventionally known coloring agents such as red, blue, green, yellow, purple, orange, green, white and black may be used, and any of pigments, dyes and pigments may be used. Specifically, a color index (issued by C.I .; The Society of Dyers and Colors) is appended. However, it is preferable that the colorant is a halogen-free colorant from the viewpoint of environmental load reduction and human influence.

Red colorant:

Examples of the red colorant include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. And the same color index number is attached.

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;

Disazo system: Pigment Red 37, 38, 41;

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 pigments: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208;

Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224, Pigment Red 174, Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, ;

Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272;

Pigment Red 220, Pigment Red 144, Pigment Red 166, Pigment Red 214, Pigment Red 220, Pigment Red 221, Pigment Red 242;

Anthraquinone series: Pigment Red 168, Pigment Red 177, Pigment Red 216, Solvent Red 149, Solvent Red 150, Solvent Red 52, Solvent Red 207;

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

Blue colorant:

Examples of the blue colorant include a phthalocyanine type and anthraquinone type, and a pigment type is a compound classified as a pigment. Specifically, the compound has a color index number as described below.

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, Blue 60;

Dyes: 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 Blue 70 Etc. may be used. In addition to the above, metal substituted or unsubstituted phthalocyanine compounds may also be used.

Green colorant:

Examples of the green colorant include phthalocyanine type, anthraquinone type and perylene type. 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, metal substituted or unsubstituted phthalocyanine compounds may also be used.

Yellow colorant:

Examples of the yellow colorant include a monoazo system, a disazo system, a condensed azo system, a benzimidazolone system, an isoindolinone system, and an anthraquinone system, and specific examples include the following colorants.

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;

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

Condensation azo pigments: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180;

Benzimidazolone pigments: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181;

Isoindolinone pigments: Pigment Yellow 110, Pigment Yellow 109, Pigment Yellow 139, Pigment Yellow 179, Pigment Yellow 185;

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

Specific examples of the purple colorant, orange colorant, and coloring agent include Pigment Violet 19, 23, 29, 32, 36, 38, 42; Solvent violet 13, 36; C.I. Pigment Orange 1, C.I. Pigment Orange 5, C.I. Pigment Orange 13, C.I. Pigment Orange 14, C.I. Pigment Orange 16, C.I. Pigment Orange 17, C.I. Pigment Orange 24, C.I. Pigment Orange 34, C.I. Pigment Orange 36, C.I. Pigment Orange 38, C.I. Pigment Orange 40, C.I. Pigment Orange 43, C.I. Pigment Orange 46, C.I. Pigment Orange 49, C.I. Pigment Orange 51, C.I. Pigment Orange 61, C.I. Pigment Orange 63, C.I. Pigment Orange 64, C.I. Pigment Orange 71, C.I. Pigment Orange 73; C.I. Pigment Brown 23, C.I. Pigment Brown 25 and the like.

White colorant:

As a white colorant, C.I. Zinc oxide represented by Pigment White 4, C.I. Titanium oxide represented by Pigment White 6, C.I. Pigments such as TR-600, TR-700, TR-750, and TR-840 manufactured by Fuji Titanium Corporation are particularly preferred because they are tin oxide, in view of tinctorial strength and non-toxicity. CR-60, CR-90, CR-97, KR-270, KR-310 and KR-60 manufactured by Titan Kogyo Co., TA-300 manufactured by Fuji Titanium Corporation, TA-300, TA-500, manufactured by Ishihara Sangyo Co., Ltd., A100 and A220 manufactured by Titan Kogyo Co., Ltd., KA-15, KA-20 and KA -35, KA-90, and the like.

Black colorant:

As the black colorant, C.I. Pigment Black 6, 7, 9 and 18, etc., C.I. Pigment Black 8, 10, etc., C.I. Pigment Black 11, 12 and 27, for example: iron oxide of KN-370 manufactured by Toda Kogyo Co., Ltd., titanium black of 13M manufactured by Mitsubishi Materials Corporation, C.I. Pigment Black 20, etc., and C.I. Pigment Black 13, 25 and 29, and the like. Pigment Black 15 and 28, and the like. Pigment Black 14 and 26, etc., C.I. Antimony oxide pigments represented by Pigment Black 23 and the like, C.I. Pigment Black 30 and the like, nickel oxide-based pigments represented by C.I. Pigment Blend pigments represented by Pigment Black 31 and 32, and molybdenum sulfide or bismuth sulfide are also preferable pigments. These pigments may be used alone or in appropriate combination. M-40, M-45, M-50, MA-8, and MA-100, and also the perylene pigments are low-halogenated pigments among organic pigments. Valid.

The colorant may be used alone or in combination of two or more. The blending amount of the colorant is not particularly limited, but it is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass based on 100 parts by mass of the (A) carboxyl group-containing resin. However, in the case of a white colorant, it is preferably 50 to 300 parts by mass, more preferably 70 to 250 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin.

