JP5564144B1 - Curable resin composition, dry film and cured product thereof, and printed wiring board using them - Google Patents

Abstract

The present invention provides a curable resin composition that is excellent in electrical characteristics, flexibility, and low warpage, and that suppresses occurrence of cracks and appearance defects.
A curable resin composition comprising (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, and (C) an organic filler whose surface is coated with silica. The organic filler (C) whose surface is coated with silica is preferably a urethane resin whose surface is coated with silica.
[Selection figure] None

Description

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

  Conventionally, an organic curable resin composition for obtaining a coating film (cured film) which is one of the constituent elements of a printed wiring board and a flexible wiring board (hereinafter abbreviated as FPC) mounted on an electronic device is used. It is known to incorporate a filler. For example, in order to make a coating film flame-retardant, a phosphorus-containing compound capable of imparting flame retardancy or an epoxy resin excellent in heat resistance is blended into a curable resin composition, and when a wiring board is cut or subjected to a thermal shock test. In some cases, cracks are likely to occur in the cured film. In order to suppress the occurrence of cracks in such a cured film, for example, Patent Document 1 discloses an alkali development type photocurable / thermosetting resin composition containing polyurethane fine particles. Moreover, in order to suppress the generation | occurrence | production of the crack of the cured film by having mix | blended the inorganic filler highly in order to provide the outstanding functional characteristic, in patent document 2, the organic filler of a specific elastic modulus and average particle diameter is included. A curable resin composition is disclosed.

JP 2002-293882 A (Claims) JP 2009-102623 A (Claims)

  However, when using an organic filler, in the printed wiring board or FPC manufacturing process, that is, in the pressing process, the organic filler is crushed, gloss is produced in the portion hit by the press, and the entire cured film becomes uneven. The occurrence of was a problem. In addition, there has been a demand for improvement in the unfamiliarity between the organic filler and the resin component and the electrical characteristics of the cured film. On the other hand, in thin FPC, there existed a problem that curvature might arise in FPC by the influence of the film formed by hardening | curing curable resin composition.

  Therefore, an object of the present invention is to provide a curable resin composition that is excellent in electrical characteristics, flexibility, and low warpage, and that suppresses the occurrence of cracks and appearance defects.

  As a result of intensive studies to solve the above problems, the present inventors have 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 contains (A) a carboxyl group-containing resin, (B) a photopolymerization initiator, and (C) an organic filler whose surface is coated with silica, and ( C) The organic filler whose surface is coated with silica is a urethane resin whose surface is coated with silica.

  In the curable resin composition of the present invention, the (A) carboxyl group-containing resin is selected from the group consisting of a bisphenol A structure, a bisphenol F structure, a biphenol structure, a biphenol novolac structure, a bisxylenol structure, a biphenyl novolac structure, and a urethane structure. A carboxyl group-containing resin having one or more partial structures is preferred.

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

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

  The phosphorus-containing compound is preferably 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 novolac 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 curable resin compositions is applied to a film and dried.

  The cured coating film of the present invention is obtained by performing at least one of thermosetting and photocuring on any one of the curable resin compositions or the dry film.

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

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

The curable resin composition of the present invention includes (A) a carboxyl group-containing resin and (B) a resin composition containing a photopolymerization initiator, and (C) containing an organic filler whose surface is coated with silica. It is a feature.
By blending the organic filler whose surface is coated with silica, it is possible to suppress the occurrence of defects in appearance during the pressing process while suppressing the occurrence of cracks in the cured film. Moreover, since the organic filler coat | covered with the silica was familiar with the resin component, it turned out that it is excellent in insulation reliability.

  In addition, (D) a phosphorus-containing compound as a flame retardant is blended with the curable resin composition of the present invention, and (E) an epoxy resin having a biphenyl novolac structure is blended, whereby the cured product has excellent flame retardancy. It was found that a curable resin composition was obtained.

  Moreover, it turned out that the curable resin composition excellent in concealability is obtained by making the curable resin composition of this invention black. In particular, it was found that, by blackening by containing a black colorant and a colorant other than black, it is possible to obtain a curable resin composition that is more excellent in concealment property despite excellent resolution. .

  Hereinafter, each component will be described in detail.

[(A) Carboxyl group-containing resin]
As said (A) carboxyl group containing resin, resin containing a well-known carboxyl group can be used. Due to the presence of the carboxyl group, the resin composition can be made alkali developable. Further, from the viewpoint of making the curable resin composition of the present invention photocurable and developing resistance, it is preferable to have an ethylenically unsaturated bond in the molecule in addition to the carboxyl group. Only a carboxyl group-containing resin having no double bond can be used as the component (A). When the resin of component (A) does not have an ethylenically unsaturated bond, a compound having at least one ethylenically unsaturated group in the molecule (photopolymerizable monomer) is used to make the composition photocurable. ) Must be used in combination. As the ethylenically unsaturated double bond, those derived from acrylic acid, 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 compounds listed below (any of oligomers and polymers).

  (1) A carboxyl group-containing resin obtained by copolymerization of an unsaturated carboxylic acid such as (meth) acrylic acid and an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, and isobutylene.

  (2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates; carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate polyols, and polyethers A carboxyl group-containing urethane resin by a polyaddition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate polyols, polyether polyols, polyester polyols, polyolefin polyols, acrylic polyols, bisphenol A systems A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

  (4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenol type epoxy resin, biphenol type epoxy resin ( Photosensitive carboxyl group-containing urethane resin by polyaddition reaction of (meth) acrylate or its modified partial anhydride, carboxyl group-containing dialcohol compound and diol compound.

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

  (6) During the synthesis of the resin of (2) or (4) above, one isocyanate group and one or more (meth) acryloyl groups are present in the molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. The carboxyl group-containing urethane resin which added the compound which has and was terminally (meth) acrylated.

  (7) dibasic acid anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. are reacted with a hydroxyl group present in the side chain by reacting a polyfunctional (solid) epoxy resin as described later. A photosensitive carboxyl group-containing resin to which a product is added.

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

  (9) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin as described later with a dicarboxylic acid and adding a dibasic acid anhydride to the resulting primary hydroxyl group.

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

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

  (12) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth) Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, and then reacting with the alcoholic hydroxyl group of the resulting reaction product, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine A carboxyl group-containing photosensitive resin obtained by reacting a polybasic acid anhydride such as an acid.

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

Since the carboxyl group-containing resin as described above has many carboxyl groups in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.
Moreover, the acid value of the said carboxyl group-containing resin has the preferable range of 20-200 mgKOH / g, More preferably, it is the range of 40-150 mgKOH / g. When the acid value of the carboxyl group-containing resin is 20 mgKOH / g or more, the adhesion of the coating film is good and the alkali development is good. On the other hand, when the acid value is 200 mgKOH / g or less, the dissolution of the exposed part by the developer can be suppressed, so that the line is thinner than necessary, or in some cases, the developer without distinguishing between the exposed part and the unexposed part The resist pattern can be satisfactorily drawn by suppressing dissolution and peeling.

  Moreover, although the weight average molecular weight of carboxyl group-containing resin used by this invention changes with resin frame | skeletons, the range of 2,000-150,000, Furthermore, 5,000-100,000 is preferable. When the weight average molecular weight is 2,000 or more, the tack-free performance is good, the moisture resistance of the coated film after exposure is good, the film loss during development can be suppressed, and the resolution can be suppressed. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is good and the storage stability is also excellent.

Among the carboxyl group-containing resins, the polyfunctional epoxy resin used for the synthesis of the resin is a group consisting of a bisphenol A structure, a bisphenol F structure, a biphenol structure, a biphenol novolac structure, a bisxylenol structure, a biphenyl novolac structure, and a urethane structure. A polyfunctional epoxy resin having one or more partial structures selected from the above or a carboxyl group-containing resin that is a hydrogenated compound thereof is preferred from the viewpoint of low warpage and bending resistance of the resulting cured product.
Among the carboxyl group-containing resins having a urethane structure, a carboxyl group-containing urethane resin obtained by using a diisocyanate in which an isocyanate group is not directly bonded to a benzene ring is used as a component having an isocyanate group (including a diisocyanate). Since there is no change, it is effective for concealment and has little UV absorption, it is preferable because it has excellent resolution when used as an alkali-developable composition.
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 blending amount of the (A) carboxyl group-containing resin as described above is preferably 5 to 60% by mass, more preferably 10 to 60% by mass, still more preferably 20 to 60% by mass, particularly preferably in the entire composition. Is 30-50 mass%. In the case of 5 to 60% by mass, the coating film strength is good, the viscosity of the composition is moderate, and coatability and the like can be improved.

[(B) Photopolymerization initiator]
(B) As a photoinitiator, a well-known photoinitiator can be used, For example, the oxime ester type photoinitiator which has an oxime ester group, (alpha) -amino acetophenone type photoinitiator, acyl phosphine oxide One or more photopolymerization initiators selected from the group consisting of system photopolymerization initiators can be suitably used.

（式中、Ｘは、水素原子、炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、フェニル基、フェニル基（炭素数1〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）を表し、Ｙ、Ｚはそれぞれ、水素原子、炭素数1〜１７のアルキル基、炭素数１〜８のアルコキシ基、ハロゲン基、フェニル基、フェニル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、ナフチル基（炭素数１〜１７のアルキル基、炭素数１〜８のアルコキシ基、アミノ基、炭素数１〜８のアルキル基を持つアルキルアミノ基又はジアルキルアミノ基により置換されている）、アンスリル基、ピリジル基、ベンゾフリル基、ベンゾチエニル基を表し、Ａｒは、結合か、炭素数１〜１０のアルキレン、ビニレン、フェニレン、ビフェニレン、ピリジレン、ナフチレン、チオフェン、アントリレン、チエニレン、フリレン、２，５−ピロール−ジイル、４，４’−スチルベン−ジイル、４，２’−スチレン−ジイルを表し、ｎは０か１の整数である。） Examples of the oxime ester photopolymerization initiator include CGI-325, Irgacure OXE01, Irgacure OXE02 manufactured by BASF Japan, N-1919, NCI-831 manufactured by ADEKA, and the like as commercially available products. Moreover, the photoinitiator which has two oxime ester groups in a molecule | numerator can also be used suitably, Specifically, the oxime ester compound which has a carbazole structure represented with the following general formula is mentioned.

