TWI533085B - A hardened resin composition, a dry film, a hardened product, and a display member - Google Patents

Description

Curable resin composition, dry film, cured product, and display member

The present invention relates to a curable resin composition (hereinafter sometimes referred to simply as "composition"), a dry film, a cured product, and a display member.

In a mobile phone or a product having a liquid crystal display unit such as a display, the touch panel surrounding the display area is hidden, and the material forming the baffle (frontal area) is required to have high light-shielding property, that is, to have a high OD value (OD3 or more). Therefore, a black resin composition containing a carbon black pigment is generally used in the past (Patent Documents 1, 2, and 3). However, since the carbon black pigment can reach a high OD value, the composition added at a high concentration tends to deteriorate in insulation, and for example, it is not suitable for directly forming a conductive portion by a baffle plate coated by a touch panel. The use of the film. Further, from the viewpoint of the photosensitive material, the carbon black pigment exhibits absorbability in a wide wavelength range from the ultraviolet region to the infrared region, so that exposure during photocuring is absorbed by the pigment, so that photohardening cannot be sufficiently performed. problem.

Further, Patent Document 4 discloses a black photosensitive resin composition containing a pigment containing specific titanium black particles as a main component. However, titanium black is likely to cause sinking in low-viscosity compositions due to high concentration addition. Therefore, even if a high OD value is obtained alone, the amount of addition has a limit.

As described above, various types of resin compositions having a black color have been proposed. However, with the development of technology in recent years, it is expected to have high insulation properties while maintaining high light-shielding properties, and in particular, materials capable of imparting photocuring properties.

[prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Publication No. 04-190362 (Application No., etc.)

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2010-519592 (Patent Patent Application, etc.)

[Patent Document 3] WO2012/133148A1 (Application Patent Range, etc.)

[Patent Document 4] JP-A-2002-275343 (Application for Patent, etc.)

[Summary of the Invention]

An object of the present invention is to provide a curable resin composition which can improve insulation properties while maintaining high light-shielding properties, and particularly has good photocurability.

As a result of a detailed review, the present inventors have found that the above-mentioned problems can be solved by adding a near-infrared ray absorbing agent to an organic color material having a maximum absorption value and a minimum absorption value in a specific wavelength range, and the present invention has been completed.

That is, the curable resin composition of the present invention contains (A) a near-infrared ray absorbing agent and (B) 380 to 780 nm in the visible light region, has a minimum absorption value at 380 to 500 nm, and has a maximum absorption value at 500 to 780 nm. The organic color material and (C) the thermosetting component are characteristic. The curable resin composition of the present invention preferably further contains (D) an alkali-soluble resin and (E) a photopolymerization initiator. Moreover, it is preferable that the curable resin composition of the present invention further contains (F) a photosensitive (meth) acrylate compound.

Further, the other curable resin composition of the present invention contains (A) a near-infrared ray absorbing agent and (B) a visible light region of 380 to 780 nm, a minimum absorption value at 380 to 500 nm, and a maximum absorption value at 500 to 780 nm. The organic color material and (F) photosensitive (meth) acrylate compound are characterized.

In the curable resin composition of the present invention, the maximum absorption wavelength of the (A) near-infrared ray absorbing agent is preferably 500 to 1000 nm. Further, as the near-infrared ray absorbing agent (A), at least one selected from the group consisting of a metal complex dye and a condensed polycyclic dye can be preferably used. Further, the curable resin composition of the present invention is preferably black, and is more suitably used for the formation of an insulating film.

Further, in the curable resin composition of the present invention, the color tone is adjusted so as to have a minimum absorption value at 380 to 500 nm in the range of 380 to 780 nm in the (B) visible light region, in the range which does not affect the photosensitivity and dispersibility. A color material other than the color material having the largest absorption value at 500 to 780 nm.

Moreover, the dry film of the present invention is characterized in that the curable resin composition of the present invention is coated on a carrier film and dried.