As described above, by setting the curable resin composition of the present invention to black, a curable resin composition having excellent hiding properties can be obtained. For curing the curable resin composition of the present invention, the curable resin composition of the present invention may contain only a black colorant as a colorant. However, in order to obtain a curable resin composition having excellent hiding properties, And at least one coloring agent other than the black coloring agent. It is considered that exposure light for photo-curing is hardly absorbed by the coloring agent while having a sufficient blackness, and the photo-curing proceeds sufficiently so that the resolution is excellent. An example of the combination of the colorants is a combination of carbon black and at least one of a blue colorant and a red colorant, and preferably a combination of carbon black, a blue colorant and a red colorant.

In the case of blackening only with a black colorant, it is preferable to use a perylene black colorant from the viewpoint of resolution.

It may also be made black by combination of two or more kinds of coloring agents other than the black coloring agent.

Specific examples of the respective colorants used in the combination of two or more kinds of colorants other than the black colorant include those described earlier.

When the curable resin composition of the present invention is black, the L ^* value of the cured product by the color difference meter is preferably 30 or less with respect to the black color tone, and the wavelength of the dry coating film (film thickness 25 m) of the curable resin composition is 410 nm Is preferably 0.5 to 1.2 from the viewpoints of the hiding power and the resolution.

Here, the L ^* value is a value measured by the method described in the performance evaluation of the later embodiment.

The absorbance at a wavelength of 410 nm can be measured using an ultraviolet visible spectrophotometer and an integrating sphere apparatus. Further, in order to prevent the deviation of the absorbance due to the variation of the coating film thickness, the coating film thickness was changed into four steps, and a graph of the coating film thickness and the absorbance at 410 nm was prepared. The absorbance of the coating film can be calculated to obtain the respective absorbances.

Therefore, the compounding ratio of the above-mentioned colorant, the aforementioned components (A) to (C), and the blending ratio of other arbitrary components are appropriately adjusted in consideration of the L ^* value and the absorbance.

(Binder polymer)

For the purpose of improving the flexibility and tackiness of the resulting cured product, a publicly known binder polymer may be used in the curable resin composition of the present invention. The binder polymer is preferably a cellulose-based, polyester-based or phenoxy resin-based polymer. Examples of the cellulose-based polymer include cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) series manufactured by Eastman Chemical Company. Examples of the polyester-based polymer include Byron series manufactured by Toyo Bosa Company; bisphenol A, bisphenol F Phenoxy resins of these hydrogenated compounds are preferred.

The addition amount of the binder polymer is preferably 50 parts by mass or less, more preferably 1 to 30 parts by mass, and particularly preferably 5 to 30 parts by mass with respect to 100 parts by mass of the carboxyl group-containing resin (A). When the blending amount of the binder polymer is 50 parts by mass or less, the alkali developability of the curable resin composition becomes favorable, and the pesticide available time for development is not too short, which is preferable.

(Photopolymerizable monomer)

In the curable resin composition of the present invention, a compound (photopolymerizable monomer) having at least one ethylenic unsaturated group in the molecule can be used. The photopolymerizable monomer is photo-cured by irradiation with active energy rays to insolubilize or insolubilize the carboxyl-containing resin (A) in the aqueous alkaline solution.

(Meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy (meth) acrylate and the like can be used as the compound used as the photopolymerizable monomer in the present invention. Acrylate, and the like. Specific examples thereof include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethyl acrylamide, N-methylol acrylamide and N, N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; Polyhydric alcohols such as hexanediol, trimethylol propane, pentaerythritol, dipentaerythritol, and tris-hydroxyethylisocyanurate, or ethylene oxide adducts thereof, propylene oxide adducts, or? -Caprolactone adducts Polyhydric acrylates such as water; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; The present invention is not limited to the above, and acrylates and melamine acrylates obtained by directly acrylating a polyol such as a polyether polyol, a polycarbonate diol, a hydroxyl-terminated polybutadiene, or a polyester polyol, or a urethane acrylate through a diisocyanate, and And at least one of the respective methacrylates corresponding to the acrylate. As the urethane (meth) acrylate, a reaction product obtained by reacting an organic isocyanate, a (meth) acrylate monomer having at least one hydroxyl group in one molecule by a known method, or a reaction product obtained by reacting the above organic isocyanate, And reaction products obtained by reacting a polyol having two or more hydroxyl groups in a molecule with a (meth) acrylate monomer having a hydroxyl group by a known method.

In addition, an epoxy acrylate resin obtained by reacting a polyfunctional epoxy resin such as a cresol novolak type epoxy resin with acrylic acid, or a hydroxy acrylate such as pentaerythritol triacrylate and an isophorone diisocyanate Or the like may be used as the photopolymerizable monomer. The epoxy urethane acrylate compound may be prepared by reacting a half urethane compound of a diisocyanate, for example. Such an epoxy acrylate resin can improve the photocurability without lowering the composition of the touch and dry.