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

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

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

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

(In the formula, R ¹ represents an alkyl group or a nitro group, a halogen atom or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms.
R ² represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkoxy group.
R ³ may be linked with an oxygen atom or a sulfur atom, and may be substituted with an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 4 carbon atoms which may be substituted with a phenyl group. Represents a good benzyl group.
R ⁴ represents a nitro group or an acyl group represented by X—C (═O) —. X represents an aryl group, a thienyl group, a morpholino group, a thiophenyl group, or a structure represented by the following formula, which may be substituted with an alkyl group having 1 to 4 carbon atoms. )

  In addition, JP-A-2004-359639, JP-A-2005-097141, JP-A-2005-220097, JP-A-2006-160634, JP-A-2008-094770, JP-A-2008-509967, Specific examples include carbazole oxime ester compounds described in JP2009-040762A and JP2011-80036A.

  It is preferable that the compounding quantity of such an oxime ester system photoinitiator shall be 0.01-5 mass parts with respect to 100 mass parts of said (A) carboxyl group-containing resin. When the amount is 0.01 parts by mass or more, the photocurability is good and the coating properties such as chemical resistance are good. On the other hand, in the case of 5 parts by mass or less, light absorption on the coating film surface becomes good, and deep part curability is improved. More preferably, it is 0.5-3 mass parts.

  As the α-aminoacetophenone photopolymerization initiator, specifically, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, N , N-dimethylaminoacetophenone and the like. Examples of commercially available products include Irgacure 907, Irgacure 369, and Irgacure 379 manufactured by BASF Japan.

  Specific examples of the acylphosphine oxide photopolymerization initiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and bis (2,6-dimethoxy). And benzoyl) -2,4,4-trimethyl-pentylphosphine oxide. Examples of commercially available products include Lucilin TPO manufactured by BASF Japan and Irgacure 819 manufactured by BASF Japan.

  The blending amount of these α-aminoacetophenone photopolymerization initiator and acylphosphine oxide photopolymerization initiator is 0.01 to 15 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. preferable. In the case of 0.01 parts by mass or more, photocurability is good, and deterioration of coating film properties such as chemical resistance can be suppressed. On the other hand, in the case of 15 parts by mass or less, the outgas is reduced, the light absorption on the coating film surface is improved, and the deep curability is improved. More preferably, it is 0.5-10 mass parts.

  In addition to the photopolymerization initiator, a photoinitiator assistant and a sensitizer can be used. Photoinitiators, photoinitiators, and sensitizers that can be suitably used for photosensitive resin compositions include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, and tertiary amine compounds. And xanthone compounds.

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

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

  Specific examples of the anthraquinone compound include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, and the like.

  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 and benzyl dimethyl ketal.

  Specific examples of the benzophenone compound include benzophenone, 4-benzoyldiphenyl sulfide, 4-benzoyl-4′-methyldiphenyl sulfide, 4-benzoyl-4′-ethyldiphenyl sulfide, and 4-benzoyl-4′-propyldiphenyl. And sulfides.

  Specifically, as the tertiary amine compound, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, such as 4,4′-dimethylaminobenzophenone (Nisso Cure MABP manufactured by Nippon Soda Co., Ltd.), 4, Dialkylaminobenzophenone such as 4′-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one (7- (diethylamino) -4-methylcoumarin), etc. Dialkylamino group-containing coumarin compounds, ethyl 4-dimethylaminobenzoate (Kayacure EPA, manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (Quantacure DMB, manufactured by International Bio-Synthetics), 4-dimethylamino Nobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthetics), p-dimethylaminobenzoic acid isoamyl ethyl ester (Kayacure DMBI manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylhexyl 4-dimethylaminobenzoic acid (Esolol 507 manufactured by Van Dyk).

  Of these, thioxanthone compounds and tertiary amine compounds are preferred. In particular, the inclusion of a thioxanthone compound is preferable from the viewpoint of deep curability. Among them, it is preferable to include a thioxanthone compound such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, and 2,4-diisopropylthioxanthone.

  As a compounding quantity of such a thioxanthone compound, it is preferable that it is 20 mass parts or less with respect to 100 mass parts of said (A) carboxyl group-containing resin. When the compounding quantity of a thioxanthone compound is 20 mass parts or less, thick film sclerosis | hardenability is favorable and it leads to the cost reduction of a product. More preferably, it is 10 parts by mass or less.

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

  As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because of its low toxicity. Dialkylamino group-containing coumarin compounds have a maximum absorption wavelength in the ultraviolet region of 350 to 410 nm, so they are less colored and use a colored pigment as well as a colorless and transparent cured coating, and a colored cured coating that reflects the color of the colored pigment itself Can be provided. In particular, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

  As a compounding quantity of such a tertiary amine compound, it is preferable that it is 0.1-20 mass parts with respect to 100 mass parts of said (A) carboxyl group-containing resin. When the compounding amount of the tertiary amine compound is 0.1 parts by mass or more, a sufficient sensitizing effect can be obtained. On the other hand, in the case of 20 parts by mass or less, light absorption on the surface of the coating film by the tertiary amine compound becomes good, and the deep curability is improved. More preferably, it is 0.1-10 mass parts.

These photopolymerization initiators, photoinitiator assistants and sensitizers may be used alone or as a mixture of two or more.
The total amount of such photopolymerization initiator, photoinitiator assistant, and sensitizer is preferably 35 parts by mass or less with respect to 100 parts by mass of the (A) carboxyl group-containing resin. In the case of 35 parts by mass or less, it is possible to suppress a decrease in deep part curability due to light absorption.

  In addition, since the above photoinitiators, photoinitiator assistants, and sensitizers absorb a specific wavelength, the sensitivity may be lowered in some cases and may function as an ultraviolet absorber. However, they are not used only for the purpose of improving the sensitivity of the composition. Absorbs light of a specific wavelength as necessary to improve the photoreactivity of the surface, change the resist line shape and opening to vertical, tapered, reverse taper, and processing accuracy of line width and opening diameter Can be improved.

[(C) Organic filler whose surface is coated with silica]
The organic filler (C) whose surface is coated with silica can be used as long as it is fine particles made of a polymer and the surface is coated with silica. The method of silica coating is not particularly limited. The thickness of the silica coating may be such that silicon (Si) can be confirmed by energy dispersive X-ray analysis (EDX). The average particle diameter of the organic filler is not particularly limited as long as it can be used as a filler. A preferable average particle diameter is 0.1 μm to 30 μm, more preferably 0.1 μm to 10 μm, as an average particle diameter obtained from a volume average particle size distribution measurement result measured by a laser diffraction particle size distribution measuring device. is there.
The blending amount of the organic filler whose surface (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. is there.

  Examples of the polymer constituting the organic filler include, for example, polyester polymers, polyurethane polymers, polyester urethane polymers, polyamide polymers, polyester amide polymers, acrylic polymers, cellulose polymers, polylactic acid polymers, and phenoxy polymers. Etc. Further, it may be a hydroxyl group-containing elastomer or another elastomer. Examples include polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyesteramide elastomers, acrylic elastomers, olefin elastomers, epoxy-containing polybutadiene elastomers, and acrylic-containing polybutadiene elastomers. In addition, a resin in which a part or all of epoxy groups of epoxy resins having various skeletons are modified with a carboxylic acid-modified butadiene-acrylonitrile rubber at both ends can be used. These polymers may be used alone or as a mixture of two or more. Among the above polymers, polyurethane-based polymers are preferable, and urethane resins are more preferable.

  The curable resin composition of the present invention may contain a filler other than the organic filler whose surface (C) is coated with silica, if necessary, in order to increase the physical strength of the resulting cured product. it can. As such a filler, publicly known and commonly used inorganic fillers can be used, and barium sulfate, spherical silica and talc are particularly preferably used. In addition, for the purpose of imparting flame retardancy, aluminum hydroxide, magnesium hydroxide, hydrotalcites, boehmite and the like can also be used. Furthermore, NANOCRYL (trade names) XP 0396, XP 0596, XP 0733, XP 0746, XP 0765 manufactured by Hanse-Chemie, in which nano silica is dispersed in a compound having one or more ethylenically unsaturated groups or the above polyfunctional epoxy resin. , XP 0768, XP 0953, XP 0954, XP 1045 (all are product grade names), NANOPOX (trade name) XP 0516, XP 0525, XP 0314 (all are product grade names) manufactured by Hanse-Chemie . These may be used alone or in combination of two or more.

  The blending amount of the filler is preferably 500 parts by mass or less, more preferably 0.1 to 300 parts by mass, and particularly preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. Part. When the compounding quantity of a filler is 500 mass parts or less, the viscosity of a curable resin composition does not become high too much, printability is favorable, and hardened | cured material becomes difficult to become weak.

((D) Flame retardant)
For 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 flame retardant containing no halogen is preferred. As the flame retardant, for example, a phosphorus-containing compound or aluminum hydroxide, magnesium hydroxide, hydrotalcite, boehmite, or the like, which is an inorganic filler that imparts flame retardancy to the curable resin composition, may be blended. Of the flame retardants, phosphorus-containing compounds are preferred. A flame retardant may be used individually by 1 type, and may use 2 or more types together.

（式中、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立に、ハロゲン原子以外の置換基を示す。） Examples of the phosphorus-containing compound include those known as organic phosphorus flame retardants. Among such organic phosphorus flame retardants, preferred are phosphoric acid esters and condensed phosphoric acid esters, phosphorus element-containing (meth) acrylates, phosphorus-containing compounds having phenolic hydroxyl groups, cyclic phosphazene compounds, phosphazene oligomers, phosphines. Examples thereof include acid metal salts and compounds represented by the following general formula (I).

(In the formula, 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 carbon atom optionally substituted by a hydrogen atom or a cyano group. Although it is preferable that it is a C1-C4 alkyl group, a 2, 5- dihydroxyphenyl group, or a 3, 5- di-t-butyl-4-hydroxyphenyl group, it is not limited to this.

  Commercially available products of the phosphorus-containing compound represented by the general formula (I) include HCA, SANKO-220, M-ESTER, HCA-HQ (all are trade names of Sankosha), and the like.

The phosphorus element-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 in the above general formula (I) and Examples include compounds in which R ⁶ is a hydrogen atom and R ⁷ is a (meth) acrylate derivative. Generally, it can be synthesized by a Michael addition reaction between 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a known and commonly used polyfunctional (meth) acrylate monomer.