Further, the cured product of the present invention is characterized in that the curable resin composition of the present invention is applied onto a substrate and dried to obtain a dried coating film, or the following coating film is cured. The film is obtained by coating the curable resin composition on a carrier film and drying the dried film to laminate the substrate.

Further, the member for light shielding of the present invention is characterized in that it has the above-described cured product of the present invention.

Further, the member for display of the present invention is characterized in that it has the above-described cured product of the present invention.

According to the present invention, it is possible to improve the insulating properties while maintaining high light-shielding properties, and in particular, a curable resin composition which can also have good photocurability.

[Formation of the Invention]

Embodiments of the present invention will be described in detail below with reference to the drawings.

The curable resin composition of the present invention contains (A) a near-infrared ray absorbing agent, and (B) a color material having a minimum absorption value at 380 to 500 nm in a visible light region of 380 to 780 nm and a maximum absorption value at 500 to 780 nm. At the same time, it is characterized by containing (C) a thermosetting component or (F) a photosensitive (meth) acrylate compound as an essential component.

(C) heat containing (A) near-infrared ray absorbing agent and (B) 380 to 780 nm in the visible light region, having a minimum absorption value at 380 to 500 nm, and having a maximum absorption value at 500 to 780 nm The curable resin composition of the second embodiment of the present invention, which is an essential component, has high light-shielding property, thermosetting property, and insulating property. Further, it contains (A) a near-infrared ray absorbing agent and (B) a color material having a minimum absorption value at 380 to 500 nm in a visible light region of 380 to 780 nm and a maximum absorption value at 500 to 780 nm, and contains (F) In the curable resin composition of the first embodiment of the present invention, which is an essential component of the photosensitive (meth) acrylate compound, high light-shielding property, photocurability, and insulating property can be obtained.

That is, the present invention contains (A) a near-infrared ray absorbing agent in the resin composition, and (B) a minimum absorption value at 380 to 500 nm in the visible light region of 380 to 780 nm, and a maximum absorption value at 500 to 780 nm. When the material (hereinafter also referred to as "(B) specific color material"), even if the color material is added at a high concentration, good light-shielding properties and photosensitivity are not produced. Realized under the problem of dispersion such as precipitation. In the composition of the present invention, particularly in the visible light region, the OD value is preferably 3 or more, preferably 3 to 5, and particularly preferably 5 to 7. The curable resin composition of the present invention can be preferably black by the above formulation.

Further, in particular, according to the curable resin composition of the present invention, a similar color tone as when a carbon black pigment is added can be obtained. As described above, when a carbon black pigment is added to obtain a high OD value, there is a problem that the electric resistance value and the photosensitivity are lowered. However, the present invention using the above (A) and (B) components can simultaneously achieve a high OD value and resistance. The present invention is useful in touch panel members that require higher OD values and shielding properties.

[(A) Near Infrared Absorber]

The (A) near-infrared ray absorbing agent used in the present invention can be used for a dye having a maximum absorption of 500 to 1000 nm, preferably a maximum absorption wavelength of 700 to 1000 nm, more preferably 800 to 1000 nm. As the dye, a metal-based dye and a condensed polycyclic dye can be used, and specific examples thereof include a phthalocyanine dye, a porphyrin dye, a cyanine dye, a Quaterrylene dye, a squaraine dye, and an azo system. Ammonium, anthraquinone, diammonium, naphthalocyanine dye, nickel complex dye, copper ion dye, dithiol metal complex, heterocyclic compound, and the like. Among them, a heterocyclic compound, a Quaterine dye, a phthalocyanine or a naphthalocyanine dye is preferably equal to the visible light region. Examples of the product include SDO-C8, SDO-C33 (the above is manufactured by Seiko Chemical Co., Ltd.), Lumogen IR 765, and Lumogen IR 788 (the above is manufactured by BASFJAPAN Co., Ltd.). Wait. Further, it is preferable to have a maximum absorption in the above wavelength range and to efficiently absorb light, and it is preferable to have a sensitizing effect and a dye having a metal complex. One type or two or more types of these can be used.