Particularly, in the present invention, polyhydric alcohols such as polyhydric alcohols or their polyhydric acrylates such as ethylene oxide adducts, propylene oxide adducts or? -Caprolactone adducts, and ethylene oxide adducts or propylene oxide adducts of phenols (Meth) acrylate-containing urethane oligomers can be preferably used from the viewpoints of low bending property and bending property.

The compounding amount of the compound having at least one ethylenic unsaturated group in the molecule used as the photopolymerizable monomer is preferably 5 to 100 parts by mass, more preferably 5 to 100 parts by mass, per 100 parts by mass of the carboxyl group-containing resin (A) To 70 parts by mass. When the blending amount is 5 parts by mass or more, the photocurability is good and the pattern formation is facilitated by the alkali development after irradiation with active energy rays. On the other hand, when it is 100 parts by mass or less, the solubility in an aqueous alkali solution becomes good and the coating film is prevented from being sagged.

(Coupling agent)

As the coupling agent used in the present invention, all conventionally known coupling agents can be used. As the coupling agent, an aluminate-based, titanate-based, zirconate-based, or silane-based coupling agent can be selected, and a silane coupling agent is most preferable.

Examples of the aluminate-based coupling agent include acetalalkoxyaluminum diisopropylate, aluminum diisopropoxymonoethylacetoacetate, aluminum trisethylacetoacetate, aluminum trisacetylacetonate, and the like.

Examples of the titanate-based coupling agent include isopropyltriisostearoyltitanate, isopropyltris (dioctylpyrophosphate) titanate, isopropyltri (N-aminoethylaminoethyl) titanate, tetraoctylbis (ditridecylphosphate ) Titanate, tetra (2-2-diallyloxymethyl-1-butyl) bis (ditridecylphosphate) titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) Nate and so on.

Examples of the zirconate coupling agent include zirconium tetrakis acetylacetonate, zirconium dibutoxybisacetylacetonate, zirconium tetrakis ethylacetoacetate, zirconium tributoxymonoethylacetoacetate, and zirconium tributoxyacetylacetonate. .

Examples of silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like.

The amount of the coupling agent to be added is preferably 0.05 to 5 parts by mass based on 100 parts by mass of the carboxyl group-containing resin (A). More preferably 0.1 to 3 parts by mass. When the addition amount is 0.05 parts by mass or more, a sufficient effect of wet dispersion on the organic or inorganic filler can be obtained. When the addition amount is 5 parts by mass or less, deterioration of the tack property can be suppressed.

(Elastomer)

The curable resin composition of the present invention can be blended with an elastomer for the purpose of imparting flexibility to the obtained cured product and improving the weakness of the cured product. Examples of the elastomer include a polyester elastomer, a polyurethane elastomer, a polyester urethane elastomer, a polyamide elastomer, a polyester amide elastomer, an acrylic elastomer and an olefin elastomer. A resin obtained by modifying an epoxy group of part or all of the epoxy resin having various skeletons with both terminal carboxylic acid modified butadiene-acrylonitrile rubber may also be used. Further, an epoxy-containing polybutadiene-based elastomer, an acrylic-containing polybutadiene-based elastomer, a hydroxyl group-containing polybutadiene-based elastomer, and a hydroxyl group-containing isoprene-based elastomer may be used. The elastomer may be used singly or as a mixture of two or more thereof.

(Adhesion promoter)

To the curable resin composition of the present invention, an adhesion promoter may be used to improve interlayer adhesion, or adhesion between the resin composition layer and the substrate. Examples of the adhesion promoter include benzimidazole, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 3-morpholinomethyl- 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, Sol, carboxybenzotriazole, amino group-containing benzotriazole, silane coupling agent, and the like.

(Antioxidant)

Most of the polymer materials are oxidized at the beginning of the oxidation once, and oxidative deterioration occurs successively, resulting in degradation of the function of the polymer material. In order to prevent oxidation of the curable resin composition of the present invention, (1) And / or (2) an antioxidant such as a peroxide decomposition agent which decomposes the generated peroxide into a harmless substance and prevents generation of new radicals.

Specific examples of the antioxidant that functions as a radical supplement include hydroquinone, 4-tert-butyl catechol, 2-t-butyl hydroquinone, hydroquinone monomethyl ether, 2,6- Methyl-6-t-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy- Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ', 5'- Phenoxy compounds such as hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) trione, quinone compounds such as methoquinone and benzoquinone, bis - tetramethyl-4-piperidyl) sebacate, phenothiazine, and the like.

Radical supplements may be commercially available, such as Adeka Staff AO-30, Adeka Staff AO-330, Adeka Staff AO-20, Adeka Staff LA-77, Adeka Staff LA-57, Adeka (Manufactured by Adeka Co., Ltd., product name), IRGANOX 1010, Irganox 1035, Irganox 1076, Irganox 1135 , TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (trade names, manufactured by BASF Japan).

Specific examples of the antioxidant functioning as a peroxide releasing agent include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetra lauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3'-thiodi And sulfur compounds such as propionate.