  Examples of the (meth) acrylate monomer include diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, and propylene glycol; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyania. Polyhydric alcohols such as nurate or polyvalent acrylates such as ethylene oxide adducts, propylene oxide adducts or caprolactone adducts; phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts or propylene oxides of these phenols Polyvalent acrylates such as adducts; and urethane acrylates of the above polyalcohols; Polyglycerides of glycidyl ethers such as diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate; and at least one of melamine acrylate and methacrylates corresponding to the acrylate Is mentioned.

The phosphorus-containing compound having a phenolic hydroxyl group has high hydrophobicity and heat resistance, does not deteriorate electrical characteristics due to hydrolysis, and has high solder heat resistance. Further, as an appropriate combination, when an epoxy resin is used among thermosetting resins, there is an advantage that it does not bleed out after curing because it reacts with the epoxy group and is taken into the network. Among the phosphorus-containing compounds having a phenolic hydroxyl group, preferred are those in which R ⁷ in the general formula (I) is a phenyl group substituted with a hydroxyl group. Commercially available products include HCA-HQ manufactured by Sanko Co., Ltd.

  Phosphorus-containing compounds that are oligomers or polymers have the advantage that there is little decrease in bendability due to the influence of the alkyl chain, and there is no bleedout after curing due to the large molecular weight. Commercially available products include M-Ester-HP manufactured by Sanko Co., Ltd. and phosphorus-containing Byron 337 manufactured by Toyobo Co., Ltd.

  As the phosphazene oligomer, a phenoxyphosphazene compound is effective, and there are a substituted or unsubstituted phenoxyphosphazene oligomer or a trimer, a tetramer, and a pentamer, and there are liquid and solid powders. It can be preferably used. Commercially available products include FP-100, FP-300, and FP-390 manufactured by Fushimi Pharmaceutical. Among these, a phenoxyphosphazene oligomer substituted with an alkyl group or a polar group such as a hydroxyl group or a cyano group is preferable because of its high solubility in a carboxyl group-containing resin and no inconvenience such as recrystallization even when added in a large amount.

Further, as another phosphazene oligomer, at least one of a phosphorus element-containing dicarboxylic acid represented by the following general formula (II) and its anhydride and an acrylate compound are obtained, and one or more in the molecule It is a compound containing (meth) acrylate.

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 and an alkenyl having 1 to 6 carbon atoms. Group, cycloalkyl group and phenyl group. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, secondary butyl group, tertiary butyl group, isobutyl group, pentyl group, isopentyl group, and tertiary pentyl group. Examples of the alkenyl group having 1 to 6 carbon atoms such as hexyl group include vinyl group, allyl group, 3-butenyl group, isobutenyl group, 4-pentenyl group, and 5-hexenyl group. The hydrocarbon group having 1 to 6 carbon atoms may be branched or substituted.

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

As the acrylate compound, an acrylate compound having a functional group that reacts with a carboxyl group or a carboxylic acid anhydride of the dicarboxylic acid or an anhydride thereof is preferable. An acrylate residue 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. Among the functional groups, an epoxy group and a hydroxyl group are more preferable.
A conventionally known reaction method can be used as the reaction method for adding with the functional group.

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

  The amount of the acrylate compound added to the phosphorus element-containing dicarboxylic acid represented by the general formula (II) or its anhydride is not particularly limited, but the phosphorus concentration of the phosphazene oligomer is in the range of 2% to 7%. It is preferable to adjust to an acrylate compound.

By using the phosphorus element-containing dicarboxylic acid represented by the general formula (II) or its anhydride, a phosphazene oligomer having both ends acrylated can be easily obtained. By using the terminal acrylated phosphazene oligomer obtained in this way, it is excellent in flexibility and low warpage, and can be obtained a flame retardant coating that does not cause bleeding out during high temperature pressing. A flame curable resin composition can be obtained.
The phosphazene oligomer is preferably a bifunctional phosphorus element-containing acrylate from the viewpoints of flexibility and low warpage. When the phosphazene oligomer is bifunctional, the heat resistance is good and the decrease in flexibility can be suppressed.
Moreover, the said phosphazene oligomer may be used individually by 1 type, and may use 2 or more types together.

  Moreover, by using a phosphinic acid metal salt, flame retardance can be improved without impairing the flexibility of the cured coating. By using such a phosphinic acid metal salt excellent in heat resistance, the bleed-out of the flame retardant can be suppressed in the hot press during 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, methandi (methylphosphinic acid), benzene-1, 4- (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. Of these, calcium, magnesium, aluminum and zinc are preferable.

  Commercially available phosphinic acid metal salts include EXOLIT OP 930, EXOLIT OP 935 and the like manufactured by Clariant.

  A phosphorus containing compound may be used individually by 1 type, and may use 2 or more types together. The compounding quantity of a phosphorus containing compound is 5-150 weight part with respect to 100 mass parts of said (A) carboxyl group-containing resin, Preferably it is 10-80 mass parts. When the amount is 150 parts by weight or less, the bending properties and the like of the obtained cured coating film are good.

  Aluminum hydroxide may be untreated surface, using a silane coupling agent having a vinyl group or an epoxy group at its end, stearic acid, oleic acid, phosphoric acid ester, etc. Also good. As a commercial item of aluminum hydroxide, Hidegilite H42M, Hidejilite H42S, Hidejilite H42T, Hidejilite H42ST-V manufactured by Showa Denko KK, B1403, B1403ST, B1403T manufactured by Nippon Light Metal Co., Ltd., and the like can be given.

  Magnesium hydroxide may be a natural product or a synthetic product, and may be untreated, a silane coupling agent having a vinyl group or an epoxy group at its terminal, stearic acid, You may use what was surface-treated with oleic acid, phosphoric acid ester, etc. Examples of commercially available magnesium hydroxide include Kisuma 5A, Kisuma 5B, Kisuma 5E, Kisuma 5J, Kisuma 5P, Kisma 5L, Kaluma Chemical, Magnifin H5, Magnifin H7, Magnifin H10, and the like.

  The amount of the inorganic filler that imparts flame retardancy such as aluminum hydroxide or magnesium hydroxide is preferably 500 parts by mass or less, more preferably 0.1 parts per 100 parts by mass of the (A) carboxyl group-containing resin. ˜300 parts by mass, particularly preferably 0.1 to 150 parts by mass. When the compounding quantity of a filler is 500 mass parts or less, the viscosity of a curable resin composition does not become high too much, printability is favorable, and hardened | cured material becomes difficult to become weak.

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

  The blending amount of the epoxy resin having the (E) biphenyl novolak structure is desirably 5 to 100 parts by mass, preferably 10 to 70 parts by mass, in terms of solid content, with respect to 100 parts by mass of the (A) carboxyl group-containing resin. The ratio of parts. In the case of 5 parts by mass or more, sufficient flame retardancy can be imparted. On the other hand, in the case of 100 parts by mass or less, low warpage and flexibility are good.

  Moreover, the curable resin composition of this invention may use another thermosetting component together with the said (E) epoxy resin which has a biphenyl novolak structure for the further heat resistant improvement. Known thermosetting components such as isocyanate compounds, blocked isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, polyfunctional epoxy compounds, polyfunctional oxetane compounds, episulfide resins, etc. Resin can be used. Among these, a preferable thermosetting component is a thermosetting component having at least one of a plurality of cyclic ether groups and cyclic thioether groups (hereinafter abbreviated as cyclic (thio) ether groups) in one molecule. . There are many commercially available thermosetting components having a cyclic (thio) ether group, and various properties can be imparted depending on the structure.

  The thermosetting component having a plurality of cyclic (thio) ether groups in the molecule includes a plurality of either one of the three-, four- or five-membered cyclic ether groups, or the cyclic thioether group, or two kinds of groups in the molecule. For example, a compound having a plurality of epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having a plurality of oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, and having a plurality of thioether groups in the molecule Examples thereof include compounds, that is, episulfide resins.

  Examples of the polyfunctional epoxy compound include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840 manufactured by DIC, Epicron 850, Epicron 1050, Epicron 2055, Epototo YD-011, YD manufactured by Tohto Kasei Co., Ltd. -013, YD-127, YD-128, D.C. E. R. 317, D.E. E. R. 331, D.D. E. R. 661, D.D. E. R. 664, Sumitomo Epoxy ESA-011, ESA-014, ELA-115, ELA-128, manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 330, A.I. E. R. 331, A.I. E. R. 661, A.I. E. R. Bisphenol A type epoxy resin such as 664 (all trade names); jERYL903 manufactured by Mitsubishi Chemical, Epicron 152, Epicron 165 manufactured by DIC, Epototo YDB-400, YDB-500 manufactured by Tohto Kasei Co., Ltd., manufactured by Dow Chemical Of D. E. R. 542, Sumitomo Epoxy ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., A.A. E. R. 711, A.I. E. R. Brominated epoxy resins such as 714 (both trade names); jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. N. 431, D.D. E. N. 438, Epicron N-730, Epicron N-770, Epicron N-865 manufactured by DIC, Epototo YDCN-701, YDCN-704 manufactured by Tohto Kasei Co., Ltd. EPPN-201, EOCN-1025, EOCN manufactured by Nippon Kayaku Co., Ltd. -1020, EOCN-104S, RE-306, Sumitomo Epoxy ESCN-195X, ESCN-220, manufactured by Sumitomo Chemical Co., Ltd. E. R. Novolak type epoxy resins such as ECN-235, ECN-299, etc. (both trade names); Epicron 830 manufactured by DIC, jER807 manufactured by Mitsubishi Chemical Co., Ltd. Epototo YDF-170, YDF-175, YDF-2004 manufactured by Tohto Kasei Co., Ltd. (All trade names) bisphenol F-type epoxy resin; hydrogenated bisphenol A-type epoxy resins such as Epototo ST-2004, ST-2007, ST-3000 (trade name) manufactured by Toto Kasei Co., Ltd .; jER604, Etototo YH-434 manufactured by Tohto Kasei Co., Ltd. Sumitomo Chemical Co., Ltd. Sumi-epoxy ELM-120, etc. (all trade names) glycidylamine type epoxy resin; Hydantoin type epoxy resin; 2021, CY179, etc. (all trade names) alicyclic epoxy resins; Mitsubishi Gakusha made of YL-933, manufactured by Dow Chemical Company of T. E. N. , EPPN-501, EPPN-502, etc. (all trade names) trihydroxyphenylmethane type epoxy resin; Mitsubishi Chemical Corporation YL-6056, YX-4000, YL-6121 (all trade names) Type or biphenol type epoxy resin or a mixture thereof; Nippon Kayaku EBPS-200, ADEKA EPX-30, DIC EXA-1514 (trade name), etc .; bisphenol S type epoxy resin; Bisphenol A novolac type epoxy resin such as jER157S (trade name); tetraphenylolethane type epoxy resin such as jERYL-931 (all trade name) made by Mitsubishi Chemical; TEPIC made by Nissan Chemical Industries (all) Product name) heterocyclic epoxy resin; diglycy such as NOF's Bremer DGT Ruphthalate resin; Tetraglycidylxylenoylethane resin such as ZX-1063 manufactured by Tohto Kasei Co., Ltd .; ESN-190, ESN-360 manufactured by Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750, EXA-4700 manufactured by DIC Naphthalene group-containing epoxy resin; epoxy resin having dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC, EXA-4816, EXA-4822, and EXA-4850 series flexible tough epoxy resin; CP made by NOF Corporation Examples include, but are not limited to, glycidyl methacrylate copolymer epoxy resins such as -50S and CP-50M; and copolymer epoxy resins of cyclohexylmaleimide and glycidyl methacrylate. These epoxy resins can be used alone or in combination of two or more.

  In the case of using other epoxy resins in addition to the epoxy resin having a biphenyl novolak structure, a bifunctional epoxy resin is preferable from the viewpoint of flexibility and low warpage, and further, a bifunctional epoxy resin is used. A powder epoxy resin is preferred from the viewpoint of low warpage.

  Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1,4-bis [(3-methyl -3-Oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, (3-methyl-3-oxetanyl) methyl acrylate, (3-ethyl-3-oxetanyl) In addition to polyfunctional oxetanes such as methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, (3-ethyl-3-oxetanyl) methyl methacrylate and oligomers or copolymers thereof, oxetane alcohol and novolac resin, Poly (p-hydroxystyrene), cardo-type bisphe Lumpur acids, calixarenes, calix resorcin arenes, or the like ethers of a resin having a hydroxyl group such as silsesquioxane and the like. In addition, a copolymer of an unsaturated monomer having an oxetane ring and an alkyl (meth) acrylate is also included.

  Examples of the 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 Tohto Kasei Co., Ltd. Moreover, episulfide resin etc. which replaced the oxygen atom of the epoxy group of the novolak-type epoxy resin with the sulfur atom using the same synthesis method can be used.

  The blending amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is preferably 0.3 to 2.5 equivalents relative to 1 equivalent of the carboxyl group of the (A) carboxyl group-containing resin. More preferably, it is the range which becomes 0.5-2.0 equivalent. When the amount of the thermosetting component having a plurality of cyclic (thio) ether groups in the molecule is 0.3 equivalents or more, carboxyl groups hardly remain in the cured film, and heat resistance, alkali resistance, electrical insulation, etc. are good. It is. On the other hand, when the amount is 2.5 equivalents or less, the low molecular weight cyclic (thio) ether group hardly remains in the dried coating film, and the strength of the cured coating film is good.

  When using the thermosetting component which has a some cyclic | annular (thio) ether group in the said molecule | numerator, 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, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole. Imidazole derivatives such as 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N -Amine compounds such as dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; and phosphorus compounds such as triphenylphosphine. Examples of commercially available products include 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (both trade names of imidazole compounds) manufactured by Shikoku Kasei Kogyo Co., Ltd., and U-CAT (registered by San Apro). Trademarks) 3503N, U-CAT3502T (all are trade names of blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all are bicyclic amidine compounds and salts thereof), and the like. In particular, the present invention is not limited to these, and any epoxy resin or oxetane compound thermosetting catalyst or any one that promotes the reaction of a carboxyl group with at least one of an epoxy group and an oxetanyl group may be used alone or in combination. A mixture of seeds or more may be used. Also, guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine and isocyanuric acid adducts and 2,4-diamino-6-methacryloyloxyethyl-S-triazine and isocyanuric acid adducts can also be used. Is also used in combination with the above thermosetting catalyst.

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

  Examples of the amino resin include amino resins such as melamine derivatives and benzoguanamine derivatives. Examples include methylol melamine compounds, methylol benzoguanamine compounds, methylol glycoluril compounds, and methylol urea compounds. Furthermore, the alkoxymethylated melamine compound, alkoxymethylated benzoguanamine compound, alkoxymethylated glycoluril compound and alkoxymethylated urea compound have the methylol group of the respective methylolmelamine compound, methylolbenzoguanamine compound, methylolglycoluril compound and methylolurea compound. Obtained by conversion to an alkoxymethyl group. The type of the alkoxymethyl group is not particularly limited and can be, for example, a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group, or the like. In particular, a melamine derivative having a formalin concentration which is friendly to the human body and the environment is preferably 0.2% or less.

  Examples of commercially available amino resins include Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, and the like. 1156, 1158, 1123, 1170, 1174, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicalak Mx-750, Mx-032, Mx-270, Mx-280, Mx -290, Mx-706, Mx-708, Mx-40, Mx-31, Ms-11, Mw-30, Mw-30HM, Mw-390, Mw-100LM, 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- Examples include xylylene diisocyanate and 2,4-tolylene dimer. Specific examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4,4-methylenebis (cyclohexyl isocyanate), and isophorone diisocyanate. Specific examples of the alicyclic polyisocyanate include bicycloheptane triisocyanate. In addition, adduct bodies, burette bodies and isocyanurate bodies of the isocyanate compounds mentioned above may be mentioned.

  The blocked isocyanate group contained in the blocked isocyanate compound is a group in which the isocyanate group is protected by reaction with a blocking agent and temporarily deactivated. When heated to a predetermined temperature, the blocking agent is dissociated to produce isocyanate groups.

  As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include isocyanurate type, biuret type, and adduct type. As an isocyanate compound used in order to synthesize | combine a block isocyanate compound, aromatic polyisocyanate, aliphatic polyisocyanate, or alicyclic polyisocyanate is mentioned, for example. Specific examples of the aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate include the compounds exemplified above.

  Examples of the isocyanate blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-palerolactam, γ-butyrolactam and β-propiolactam; Active methylene blocking agents such as ethyl acetoacetate and acetylacetone; 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, benzyl Ether, methyl glycolate, butyl glycolate, diacetone alcohol, Alcohol blocking agents such as methyl acid and ethyl lactate; oxime blocking agents such as formaldehyde oxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, cyclohexane oxime; butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol Mercaptan blocking agents such as methylthiophenol and ethylthiophenol; acid amide blocking agents such as acetic acid amide and benzamide; imide blocking agents such as succinimide and maleic imide; xylidine, aniline, butylamine, dibutylamine, etc. Amine-based blocking agents; imidazole-based blocking agents such as imidazole and 2-ethylimidazole; imine-based blocks such as methyleneimine and propyleneimine Agents and the like.

  The block isocyanate compound may be commercially available, for example, Sumidur BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117. , Desmotherm 2170, Desmotherm 2265 (above, Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, Nihon Polyurethane Industry Co., Ltd., trade name), B-830, B-815, B- 846, B-870, B-874, B-882 (above, Mitsui Takeda Chemicals, trade name), TPA-B80E, 17B-60PX, E402-B80T (above, Asahi Kasei Chemicals, trade name), etc. Can be mentioned. Sumijoules BL-3175 and BL-4265 are obtained using methyl ethyl oxime as a blocking agent.

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

  A urethanization catalyst can be added to the curable resin composition of the present invention in order to accelerate the curing reaction of hydroxyl groups, carboxyl groups, and isocyanate groups. As the urethanization catalyst, one or more urethanization catalysts selected from the group consisting of tin-based catalysts, metal chlorides, metal acetylacetonate salts, metal sulfates, amine compounds, and amine salts are used. It is preferable to do.

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

  The metal chloride is a metal chloride selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu, and Al. For example, cobaltous chloride, ferrous nickel chloride, ferric chloride, and the like. Can be mentioned.

  The metal acetylacetonate salt is a metal acetylacetonate salt selected from the group consisting of Cr, Mn, Co, Ni, Fe, Cu and Al. For example, cobalt acetylacetonate, nickel acetylacetonate, iron acetyl Examples include acetonate.

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

  Examples of the amine compound include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′. , N ", N" -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine, dimorpholinodiethyl ether, N-methylimidazole, dimethylaminopyridine, triazine, N'- (2-hydroxyethyl) -N, N, N′-trimethyl-bis (2-aminoethyl) ether, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethyl -N '-(2-hydroxyethyl) ethylenediamine, N- (2-hydroxyethyl) ) -N, N ', N ", N" -tetramethyldiethylenetriamine, N- (2-hydroxypropyl) -N, N', N ", N" -tetramethyldiethylenetriamine, N, N, N'-trimethyl -N '-(2-hydroxyethyl) propanediamine, N-methyl-N'-(2-hydroxyethyl) piperazine, bis (N, N-dimethylaminopropyl) amine, bis (N, N-dimethylaminopropyl) Isopropanolamine, 2-aminoquinuclidine, 3-aminoquinuclidine, 4-aminoquinuclidine, 2-quinuclidol, 3-quinuclidinol, 4-quinuclidinol, 1- (2′-hydroxypropyl) imidazole, 1 -(2'-hydroxypropyl) -2-methylimidazole, 1- (2'-hydroxyethyl) imida 1- (2′-hydroxyethyl) -2-methylimidazole, 1- (2′-hydroxypropyl) -2-methylimidazole, 1- (3′-aminopropyl) imidazole, 1- (3′- Aminopropyl) -2-methylimidazole, 1- (3′-hydroxypropyl) imidazole, 1- (3′-hydroxypropyl) -2-methylimidazole, N, N-dimethylaminopropyl-N ′-(2-hydroxy) Ethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminopropyl-N ′, N′-bis (2-hydroxypropyl) amine, N, N-dimethylaminoethyl-N ′, N′-bis (2-hydroxyethyl) amine, N, N-dimethylaminoethyl-N ′, N′-bis (2-hydroxypropyl) amine, melamine, and / or benzoguanamine can be used.