The release of the peroxide may be commercially available, and examples thereof include Adekastab TPP (trade name, product of Adeka Co., Ltd.), Mark AO-412S (trade name, manufactured by Adeka Co., Ltd.), Sumilayer TPS (trade name, And the like.

The above-mentioned antioxidants may be used singly or in combination of two or more.

(Ultraviolet absorber)

The ultraviolet absorber may be used in addition to the antioxidant in the curable resin composition of the present invention in order to take measures to stabilize the ultraviolet rays because the polymer material absorbs light and causes decomposition and deterioration thereof.

Examples of ultraviolet absorbers include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives and dibenzoylmethane derivatives. Specific examples of the benzophenone derivative include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy- 4-dihydroxybenzophenone and the like; Examples of specific benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3,5-di- Hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate; Specific examples of the benzotriazole derivatives include 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, Chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole; Specific examples of the triazine derivatives include hydroxyphenyltriazine and bisethylhexyloxyphenol methoxyphenyltriazine.

Examples of the ultraviolet absorber include Tinuvin PS, Tinuvin 99-2, Tinuvin 109, Tinuvin 384-2, Tinuvin 900, Tinuvin 928, Tinuvin 1130, Tinuvin 400, Nubin 405, Tinuvin 460, and Tinuvin 479 (all trade names, manufactured by BASF Japan).

The above ultraviolet absorbers may be used alone or in combination of two or more. By using this antioxidant in combination, it is possible to stabilize the cured coating obtained from the curable resin composition of the present invention.

(Other additives)

The curable resin composition of the present invention may contain, if necessary, a known thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, pyrogallol, phenothiazine and the like, a known system such as finely divided silica, organic bentonite, montmorillonite Based additives such as a thickener, a defoaming agent such as a silicone type, a fluorine type or a high molecular type, and a leveling agent, a silane coupling agent such as an imidazole type, a thiazole type or a triazole type and an antirusting agent .

The thermal polymerization inhibitor may be used to prevent thermal polymerization or polymerization over time of the curable resin composition. Examples of the thermal polymerization inhibitor include 4-methoxyphenol, hydroquinone, alkyl or aryl substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy- (4-methyl-6-t-butoxycarbonyl) -2-methyl- Butylphenol), a reagent such as pyridine, nitrobenzene, dinitrobenzene, picric acid, 4-toluidine, methylene blue, copper and an organic chelating agent, methyl salicylate, phenothiazine, nitroso compound, .

(Organic solvent)

The curable resin composition of the present invention can be used for the synthesis of the carboxyl group-containing resin (A), for the preparation of the composition, or for adjusting the viscosity for application to a substrate or a carrier film.

Examples of such organic solvents include ketones, aromatic hydrocarbons, glycol ethers, glycol ether acetates, esters, alcohols, aliphatic hydrocarbons, petroleum solvents and the like. More specifically, ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether And the like; Esters such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol butyl ether acetate; Alcohols such as ethanol, propanol, ethylene glycol and propylene glycol; Aliphatic hydrocarbons such as octane and decane; Petroleum ether such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha. These organic solvents may be used singly or as a mixture of two or more kinds.

The curable resin composition of the present invention is useful for forming a pattern layer of a printed wiring board and a flexible wiring board, and is particularly useful as a material of a solder resist or an interlayer insulating layer.

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 containing the 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 the above organic solvent and adjusted to an appropriate viscosity, and the resulting mixture is applied to a substrate such as a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, Coater or the like to a uniform thickness on the carrier film and dried at a temperature of usually 50 to 130 DEG C for 1 to 30 minutes to obtain a film. The thickness of the coating film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 占 퐉, preferably 20 to 60 占 퐉 in film thickness after drying.

As the carrier film, a plastic film is used, and it is preferable to use a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film. The thickness of the carrier film is not particularly limited, but is generally appropriately selected in the range of 10 to 150 mu m.

It is preferable to further laminate a peelable cover film on the surface of the film for the purpose of preventing the adhesion of dust to the surface of the film after the curable resin composition of the present invention is formed on the carrier film.

As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface treated paper, or the like can be used. When peeling the cover film, the peelability of the film and the cover film The adhesive force may be smaller.

The curable resin composition of the present invention can be prepared, for example, by adjusting the viscosity with a suitable viscosity for the application method with the organic solvent described above, and coating the surface of the substrate with an organic solvent such as an immersion coating method, a flow coating method, a roll coating method, a bar coater method, , And the organic solvent contained in the composition is volatilized and dried (dried) at a temperature of about 60 to 100 占 폚 to form a coat free film. Further, in the case of a dry film obtained by applying the above composition onto a carrier film and drying it and then winding it as a film, the curable resin composition layer is laminated on the substrate so as to be in contact with the substrate by a laminator or the like, Can be formed.