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

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

(Coloring agent)
The curable resin composition of the present invention can contain a colorant. As the colorant, conventionally known colorants such as red, blue, green, yellow, purple, orange, brown, white, and black can be used, and any of pigments, dyes, and pigments may be used. Specifically, the color index (CI; issued by The Society of Dyers and Colorists) number is given. However, it is preferable that the colorant does not contain a halogen from the viewpoint of reducing environmental burden and affecting the human body.

Red colorant:
Examples of red colorants include monoazo, diazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. Examples of color index numbers are listed.

Monoazo: 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: Pigment Red 37, 38, 41;
Monoazo lakes: Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57 : 1, 58: 4, 63: 1, 63: 2, 64: 1, 68;
Benzimidazolone series: Pigment Red 171, Pigment Red 175, Pigment Red 176, Pigment Red 185, Pigment Red 208;
Perylenes: Solvent Red 135, Solvent Red 179, Pigment Red 123, Pigment Red 149, Pigment Red 166, Pigment Red 178, Pigment Red 179, Pigment Red 190, Pigment Red 194, Pigment Red 224;
Diketopyrrolopyrrole: Pigment Red 254, Pigment Red 255, Pigment Red 264, Pigment Red 270, Pigment Red 272;
Condensed azo: 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;
Kinacridone series: Pigment Red 122, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209.

Blue colorant:
Blue colorants include phthalocyanine-based and anthraquinone-based pigments, and pigment-based compounds include those classified as Pigment. Specifically, those with the following color index numbers are listed. Can do.
Pigment Blue: Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 16, Pigment Blue 60;
Dye system: Solvent Blue 35, Solvent Blue 63, Solvent Blue 68, Solvent Blue 70, Solvent Blue 83, Solvent Blue 87, Solvent Blue 94, Solvent Blue 97, Solvent Blue 122, Solvent Blue 136, Solvent Blue 67, Solvent Blue 70 Etc. can be used. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Green colorant:
Similarly, there are phthalocyanine, anthraquinone, and perylene types of green colorants. Specifically, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, etc. are used. can do. In addition to the above, a metal-substituted or unsubstituted phthalocyanine compound can also be used.

Yellow colorant:
Examples of the yellow colorant include monoazo series, disazo series, condensed azo series, benzimidazolone series, isoindolinone series, anthraquinone series, and the like, and specific examples include the following colorants.
Monoazo: 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: Pigment Yellow 12, 13, 14, 16, 17, 55, 63, 81, 83, 87, 126, 127, 152, 170, 172, 174, 176, 188, 198;
Condensed azo: Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 128, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 180;
Benzimidazolone series: Pigment Yellow 120, Pigment Yellow 151, Pigment Yellow 154, Pigment Yellow 156, Pigment Yellow 175, Pigment Yellow 181;
Isoindolinone: 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 purple colorant, orange colorant, and brown colorant include Pigment Violet 19, 23, 29, 32, 36, 38, 42; Solvent Violet 13, 36; CIPigment Orange 1, CIPigment Orange 5, CIPigment Orange 13, CIPigment Orange 14, CIPigment Orange 16, CIPigment Orange 17, CIPigment Orange 24, CIPigment Orange 34, CIPigment Orange 36, CIPigment Orange 38, CIPigment Orange 40, CIPigment Orange 43, CIPigment Orange 46, CIPigment Orange 49, CIPigment Orange 51, CIPigment Orange 61, CIPigment Orange 63, CIPigment Orange 64, CIPigment Orange 71, CIPigment Orange 73; CI Pigment Brown 23, CI Pigment Brown 25 etc. are mentioned.

White colorant:
Examples of the white colorant include zinc oxide shown in CIPigment White 4, titanium oxide shown in CIPigment White 6, and zinc sulfide shown in CIPigment White 7. Particularly preferable from the viewpoint of coloring power and non-toxicity. For example, TR-600, TR-700, TR-750, TR-840, Ishihara Sangyo R-550, R-580, R-630, R-820, CR-50 manufactured by Fuji Titanium Industry Co., Ltd. , CR-60, CR-90, CR-97, rutile titanium oxide such as KR-270, KR-310, KR-380 manufactured by Titanium Industry Co., Ltd., TA-100, TA-200, TA- manufactured by Fuji Titanium Industry Co., Ltd. 300, TA-500, A100, A220 manufactured by Ishihara Sangyo Co., Ltd., an anatase type titanium oxide such as KA-15, KA-20, KA-35, KA-90 manufactured by Titanium Industrial Co., Ltd.

Black colorant:
Examples of black colorants include carbon black pigments such as CIPigment Black 6, 7, 9 and 18; graphite pigments such as CIPigment Black 8, 10 and the like; and CIPigment Black 11, 12 and 27 etc. Iron oxide pigments: For example, iron oxide of KN-370 manufactured by Toda Kogyo, 13M titanium black manufactured by Mitsubishi Materials, anthraquinone pigment expressed by CIPigment Black 20, etc., shown by CIPigment Black 13, 25, 29, etc. Cobalt oxide pigments, copper oxide pigments such as CIPigment Black 15 and 28, manganese pigments such as CIPigment Black 14 and 26, antimony oxide pigments such as CIPigment Black 23, CIPigment Examples of suitable pigments include nickel oxide pigments such as Black 30 and the like, perylene pigments represented by CIPigment Black 31 and 32, molybdenum sulfide and bismuth sulfide. These pigments are used alone or in appropriate combination. Particularly preferred is carbon black. For example, carbon black, M-40, M-45, M-50, MA-8, MA-100 manufactured by Mitsubishi Chemical Corporation, and perylene pigments are low among organic pigments. Effective for halogenation.

  A coloring agent can be used individually by 1 type or in combination of 2 or more types. Although the compounding quantity of a coloring agent is not specifically limited, Preferably it is 0.01-10 mass parts with respect to 100 mass parts of (A) carboxyl group-containing resin, More preferably, it is 0.1-7 mass parts. 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 (A) 100 parts by mass of the 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 concealability can be obtained. In order to blacken, the curable resin composition of the present invention may contain only a black colorant as a colorant, but as described above, it is more excellent in concealment property despite excellent resolution. It is preferable to contain 1 or more types of coloring agents other than a black coloring agent and a black coloring agent from the curable resin composition obtained. By blackening with the combination of the colorants, the exposure light for photocuring becomes difficult to be absorbed by the colorant while having sufficient blackness, and the photocuring proceeds sufficiently so that resolution is improved. It is also considered excellent. An example of the colorant combination is carbon black and a combination of 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.

  When blackening only with a black colorant, it is preferable to use a perylene-based black colorant from the viewpoint of resolution.

  Moreover, it can also blacken by the combination of 2 or more types of colorants other than a black colorant.

  Specific examples of each colorant used in combination of two or more colorants other than the black colorant include those described above.

When the curable resin composition of the present invention is black, the L ^* value of the cured product with a color difference meter with respect to the black color tone is preferably 30 or less, and the curable resin composition is applied by dry coating. It is preferable from a viewpoint of concealability and resolution that the light absorbency in wavelength 410nm of a film | membrane (film thickness of 25 micrometers) is 0.5-1.2.
Here, the L ^* value is a value measured by the method described in the performance evaluation of the examples described later.
The absorbance at a wavelength of 410 nm can be measured using an ultraviolet-visible spectrophotometer and an integrating sphere device. In addition, in order to prevent a shift in absorbance due to a shift in coating thickness, the coating thickness is changed in four stages, a graph of coating thickness and absorbance at 410 nm is created, and a dry coating film with a thickness of 25 μm is calculated from the approximate expression. The absorbance of each can be calculated and the respective absorbances can be obtained.

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

(Binder polymer)
In the curable resin composition of the present invention, a conventionally known binder polymer can be used for the purpose of improving the flexibility and the touch drying property of the obtained cured product. As the binder polymer, cellulose-based, polyester-based, and phenoxy resin-based polymers are preferable. Examples of the cellulose-based polymer include cellulose acetate butyrate (CAB) and cellulose acetate propionate (CAP) series manufactured by Eastman Co., Ltd., a polyester-based polymer byron series manufactured by Toyobo, and a phenoxy resin-based polymer including bisphenol A Bisphenol F and phenoxy resins of their 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 (A) carboxyl group-containing resin. When the blending amount of the binder polymer is 50 parts by mass or less, the alkali developability of the curable resin composition becomes good and the usable potable 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 one or more ethylenically unsaturated groups in the molecule can be used. The photopolymerizable monomer is photocured by irradiation with active energy rays to insolubilize or assist insolubilization of the above (A) carboxyl group-containing resin in an alkaline aqueous solution.

  Examples of the compound used as the photopolymerizable monomer in the present invention include conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, and epoxy (meth) acrylate. It is done. Specifically, 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; N, N-dimethylacrylamide Acrylamides such as N-methylol acrylamide and N, N-dimethylaminopropyl acrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or the like; Polyhydric acrylates such as lenoxide adducts, propylene oxide adducts, or ε-caprolactone adducts; polyvalent acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide or propylene oxide adducts of these phenols Acrylates: glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyglycerides of glycidyl ether such as triglycidyl isocyanurate; not limited to the above, polyether polyol, polycarbonate diol, hydroxyl-terminated polybutadiene, Directly acrylated polyol such as polyester polyol, or urethane acrylate via diisocyanate Acrylates and melamine acrylates, and at least one of each methacrylate corresponding to the acrylate may be used. Moreover, as urethane (meth) acrylate, organic isocyanate, (meth) acrylate monomer having at least one hydroxyl group in the molecule, a reaction product obtained by reacting by a known method, or the organic isocyanate, 1 In addition to the (meth) acrylate monomer having at least one hydroxyl group in the molecule, a reaction product obtained by reacting a polyol having two or more hydroxyl groups in one molecule by a known method may be used.

  Further, an epoxy acrylate resin obtained by reacting acrylic acid with a polyfunctional epoxy resin such as a cresol novolac type epoxy resin, or a hydroxy acrylate such as pentaerythritol triacrylate and a diisocyanate such as isophorone diisocyanate on the hydroxyl group of the epoxy acrylate resin. An epoxy urethane acrylate compound obtained by reacting a half urethane compound may be used as a photopolymerizable monomer. Such an epoxy acrylate resin can improve photocurability without deteriorating the touch drying property.

  In particular, in the present invention, polyhydric acrylates such as polyhydric alcohols or their ethylene oxide adducts, propylene oxide adducts, or ε-caprolactone adducts, and polyphenols such as ethylene oxide adducts or propylene oxide adducts of phenols. Can be suitably used from the viewpoint of low warpage and bendability.