As the above substrate, in addition to a printed circuit board or a flexible printed circuit board which has been formed in advance, a substrate such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluoropolymer (FR-4 or the like), other polyimide film, PET film, glass substrate, ceramic substrate, or the like using materials such as a copper clad laminate for a high frequency circuit using an epoxy, ether, polyphenylene oxide, cyanate ester, A wafer plate and the like.

The volatile drying performed after application of the curable resin composition of the present invention can be carried out by a hot air circulating drying furnace, a hot plate, a convection oven or the like (by using an air heating type heat source by steam) A method of contacting the substrate and a method of spraying the substrate from the nozzle).

When the curable resin composition of the present invention contains a thermosetting component, the thermosetting component is heated to a temperature of, for example, about 140 to 180 ° C, whereby the carboxyl group of the carboxyl-containing resin (A) reacts with the thermosetting component, , A cured coating film excellent in various properties such as chemical resistance, hygroscopicity, adhesion, electrical properties and the like can be formed.

When the coating film containing the photopolymerization initiator and the photopolymerizable monomer is applied and the solvent is volatilized and dried, the resulting coating film is subjected to exposure (irradiation with active energy rays) to expose the exposed portion (the portion irradiated with the active energy rays) do. Alternatively, the resist pattern may be directly pattern-exposed through a photomask having a pattern formed by a contact-type (or non-contact-type) method selectively with an activating energy beam or by a laser direct exposure machine to form an unexposed portion in a dilute alkali aqueous solution 3 wt% aqueous sodium carbonate solution) to form a resist pattern.

As an exposure device used for the irradiation of the active energy rays, an apparatus for irradiating ultraviolet rays in a range of 350 to 450 nm may be used as long as it is equipped with a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp and a mercury short arc lamp. For example, a laser direct imaging apparatus which draws an image with a laser directly by CAD data from a computer) can also be used. As the laser light source of the direct game, either a gas laser or a solid laser may be used if laser light having a maximum wavelength in the range of 350 to 410 nm is used. Light exposure for image formation varies depending on the thickness, in general, it can be set within 20 to 800mJ / cm ^2, preferably in the range of 20 to a range of 600mJ / cm ^2.

As the developing method, a dipping method, a shower method, a spray method, a brush method, or the like can be used. As the developing solution, an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, have.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited by the examples and the comparative examples. The parts representing the blending amount are parts by mass unless otherwise specified.

(Synthesis or production of a carboxyl group-containing resin)

[A-1: Production of resin corresponding to the carboxyl group-containing resin (8)

(ZFR-1401H (solid content: 65%, acid value as a resin: 98 mgKOH / g) manufactured by Nippon Kayaku Co., Ltd.) corresponding to the above carboxyl group-containing resin (8) and containing a photosensitive group and using a polyfunctional epoxy of bisphenol F type, Respectively. The varnish is hereinafter referred to as A-1.

[A-2: Synthesis of resin corresponding to the carboxyl group-containing resin (5)] [

A reaction vessel equipped with a stirrer, a thermometer and a condenser was charged with 2400 g (3 parts) of a polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol (manufactured by Asahi Kasei Chemicals Co., Ltd., T5650J, number average molecular weight 800) Mol), 603 g (4.5 mol) of dimethylolpropionic acid, and 238 g (2.6 mol) of 2-hydroxyethyl acrylate as a monohydroxyl compound. Subsequently, 1887 g (8.5 mol) of isophorone diisocyanate was added as polyisocyanate, and the mixture was heated to 60 DEG C with stirring and stopped. When the temperature in the reaction vessel began to decrease, the mixture was heated again and stirred at 80 DEG C, The absorption spectrum (2280 cm ^-1 ) of the isocyanate group was confirmed to be lost, and the reaction was terminated. Carbitol acetate was added so that the solid content was 50 mass%. The acid value of the solid content of the obtained carboxyl group-containing resin was 50 mgKOH / g. The obtained varnish is hereinafter referred to as A-2.

[A-3: Production of resin corresponding to the carboxyl group-containing resin (4)

Containing resin having a urethane structure containing a photosensitive group corresponding to the above carboxyl group-containing resin (4) (UXE-3000 manufactured by Nippon Kayaku Co., Ltd. (solid content: 65%, acid value as resin: 98 mgKOH / g)] was used. The varnish is hereinafter referred to as A-3.

[A-4: Production of resin corresponding to the carboxyl group-containing resin (7)

Containing resin (ZCR-1601H (solid content: 65%, acid value as a resin: 98 mgKOH / g) manufactured by Nippon Kayaku Co., Ltd.) corresponding to the above-mentioned carboxyl group-containing resin (7) and containing a photosensitive group and having biphenyl novolak type polyfunctional epoxy, ] Was used. The varnish is hereinafter referred to as A-4.