  The compounding amount of the compound having one or more ethylenically unsaturated groups in the molecule used as the photopolymerizable monomer is preferably 5 to 100 mass with respect to 100 mass parts of the (A) carboxyl group-containing resin. Part, more preferably 5 to 70 parts by weight. When the said compounding quantity is 5 mass parts or more, photocurability is favorable and pattern formation becomes easy by the alkali image development after active energy ray irradiation. On the other hand, when the amount is 100 parts by mass or less, the solubility in an alkaline aqueous solution is improved, and the coating film is suppressed from becoming brittle.

(Coupling agent)
Any conventionally known coupling agent can be used in the present invention. The coupling agent can be selected from aluminate, titanate, zirconate, silane, and the like, and silane is most preferable.

  Examples of the aluminate coupling agent include acetoalkoxy aluminum diisopropylate, aluminum diisopropoxy monoethyl acetoacetate, aluminum trisethyl acetoacetate, aluminum trisacetylacetonate and the like.

  Titanate coupling agents include isopropyl tristearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl / aminoethyl) titanate, tetraoctyl bis (ditridecyl phosphate) titanate, tetra (2-2 -Diallyloxymethyl-1-butyl) bis (ditridecyl) phosphate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate and the like.

  Examples of the zirconate coupling agent include zirconium tetrakisacetylacetonate, zirconium dibutoxybisacetylacetonate, zirconium tetrakisethylacetoacetate, zirconium tributoxymonoethylacetoacetate, zirconium tributoxyacetylacetonate and the like.

  Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, Examples include 3-methacryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane.

  The addition amount of the coupling agent is preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the (A) carboxyl group-containing resin. More preferably, it is 0.1-3 mass parts. When the addition amount is 0.05 parts by mass or more, a sufficient wet dispersion effect can be obtained for the organic or inorganic filler, and when it is 5 parts by mass or less, a decrease in tackiness 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 resulting cured product and improving the brittleness of the cured product. Examples of the elastomer include polyester elastomers, polyurethane elastomers, polyester urethane elastomers, polyamide elastomers, polyesteramide elastomers, acrylic elastomers, and olefin elastomers. Moreover, the resin etc. which modified the one part or all part of the epoxy resin which has various frame | skeleton with the both-ends carboxylic acid modified butadiene-acrylonitrile rubber | gum can be used. Furthermore, epoxy-containing polybutadiene elastomers, acrylic-containing polybutadiene elastomers, hydroxyl group-containing polybutadiene elastomers, hydroxyl group-containing isoprene elastomers and the like can also be used. One type of elastomer may be used alone, or a mixture of two or more types may be used.

(Adhesion promoter)
In the curable resin composition of the present invention, an adhesion promoter can be used in order to improve the adhesion between layers or the adhesion between the resin composition layer and the substrate. Examples of the adhesion promoter include benzimidazole, benzoxazole, benzthiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzthiazole, 3-morpholinomethyl-1-phenyl-triazole-2-thione, Examples include 5-amino-3-morpholinomethyl-thiazole-2-thione, 2-mercapto-5-methylthio-thiadiazole, triazole, tetrazole, benzotriazole, carboxybenzotriazole, amino group-containing benzotriazole, and silane coupling agents.

(Antioxidant)
In many polymer materials, once oxidation starts, oxidative degradation occurs one after another in a chain, resulting in a decrease in the function of the polymer material. Therefore, the curable resin composition of the present invention has a (1) ) Antioxidants such as radical scavengers that invalidate the generated radicals and / or (2) peroxide decomposers that decompose the generated peroxides into harmless substances and prevent the generation of new radicals. An agent can be added.

  Specific compounds of antioxidants that function as radical scavengers include hydroquinone, 4-tert-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2 , 2-methylene-bis- (4-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5- Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5-tris (3 ′, 5′di-t-butyl-4-hydroxybenzyl) ) -S-triazine-2,4,6- (1H, 3H, 5H) trione and other phenolic compounds, quinone compounds such as metaquinone and benzoquinone, bis (2,2,6,6-te And amine compounds such as tramethyl-4-piperidyl) -sebacate and phenothiazine.

  The radical scavenger may be commercially available, for example, ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STAB LA-68, ADK STAB LA-87 (above, manufactured by ADEKA, trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN S Japan 5100, manufactured by TINUVIN S ) And the like.

  Specific examples of the antioxidant that acts as a peroxide decomposer include phosphorus compounds such as triphenyl phosphite, pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3,3 ′. -Sulfur compounds such as thiodipropionate.

  The peroxide decomposing agent may be commercially available, for example, ADK STAB TPP (manufactured by ADEKA, trade name), Mark AO-412S (manufactured by ADEKA, trade name), Sumilizer TPS (manufactured by Sumitomo Chemical Co., Ltd., commodity) Name).

  Said antioxidant may be used individually by 1 type, and may be used in combination of 2 or more type.

(UV absorber)
Since the polymer material absorbs light and thereby decomposes and deteriorates, the curable resin composition of the present invention contains an ultraviolet absorber in addition to the above-mentioned antioxidants in order to take a countermeasure against stabilization against ultraviolet rays. Can be used.
Examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, benzotriazole derivatives, triazine derivatives, benzothiazole derivatives, cinnamate derivatives, anthranilate derivatives, dibenzoylmethane derivatives, and the like. Specific examples of benzophenone derivatives include 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, and 2,2′-dihydroxy-4-methoxybenzophenone. And 2,4-dihydroxybenzophenone and the like; specific examples of benzoate derivatives include 2-ethylhexyl salicylate, phenyl salicylate, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl -3,5-di-t-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate; specific examples of benzotriazole derivatives include 2- (2'- Hydroxy-5'-tert-butylphenyl) benzotriazole, 2 (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2 ′ -Hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-3' , 5'-di-t-amylphenyl) benzotriazole; Examples of specific triazine derivatives include hydroxyphenyl triazine, bisethylhexyloxyphenol methoxyphenyl triazine, and the like.

Ultraviolet absorbers may be commercially available, for example, TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (above, manufactured by BASF Japan Ltd., trade name).
Said ultraviolet absorber may be used individually by 1 type, and can also be used in combination of 2 or more type. By using together with the above antioxidant, the cured coating obtained from the curable resin composition of the present invention can be stabilized.

(Other additives)
If necessary, the curable resin composition of the present invention may be a known conventional thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butylcatechol, pyrogallol, phenothiazine, fine powder silica, organic bentonite, montmorillonite, and the like. At least one of conventional thickeners, silicone-based, fluorine-based, polymer-based antifoaming agents and leveling agents, imidazole-based, thiazole-based, triazole-based silane coupling agents, rust preventives, etc. Such known and commonly used additives can be blended.

  The thermal polymerization inhibitor can be used to prevent unintentional thermal polymerization or temporal polymerization of the curable resin composition. Examples of thermal polymerization inhibitors include 4-methoxyphenol, hydroquinone, alkyl or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, 2-hydroxybenzophenone, 4-methoxy-2-hydroxybenzophenone, cuprous chloride, phenothiazine, chloranil. , Naphthylamine, β-naphthol, 2,6-di-tert-butyl-4-cresol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), pyridine, nitrobenzene, dinitrobenzene, picric acid, 4 -Toluidine, methylene blue, copper and organic chelating agent reactant, methyl salicylate, and phenothiazine, nitroso compound, chelate of nitroso compound and Al, and the like.

(Organic solvent)
Furthermore, the curable resin composition of the present invention uses an organic solvent for the synthesis of the above (A) carboxyl group-containing resin and the preparation of the composition, or for adjusting the viscosity for application to a substrate or a carrier film. be able to.

  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; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl Glycol ethers such as ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate , Esters such as propylene glycol butyl ether acetate; ethanol, propano , Ethylene glycol, alcohols such as propylene glycol; octane, aliphatic hydrocarbons decane; petroleum ether is petroleum naphtha, hydrogenated petroleum naphtha, and petroleum solvents such as solvent naphtha. Such an organic solvent may be used individually by 1 type, and may be used as a 2 or more types of mixture.

  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 for a solder resist or an interlayer insulating layer.

The curable resin composition of this invention can also be made into the form of the dry film provided with the carrier film (support body) and the layer which consists of the said curable resin composition formed on this carrier film.
When forming a dry film, the curable resin composition of the present invention is diluted with the above organic solvent to adjust to an appropriate viscosity, and is applied to a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater. A film can be obtained by applying a uniform thickness on a carrier film with a gravure coater, spray coater or the like, and drying usually at a temperature of 50 to 130 ° C. for 1 to 30 minutes. Although there is no restriction | limiting in particular about a coating film thickness, Generally, it is 10-150 micrometers by the film thickness after drying, Preferably it selects suitably in the range of 20-60 micrometers.

  As the carrier film, a plastic film is used, and a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, or a polystyrene film is preferably used. Although there is no restriction | limiting in particular about the thickness of a carrier film, Generally, it selects suitably in the range of 10-150 micrometers.

After the curable resin composition of the present invention is formed on the carrier film, a peelable cover film may be laminated on the film surface for the purpose of preventing dust from adhering to the film surface. preferable.
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, and when the cover film is peeled off, the adhesive strength between the film and the carrier film is exceeded. What is necessary is just to have a smaller adhesive force between the membrane and the cover film.

  The curable resin composition of the present invention is adjusted to a viscosity suitable for a coating method using, for example, the above organic solvent, and on a substrate, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, A tack-free coating film can be formed by applying the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. by volatile drying (preliminary drying) at a temperature of about 60 to 100 ° C. Further, in the case of a dry film obtained by applying the above composition on a carrier film and drying and winding it as a film, after laminating the curable resin composition layer on the substrate with a laminator or the like The resin insulating layer can be formed by peeling off the carrier film.

  Examples of the base material include printed circuit boards and flexible printed circuit boards in which circuits are formed in advance, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth / paper epoxy, synthetic fiber. Copper graded laminates of all grades (FR-4 etc.) and other polyimides using materials such as epoxy, fluorine, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate ester, etc. A film, a PET film, a glass substrate, a ceramic substrate, a wafer plate, etc. can be mentioned.

  Volatile drying performed after the application of the curable resin composition of the present invention is performed using hot air circulation drying oven, IR oven, hot plate, convection oven, etc. Can be carried out by using a counter-current contact method and a method of spraying a nozzle on a support.