[Synthesis Example of Urethane Acrylate]

336 g (2 mol) of 1,6-hexamethylene diisocyanate (HDI) and 0.05 g of stannous chloride were introduced into a reaction vessel immersed in an oil bath, equipped with a stirring blade, a thermometer, an addition funnel and a dry air inlet, 530 g (1 mol) of polycaprolactone (Placcel 205, polycaprolactone diol having a molecular weight of 530 / Daicel Kagaku Co., Ltd.) was added from an addition funnel when isophorone diisocyanate (IPDI) reached 70 캜 . After the addition, the temperature in the reaction vessel was maintained at 70 占 폚 until the residual NCO concentration became the theoretical value to prepare a polycaprolactone urethane prepolymer. Thereafter, 232 g (2 mol) of 2-hydroxyethyl acrylate (HEA) was added, and the inside of the reaction vessel was kept at 70 캜 until the residual NCO concentration in the extracted sample of the reaction product was confirmed to be 0.1% . Thereby, urethane acrylate F was obtained.

[Examples 1 to 13, Comparative Examples 1 to 4]

The above-mentioned resin solution (varnish) was compounded with various components shown in Table 1 in the ratio shown in Table 1 (mass part), preliminarily mixed with a stirrer, and kneaded by a three-roll mill to prepare a curable resin composition . Here, the degree of dispersion of each of the obtained curable resin compositions was evaluated by particle size measurement by a grindmeter manufactured by Ericensa and found to be 15 탆 or less.

* 1: Carbitol acetate solution (solid content: 75%) of an epoxy resin having a biphenyl novolac structure NC-3000-H-CA75 manufactured by Nippon Kayaku Co.,

* 2: Beecylenol type epoxy resin, manufactured by Mitsubishi Chemical Corporation

* 3: Bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation

* 4: An organic filler whose surface was not coated with silica, BP-01-5 manufactured by Climate Control Co.

* 5: Organic filler whose surface is coated with silica, AK-800TR

* 6: SPE-100 manufactured by Otsuka Chemical Co.

* 7: Exolite OP935 manufactured by Clariant

* 8: HFA-6065E manufactured by Showa Denko K.K.

* 9: Higilit H-42M manufactured by Showa Denko K.K.

* 10: Rasirin TPO manufactured by BASF Japan

* 11 Irgacure 389 manufactured by BASF Japan

* 12: Irgacure OXE-02 manufactured by BASF Japan

* 13: BPE-500 manufactured by Shin-Nakamura Chemical Co.

* 14: DPCA-60 manufactured by Nippon Kayaku Co.

* 15: UX-2201 manufactured by Nippon Kayaku Co.

* 16: KBM-403 manufactured by Shin-Etsu Silicone Co.

* 17: manufactured by Ishihara Sangyo Co., Ltd. CR-97

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

* 19: C.I. Pigment Yellow 147

* 20: KS-66 manufactured by Shin-Etsu Silicone Co.

* 21: Dipropylene glycol monomethyl ether

Performance evaluation:

<Optimum exposure dose>

The composition of each of the above Examples and Comparative Examples was buffed, polished, buffed, dried, and then applied to the entire surface by a screen printing method in a hot air circulating type drying furnace at 80 캜 for 30 minutes Lt; / RTI &gt; (30 ° C, 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution) was exposed using a step tablet (Kodak No. 2) using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp 60 seconds. When the pattern of the remaining step tablets was six, the optimum exposure amount was determined.

&Lt; Evaluation method of appearance >

The compositions of the above Examples and Comparative Examples were coated on the entire surface by screen printing on a patterned polyimide film substrate, dried at 80 DEG C for 30 minutes, and then allowed to cool to room temperature. The obtained substrate was exposed to a solder resist pattern at an optimum exposure dose using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C was sprayed under a spray pressure of 2 kg / cm ² And development was carried out for 60 seconds to obtain a resist pattern. The substrate was cured by heating at 150 DEG C for 60 minutes. The resulting printed board (evaluation board) was sandwiched by a cushioning material, and subjected to a vacuum press at 150 DEG C for 60 minutes by applying a load of ²⁰ kgf / cm &lt; ² &gt; The surface of the substrate after the press was observed with the naked eye and the appearance was evaluated based on the following criteria.

○: No bad appearance on the surface of the coating film and the cushioning material contact portion at the time of pressing.

X: Appearance defective at the portion of the coating film surface contacting the cushioning material during pressing.

&Lt; Flexibility (Endurance) >

The composition of each of the above Examples and Comparative Examples was applied to the entire surface by screen printing on a polyimide film (Capton 100H, manufactured by Du Pont DuPont) having a thickness of 25 占 퐉, dried at 80 占 폚 for 30 minutes and cooled to room temperature. The obtained substrate was exposed to a resist pattern at an optimal exposure dose using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp and developed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C for 60 seconds under a spray pressure of 0.2 MPa To obtain a resist pattern, and the substrate was cured by heating at 150 DEG C for 60 minutes.

The obtained evaluation substrate was repeatedly bent 180 degrees by bending to observe the occurrence of cracks in the coating film at this time with naked eyes and a 200-fold optical microscope, and the number of times of bending performed until cracking was measured was measured , And evaluated according to the following criteria.