  When the curable resin composition of the present invention contains a thermosetting component, for example, by heating to a temperature of about 140 to 180 ° C. and thermosetting, the (A) carboxyl group of the carboxyl group-containing resin, A thermosetting component reacts to form a cured coating film excellent in various properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical characteristics.

  In the case of containing a photopolymerization initiator and a photopolymerizable monomer, the exposed portion (active energy ray) is obtained by performing exposure (irradiation of active energy rays) on the coating film obtained after coating and volatile drying of the solvent. The portion irradiated by (3) is cured. Further, by a contact method (or non-contact method), exposure is selectively performed with an active energy ray through a photomask having a pattern formed thereon or direct pattern exposure is performed by a laser direct exposure machine, and an unexposed portion is diluted with a dilute alkaline aqueous solution (for example, 0.3 The resist pattern is formed by development with a 3 wt% sodium carbonate aqueous solution.

As an exposure machine used for the active energy ray irradiation, a high-pressure mercury lamp lamp, an ultra-high pressure mercury lamp lamp, a metal halide lamp, a mercury short arc lamp, and the like may be used as long as the apparatus irradiates ultraviolet rays in a range of 350 to 450 nm. Furthermore, a direct drawing apparatus (for example, a laser direct imaging apparatus that directly draws an image with a laser using CAD data from a computer) can also be used. As a laser light source of the direct drawing machine, either a gas laser or a solid laser may be used as long as laser light having a maximum wavelength in the range of 350 to 410 nm is used. The amount of exposure for image formation varies depending on the film thickness and the like, but is generally 20 to 800 mJ / cm ² , preferably 20 to 600 mJ / cm ² .

  The developing method can be a dipping method, a shower method, a spray method, a brush method, etc., and as a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, Alkaline aqueous solutions such as ammonia and amines can be used.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not restrict | limited by an Example and a comparative example. In addition, the part showing a compounding quantity is a mass part unless there is particular description.

(Synthesis or preparation of carboxyl group-containing resin)
[A-1: Preparation of a resin corresponding to the carboxyl group-containing resin (8)]
It corresponds to the carboxyl group-containing resin (8) and contains a photosensitive group and a photosensitive carboxyl group-containing resin using a bisphenol F type polyfunctional epoxy [ZFR-1401H manufactured by Nippon Kayaku Co., Ltd. (solid content: 65%, as resin) The acid value of 98 mgKOH / g) was used. The varnish is hereinafter referred to as A-1.

[A-2: Synthesis of resin corresponding to the carboxyl group-containing resin (5)]
In a reaction vessel equipped with a stirrer, a thermometer, and a condenser, 2400 g (3 of polycarbonate diol derived from 1,5-pentanediol and 1,6-hexanediol (manufactured by Asahi Kasei Chemicals, 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. Next, 1887 g (8.5 mol) of isophorone diisocyanate was added as a polyisocyanate, and the mixture was stopped by heating to 60 ° C. while stirring. When the temperature in the reaction vessel began to decrease, the mixture was heated again and stirred at 80 ° C. The reaction was terminated after confirming that the absorption spectrum of the isocyanate group (2280 cm ⁻¹ ) had disappeared in the infrared absorption spectrum. Carbitol acetate was added so that the solid content was 50% by 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: Preparation of resin corresponding to carboxyl group-containing resin (4)]
Corresponding to the carboxyl group-containing resin (4), a carboxyl group-containing resin containing a photosensitive group and having a urethane structure [UXE-3000 manufactured by Nippon Kayaku Co., Ltd. (solid content 65%, acid value as a resin is 98 mgKOH / g) ] Was used. The varnish is hereinafter referred to as A-3.

[A-4: Preparation of resin corresponding to the carboxyl group-containing resin (7)]
It corresponds to the carboxyl group-containing resin (7) and is a photosensitive carboxyl group-containing resin using a polyfunctional epoxy of a biphenyl novolac type containing a photosensitive group [ZCR-1601H manufactured by Nippon Kayaku Co., Ltd. (solid content: 65%, as resin) The acid value of 98 mgKOH / g) was used. The varnish is hereinafter referred to as A-4.

[Synthesis example of urethane acrylate]
A reaction vessel immersed in an oil bath and equipped with a stirring blade, a thermometer, an addition funnel and a dry air supply port was charged with 336 g (2 mol) of 1,6-hexamethylene diisocyanate (HDI) and 0.05 g of stannous chloride. When isophorone diisocyanate (IPDI) reached 70 ° C., 530 g (1 mol) of polycaprolactone [Placcel 205, polycaprolactone diol having a molecular weight of 530 / manufactured by Daicel Chemical Industries, Ltd.] was added from the addition funnel. After the addition, a polycaprolactone urethane prepolymer is produced by keeping the temperature in the reaction vessel at 70 ° C. until the residual NCO concentration reaches a theoretical value. Thereafter, 232 g (2 mol) of 2-hydroxyethyl acrylate (HEA) was added, and then the inside of the reaction vessel was kept at 70 ° C. until it was confirmed that the residual NCO concentration in the sample withdrawn from the reaction product was 0.1% or less. Keep aging and ripen. Thereby, urethane acrylate F was obtained.

[Examples 1 to 13, Comparative Examples 1 to 4]
The above resin solution (varnish) is blended in the proportions (parts by mass) shown in Table 1 together with various components shown in Table 1, premixed with a stirrer, kneaded with a three-roll mill, and curable resin composition A product was prepared. Here, it was 15 micrometers or less when the dispersion degree of each obtained curable resin composition was evaluated by the particle size measurement by the grindometer by Eriksen.

＊１：ビフェニルノボラック構造を有するエポキシ樹脂のカルビトールアセテート溶液（固形分７５％）日本化薬社製ＮＣ−３０００−Ｈ−ＣＡ７５
＊２：ビキシレノール型エポキシ樹脂、三菱化学社製
＊３：ビスフェノールＡ型エポキシ樹脂、三菱化学社製
＊４：表面がシリカで覆われていない有機フィラー、岐阜セラック社製ＢＰ−０１−５
＊５：表面がシリカで覆われている有機フィラー、根上工業社製ＡＫ−８００ＴＲ
＊６：大塚化学社製ＳＰＥ−１００
＊７：クラリアント社製エクソリットＯＰ９３５
＊８：昭和電工社製ＨＦＡ−６０６５Ｅ
＊９：昭和電工社製ハイジライトＨ−４２Ｍ
＊１０：ＢＡＳＦジャパン社製ルシリン ＴＰＯ
＊１１：ＢＡＳＦジャパン社製イルガキュア３８９
＊１２：ＢＡＳＦジャパン社製イルガキュアＯＸＥ−０２
＊１３：新中村化学社製ＢＰＥ−５００
＊１４：日本化薬社製ＤＰＣＡ−６０
＊１５：日本化薬社製ＵＸ−２２０１
＊１６：信越シリコーン社製 ＫＢＭ−４０３
＊１７：石原産業社製ＣＲ−９７
＊１８：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：３
＊１９：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １４７
＊２０：信越シリコーン社製ＫＳ−６６
＊２１：ジプロピレングリコールモノメチルエーテル

* 1: Carbitol acetate solution of epoxy resin having biphenyl novolac structure (solid content: 75%) NC-3000-H-CA75 manufactured by Nippon Kayaku Co., Ltd.
* 2: Bixylenol type epoxy resin, manufactured by Mitsubishi Chemical Corporation * 3: Bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation * 4: Organic filler whose surface is not covered with silica, BP-01-5 manufactured by Gifu Shellac Co., Ltd.
* 5: Organic filler whose surface is covered with silica, AK-800TR manufactured by Negami Kogyo Co., Ltd.
* 6: SPE-100 manufactured by Otsuka Chemical Co., Ltd.
* 7: Clariant Exolit OP935
* 8: Showa Denko HFA-6065E
* 9: Showa Denko Hijilite H-42M
* 10: Lucilin TPO manufactured by BASF Japan
* 11: BASF Japan Irgacure 389
* 12: Irgacure OXE-02 manufactured by BASF Japan
* 13: Shin-Nakamura Chemical BPE-500
* 14: DPCA-60 manufactured by Nippon Kayaku Co., Ltd.
* 15: UX-2201 manufactured by Nippon Kayaku Co., Ltd.
* 16: Shin-Etsu Silicone KBM-403
* 17: CR-97 manufactured by Ishihara Sangyo Co., Ltd.
* 18: C.I. I. Pigment Blue 15: 3
* 19: C.I. I. Pigment Yellow 147
* 20: Shin-Etsu Silicone KS-66
* 21: Dipropylene glycol monomethyl ether

Performance evaluation:
<Optimum exposure amount>
The circuit pattern substrate having a copper thickness of 35 μm was polished with buffalo, washed with water, dried, and then applied to the entire surface by a screen printing method. Let dry for minutes. Exposure is performed through a step tablet (Kodak No. 2) using an exposure apparatus (HMW-680-GW20) equipped with a metal halide lamp, and development (30 ° C., 0.2 MPa, 1 wt% Na ₂ CO ₃ aqueous solution) is performed for 60 seconds. The amount of exposure of the step tablet remaining when the step was performed was determined as the optimum exposure amount.

<Appearance evaluation method>
The compositions of each of the above Examples and Comparative Examples were applied onto the patterned polyimide film substrate by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. The obtained substrate is exposed to a solder resist pattern at an optimum exposure amount 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. is applied at a spray pressure of 2 kg / cm ² . Development was performed under conditions for 60 seconds to obtain a resist pattern. This substrate was cured by heating at 150 ° C. for 60 minutes. The obtained printed circuit board (evaluation board) was sandwiched between cushion materials and a SUS plate was used to give a load of 20 kgf / cm ² and vacuum pressing was performed at 150 ° C. for 60 minutes. The surface of the substrate after pressing was visually observed, and the appearance was evaluated according to the following criteria.
○: No appearance defect on the coating film surface and the cushion material contact portion during pressing.
X: Appearance defects on the coating film surface and the cushion material contact portion during pressing.