◎: Bending frequency is 6 or more times.

O: The number of bending times is 4 to 5 times.

B: Bending frequency is 2 to 3 times.

X: The number of times of bending is 0 to 1.

<Low bending property>

Similarly to the sample for evaluation of flexibility (bending resistance), the prepared sample was cut into 50 mm x 50 mm square, and the warpage of the quadrangle was measured, and an average value was obtained and evaluated according to the following criteria.

◯: The flexure is less than 4 mm.

B: The warpage is 4 mm or more and less than 8 mm.

X: The warpage is 8 mm or more.

<Insulation reliability>

The compositions of the above Examples and Comparative Examples were applied on a polyimide substrate (Espinex manufactured by Shin-Etsu Chemical Co., Ltd.) having an L / S ratio of 50/50 μm by screen printing, dried at 80 ° C for 30 minutes, Followed by cooling. The obtained substrate was exposed to a resist pattern at an optimal exposure dose using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp and developed with a 1 wt% Na ₂ CO ₃ aqueous solution at 30 ° C for 60 seconds under a spray pressure of 0.2 MPa To obtain a resist pattern, and the substrate was cured by heating at 150 DEG C for 60 minutes. A bias voltage of 50 V DC was applied to the evaluation substrate thus obtained, and the resistance value was continuously measured at 85 캜 and 85% RH in a constant temperature and humidity bath. The criteria are as follows.

?: No discoloration of the shot and the copper foil occurred after 1000 hours passed.

?: No shot occurred after 1000 hours passed, but there was discoloration of the copper foil.

X: Shot occurred within 1000 hours.

The results of the above evaluation tests are summarized in Table 1.

<Flammability>

The composition of each of the above Examples was applied to the entire surface by screen printing on a polyimide film (25 m, Capton 50H (12.5 m) manufactured by Toray DuPont) having a thickness of 25 m and a thickness of 12.5 m, Dried and allowed to cool to room temperature. Further, the entire back side was similarly coated with screen printing, dried at 80 占 폚 for 30 minutes, and cooled to room temperature to obtain a double-side coated substrate. Exposing the metal halide lamp with the resulting double-sided board apparatus (HMW-680-GW20) If the total of the solder resist as the optimal exposure amount exposed by the, and the 1wt% Na ₂ CO ₃ aqueous solution for 30 ℃ spray pressure of 2kg / cm ² Under the conditions of 60 seconds, and thermally cured at 150 DEG C for 60 minutes to obtain an evaluation sample. This flame retardancy evaluation sample was subjected to a thin film vertical burning test in accordance with the UL94 standard. The results of the flame retardancy test were evaluated as?, VTM-1?, And?

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

[Examples 14 to 23]

The curable resin compositions of Examples 1 to 10 shown in Table 1 were diluted with methyl ethyl ketone, coated on a carrier film (PET), and dried by heating to obtain a curable resin composition having a thickness of 20 占 퐉 A photosensitive resin composition layer was formed, and a cover film (PE) was bonded thereon to obtain a dry film. Thereafter, the cover film was peeled off, and a film was bonded to the patterned copper foil board using a laminator to prepare a test board. Evaluation tests of respective characteristics were carried out in the same manner as in the test method and evaluation method described above. When the dry film according to the composition of Example 1 had the composition of Example 14, the composition of Example 2 was Example 15, the composition of Example 3 was Example 16, the composition of Example 4 was that of Example 17, The compositions of Examples 18 and 6 were the same as those of Example 19 and Example 7, the compositions of Example 20 and Example 8 were those of Example 21, and the compositions of Example 9 were Examples 22 and 10 And the composition corresponds to Example 23, respectively. The results are shown in Tables 3 and 4 below.

[Examples 24 to 31, Comparative Examples 5 to 7]

The above-mentioned resin solution (varnish) was blended with the various components shown in Table 5 in the ratio shown in Table 5 (mass part), premixed with a stirrer, and kneaded with a three-roll mill to prepare a curable resin composition. Here, the degree of dispersion of each of the obtained curable resin compositions was evaluated by particle size measurement by a grindmeter manufactured by Ericensa and found to be 15 탆 or less.

* 22: MA-100 manufactured by Mitsubishi Chemical Corporation

* 23: diketopyrrolopyrrole-based red colorant

* 24: C.I. Pigment Black 31

Performance evaluation:

Evaluation tests of the optimum exposure amount, resolution, appearance, flexibility, low warpage, and insulation reliability were carried out in the same manner as the above-mentioned test method and evaluation method. Further, L ^* value, resolution and concealability were evaluated by the following evaluation method. The results are shown in Table 5.