<Flexibility (fold resistance)>
The compositions of the above Examples and Comparative Examples were applied to the entire surface of a 25 μm thick polyimide film (Kapton 100H manufactured by Toray DuPont) by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature. The obtained substrate is exposed to a resist pattern with an optimal exposure amount 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. is sprayed at a pressure of 0.2 MPa. Development was performed for 60 seconds to obtain a resist pattern, and this substrate was cured by heating at 150 ° C. for 60 minutes.
The obtained evaluation substrate was subjected to 180 ° folding by goblet folding several times, and the occurrence of cracks in the coating film at that time was observed visually and with a 200-fold optical microscope until cracks were generated. The number of bendings was measured and evaluated according to the following criteria.
A: The number of times of bending is 6 times or more.
○: The number of bending is 4 to 5 times.
(Triangle | delta): The frequency | count of bending is 2-3 times.
X: The number of times of bending is 0 to 1 times.

<Low warpage>
A sample prepared in the same manner as the sample for evaluation of flexibility (folding resistance) was cut into 50 mm × 50 mm □, and the average value was obtained by measuring the four corners, and evaluated according to the following criteria.
○: The warp is less than 4 mm.
(Triangle | delta): The curvature is 4 mm or more and less than 8 mm.
X: The warp is 8 mm or more.

<Insulation reliability>
The compositions of the above Examples and Comparative Examples were applied to the entire surface of a polyimide substrate (Espanex manufactured by Nippon Steel Chemical Co., Ltd.) with L / S = 50/50 μm by screen printing, dried at 80 ° C. for 30 minutes, and room temperature. It was left to cool. The obtained substrate is exposed to a resist pattern with an optimal exposure amount 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. is sprayed at a pressure of 0.2 MPa. Development was performed for 60 seconds to obtain a resist pattern, and this substrate was cured by heating at 150 ° C. for 60 minutes. A bias voltage of DC 50 V was applied to the obtained evaluation substrate, and 85 ° C., 85% R.D. H. The resistance value was confirmed by continuous measurement in a constant temperature and humidity chamber. The judgment criteria are as follows.
○: No occurrence of short circuit and discoloration of copper foil after 1000 hours.
Δ: No short circuit occurred after 1000 hours, but there was discoloration of the copper foil.
×: Short circuit occurred within 1000 hours.
The results of each evaluation test are summarized in Table 1.

<Flame retardance>
The composition of each of the above examples was applied to the entire surface of a polyimide film having a thickness of 25 μm and a thickness of 12.5 μm (manufactured by Toray DuPont, Kapton 100H (25 μm), Kapton 50H (12.5 μm)) at 30 ° C. The mixture was dried and allowed to cool to room temperature. Further, the entire back surface was similarly applied by screen printing, dried at 80 ° C. for 30 minutes, and allowed to cool to room temperature to obtain a double-side coated substrate. The obtained double-sided substrate was exposed to the entire surface of the solder resist with an optimal exposure amount 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 at a pressure of 2 kg / cm ^2. Development was performed for 60 seconds under the above conditions, and thermosetting was performed at 150 ° C. for 60 minutes to obtain an evaluation sample. This flame retardant evaluation sample was subjected to a thin material vertical combustion test based on the UL94 standard. As a result of the flame retardancy test, VTM-0 was evaluated as ◯, VTM-1 was evaluated as Δ, and rejection was evaluated as ×.
Table 2 shows the results of the evaluation tests.

[Examples 14 to 23]
A curable resin composition prepared by adding the curable resin compositions of Examples 1 to 10 shown in Table 1 without adding a silicone-based antifoaming agent was diluted with methyl ethyl ketone, applied onto a carrier film (PET), and heated. It dried and formed the photosensitive resin composition layer of thickness 20 micrometers, and bonded the cover film (PE) on it and obtained the dry film. Thereafter, the cover film was peeled off, and the film was bonded to the patterned copper foil substrate using a laminator to prepare a test substrate. In the same manner as the test method and the evaluation method described above, an evaluation test of each characteristic was performed. The dry film according to the composition of Example 1 is Example 14, the composition of Example 2 is Example 15, the composition of Example 3 is Example 16, the composition of Example 4 is Example 17, and the composition of Example 5 The composition of Example 18, Example 6 is Example 19, the composition of Example 7 is Example 20, the composition of Example 8 is Example 21, the composition of Example 9 is Example 22, and the composition of Example 10 Corresponds to Example 23, respectively. The results are shown in Tables 3 and 4 below.

[Examples 24-31, Comparative Examples 5-7]
The above resin solution (varnish) is blended in the proportions (parts by mass) shown in Table 5 together with various components shown in Table 5, premixed with a stirrer, kneaded with a three-roll mill, and curable resin composition A product was prepared. Here, it was 15 micrometers or less when the dispersion degree of each obtained curable resin composition was evaluated by the particle size measurement by the grindometer by Eriksen.

＊２２：三菱化学社製ＭＡ−１００
＊２３：ジケトピロロール系赤色着色剤
＊２４：Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌａｃｋ ３１

* 22: MA-100 manufactured by Mitsubishi Chemical Corporation
* 23: Diketopyrrole red colorant * 24: C.I. I. Pigment Black 31

Performance evaluation:
In the same manner as in the test method and the evaluation method described above, evaluation tests for optimum exposure amount, resolution, appearance, flexibility, low warpage, and insulation reliability were performed. Moreover, L ^* value, resolution, and concealment were evaluated by the following evaluation methods. The results are shown in Table 5.

<L ^* value>
The curable resin compositions of Examples 24 to 31 and Comparative Examples 5 to 7 were each coated on a copper-clad substrate by screen printing, dried at 80 ° C. for 30 minutes in a hot-air circulating oven, and then wavelength 365 nm Were exposed to a light amount of 500 mJ / cm ² on the resist using an integrating light meter manufactured by Oak Manufacturing Co., Ltd. and exposed. Thereafter, development was performed with a 1 mass% Na ₂ CO ₃ aqueous solution having a spray pressure of 0.2 MPa for 60 seconds, and then a heat-curing treatment was performed at 150 ° C. for 60 minutes using a hot-air circulating drying oven to obtain a cured coating film. For the cured coating film thus obtained, the L ^* a ^* b ^* color system value on copper was measured according to JIS Z 8729 using the following color difference meter, and L ^* value which is an index representing lightness. Was evaluated as an index of blackness. A smaller L ^* value means better blackness.
Color difference meter: 45 ° ring illumination vertical light receiving high-performance color difference meter (CR-221 manufactured by Konica Minolta)

<Resolution>
The curable resin compositions of Examples 24 to 31 and Comparative Examples 4 to 6 were applied by screen printing onto a copper-clad substrate on which a circuit was formed, and dried at 80 ° C. for 30 minutes in a hot air circulation type drying furnace. An ultraviolet ray having a wavelength of 365 nm was irradiated with light of 500 mJ / cm ² on the resist through a photomask (having a line of 30 to 120 μm) using an integrating photometer manufactured by Oak Manufacturing Co., Ltd. and exposed. Next, development was carried out with a 1 mass% Na ₂ CO ₃ aqueous solution having a spray pressure of 0.2 MPa for 60 seconds, and the line remaining and the space slippage at the exposed area were visually determined. The case where 50 μm was missing was evaluated as “◯”, and the case where it was not missing was evaluated as “X”.

<Concealment>
The substrate manufactured with the above resolution was heated at 150 ° C. for 60 minutes. The color change of the copper circuit of the part coat | covered with the soldering resist was confirmed visually, and the following references | standards evaluated.
○: The discolored portion of the copper circuit is not known.
(Triangle | delta): The discolored part of a copper circuit is understood slightly.
X: The discolored part of the copper circuit can be seen.

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

From the results shown in Tables 1 to 6, the cured products obtained from the curable resin compositions or dry films of Examples 1 to 31 have good flexibility, low warpage, and insulation reliability, and It can be seen that the appearance defects are suppressed. Moreover, those hardened | cured materials are excellent also in the flame retardance, and especially the curable resin composition or dry matter of Examples 1-10 and 14-31 containing the phosphorus containing compound and the epoxy resin which has a biphenyl novolak structure. It turns out that the hardened | cured material obtained from the film has the more outstanding flame retardance. It can be seen that the curable resin compositions of Examples 24-31 are excellent in resolution despite being black, and the cured products obtained from these are excellent in concealment. In particular, the cured products obtained from the curable resin compositions of Examples 24-29 containing a black colorant and one or more colorants other than the black colorant have better concealing properties. I understand that.
On the other hand, the comparative example 1 which does not contain the silica-coated organic filler was inferior in appearance, flexibility and low warpage. Similarly, Comparative Example 2 is inferior in appearance and flexibility, Comparative Example 3 is inferior in appearance, and Comparative Example 4 is inferior in appearance, flexibility, and low warpage. . Comparative Example 5 is inferior in appearance, flexibility and low warpage, Comparative Example 6 is inferior in appearance and flexibility, and Comparative Example 7 is in appearance, flexibility and low warpage. It was inferior.

Claims (11)

(A) a carboxyl group-containing resin,
(B) a photopolymerization initiator, and
(C) containing an organic filler whose surface is coated with silica , and
(C) The curable resin composition, wherein the organic filler whose surface is coated with silica is a urethane resin whose surface is coated with silica .   The carboxyl group-containing resin (A) is a carboxyl having one or more partial structures selected from the group consisting of a bisphenol A structure, a bisphenol F structure, a biphenol structure, a biphenol novolak structure, a bisxylenol structure, a biphenyl novolak structure, and a urethane structure. The curable resin composition according to claim 1, which is a group-containing resin. Furthermore, (D) a flame retardant is contained, The curable resin composition of Claim 1 or 2 characterized by the above-mentioned. The curable resin composition according to claim 3 , wherein the flame retardant (D) is a phosphorus-containing compound. The cured resin composition according to claim 4 , wherein the phosphorus-containing compound is a phenoxyphosphazene oligomer or a phosphinic acid metal salt. Furthermore, (E) the epoxy resin which has a biphenyl novolak structure is contained, The cured resin composition as described in any one of Claims 1-5 characterized by the above-mentioned. It is an object for solder resist formation, The curable resin composition as described in any one of Claims 1-6 characterized by the above-mentioned. The curable resin composition of any one of claims 1-7, characterized in that the black. A dry film obtained by applying and drying the curable resin composition according to any one of claims 1 to 8 on a film. The curable resin composition according to any one of claims 1 to 8 , or a dry film obtained by applying and drying the curable resin composition on a film is subjected to at least one of thermosetting and photocuring. A cured film obtained by the method.   A printed wiring board comprising the cured coating according to claim 10.