<L ^* value>

Each of the curable resin compositions of Examples 24 to 31 and Comparative Examples 5 to 7 was coated on the entire surface by screen printing on a copper substrate and dried at 80 DEG C for 30 minutes in a hot air circulating type drying furnace, And the resist was irradiated with an amount of light of 500 mJ / cm ² by using an integrated light meter manufactured by Oak Seisakusho Co., Ltd. and exposed. Thereafter, the film was developed with a 1 mass% Na ₂ CO ₃ aqueous solution having a spray pressure of 0.2 MPa for 60 seconds and then subjected to a heat curing treatment at 150 ° C for 60 minutes using a hot air circulation type drying furnace to obtain a cured coating film. The thus obtained cured coating film was measured for L ^* a ^* b ^* colorimetric value on a copper basis according to JIS Z 8729 using the following colorimetric system, and the L ^* value representing the brightness was evaluated as an index of blackness degree . The smaller the L ^* value, the better the blackness.

Color color difference system: 45 ° circular color illumination Vertical light reception system High performance color colorimeter (CR-221 manufactured by Konica Minolta)

<Resolution>

The curable resin compositions of Examples 24 to 31 and Comparative Examples 5 to 7 were applied by screen printing on a circuit substrate having a circuit formed thereon, dried at 80 DEG C for 30 minutes in a hot air circulating type drying furnace, 120 mu m) was irradiated with ultraviolet rays having a wavelength of 365 nm at a dose of 500 mJ / cm &lt; ² &gt; onto the resist using an integrating photometer manufactured by Orksay Sakusho Co., Ltd. and exposed. Subsequently, the resist film was developed for 60 seconds in a 1 mass% Na ₂ CO ₃ aqueous solution having a spray pressure of 0.2 MPa, and the line remained and spacing of the exposed portion were judged visually. &Quot; o &quot; and &quot; x &quot;

<Concealability>

The above-prepared substrate with the resolution was heated at 150 DEG C for 60 minutes. The discoloration of the copper circuit of the portion covered with the solder resist was visually confirmed and evaluated according to the following criteria.

○: The discoloration part of the copper circuit is unknown.

△: The discoloration part of the copper circuit can be slightly recognized.

X: The discolored part of the copper circuit can be recognized.

The flame retardancy was evaluated in the same manner as in the test method and the evaluation method described above. The evaluation results are shown in Table 6.

From the results shown in Tables 1 to 6, it was found that the cured products obtained from the curable resin composition or the dry film of Examples 1 to 31 had good flexibility, low warpage and insulation reliability, . Further, these cured products were also excellent in flame retardancy, and in particular, the cured products obtained from the curable resin compositions or the dry films of Examples 1 to 10 and 14 to 31 containing an epoxy resin having a phosphorus-containing compound and a biphenyl novolac structure It can be seen that it has excellent flame retardancy. It can be seen that the curable resin compositions of Examples 24 to 31 are excellent in resolution even though they are black, and the cured products obtained therefrom are excellent in hiding ability. In particular, it can be seen that the cured products obtained from the curable resin compositions of Examples 24 to 29 containing at least one colorant other than the black colorant and the black colorant have better hiding properties.

On the other hand, Comparative Example 1 containing no silica-coated organic filler had poor appearance, flexibility and low warpage. Similarly, Comparative Example 2 had poor appearance and flexibility, Comparative Example 3 had a poor appearance, and Comparative Example 4 had poor appearance, flexibility, and low warpage. Comparative Example 5 was poor in appearance, flexibility and low warpability, Comparative Example 6 was inferior in appearance and flexibility, and Comparative Example 7 was inferior in appearance, flexibility and low warpability.

Claims (12)

(A) a carboxyl group-containing resin,
(B) a photopolymerization initiator, and
(C) an organic filler whose surface is coated with silica
And a curing agent. The curable resin composition according to claim 1, wherein the organic filler (C) whose surface is coated with silica is a urethane resin whose surface is coated with silica. The resin composition according to claim 1, wherein the carboxyl-containing resin (A) is selected from the group consisting of a bisphenol A structure, a bisphenol F structure, a biphenol structure, a biphenol novolak structure, a biscensilene structure, a biphenyl novolak structure, and a urethane structure Containing resin having at least one partial structure which is a carboxyl group-containing resin. The curable resin composition according to claim 1, further comprising (D) a flame retardant. The curable resin composition according to claim 4, wherein the flame retardant (D) is a phosphorus-containing compound. The curable resin composition according to claim 5, wherein the phosphorus-containing compound is a phenoxyphosphazene oligomer or a phosphinic acid metal salt. The curable resin composition according to any one of claims 1 to 6, further comprising (E) an epoxy resin having a biphenyl novolak structure. The curable resin composition according to any one of claims 1 to 6, which is for forming a solder resist. The curable resin composition according to any one of claims 1 to 6, wherein the curable resin composition is black. A dry film obtained by applying and drying the curable resin composition according to any one of claims 1 to 6 to a film. A curable resin composition according to any one of claims 1 to 6, or a curable resin composition obtained by applying and drying the curable resin composition to at least one of a thermal curing and a photo curing, film. A printed wiring board comprising the cured coating film according to claim 11.