The content of the (A) near-infrared ray absorbing agent is preferably 0.001 to 50% by mass, preferably 0.005 to 30% by mass, and 0.005 to 20% by mass, based on the curable resin composition (solid content). Better. When the (A) near-infrared absorbing agent is in the above range and (B) the specific color material is used, particularly in the visible light region, a desired higher OD value can be obtained. Further, the absorption of the desired visible light wavelength portion can be further improved.

[(B) specific color material]

The (B) specific color material used in the present invention may be a color material having a minimum absorption value at 380 to 500 nm in the visible light region of 380 to 780 nm and a maximum absorption value at 500 to 780 nm. Although there are organic color materials and inorganic color materials in the color material, it is preferred to use an organic color material in the present invention. As the specific color material (B) used in the present invention, although there are pigments or dyes, it may be a chemical synthesis other than the naturally occurring one, and the organic (synthetic) dye may be composed of an anthraquinone synthetic dye, A well-known organic (synthetic) dye which is a group of azo synthetic dyes, methine-based synthetic dyes, quinoline-based synthetic dyes, fluorene-based synthetic dyes, and azine-based synthetic dyes, but has excellent light-shielding properties in particular. Specifically, the aniline black formed by the compound having a phenazine skeleton can be exemplified. Especially for COLOR INDEX C.I.No.Acid Black 2, Solvent Black 5, Solvent Black 7, Solvent Black 22, Solvent Black 27, Solvent Black 29, Solvent Black 34 and the like, in particular, a metal salt-salt dye which is subjected to a salt-salting metal such as chromium, cobalt, nickel, copper or iron on the skeleton, is preferably in the form of coloring power or heat resistance. The organic pigment is a known organic pigment having a maximum absorption value at 380 to 500 nm in the visible light region at 380 to 780 nm, and a maximum absorption value at 500 to 780 nm, and also photocurability and coloring property. The phthalocyanine system, the dioxazine system, and the oxime system which are excellent in the shielding property in the visible light region are preferred. Specific examples of the phthalocyanine-based Pigment Blue 15:3, 15:4, 15:6, lanthanide Lumogen Black FK4280, Lumogen Black FK4281, and oxazide-based PigmentViolet 23, 37 are preferred. One type is used, or two or more types are used as appropriate. In addition, as the inorganic color material, cobalt tetraoxide, titanium black, or the like may be mentioned, and one type may be used alone or two or more types may be suitably mixed.

The inventors have found the following points after detailed research results. That is, it has been found that although the color material has a pigment or a dye, it is preferably a chemically synthesized person other than the naturally occurring one, and the chroma, the absorption wavelength, and the coloring property as a composition are compared with the naturally occurring one. Since the selectivity of the compatibility characteristics is varied, a good balance of the photosensitive composition having a high OD value can be achieved.

Further, it has been found that, in the case of the (B) specific color material used in the present invention, a high OD value can be achieved with a small amount of addition similar to carbon black by an excellent coloring power, and it has an absorption property as a target. Excellent photohardenability is obtained. Further, it has been found that among the specific color materials (B) used in the present invention, in particular, organic dyes have excellent photocurability and coloring properties, and The balance of the bulkiness can be applied to the curable resin composition for masking.

Therefore, in the specific color material (B), an organic dye is preferred from the viewpoint that a high OD value can be obtained in a small amount of addition. Among them, a nigrosine compound having a phenazine skeleton of condensed aniline ‧ nitrobenzene is preferred from the viewpoint of obtaining a higher OD value. This is a black condensation mixture obtained by adding hydrochloric acid to aniline or aniline hydrochloride and nitrobenzene, dehydrating, deamination, oxidation and redox Condensation under a catalyst such as copper or iron, by condensation. The condition is a multicomponent having a compound of various phenazine skeletons. Aniline black is produced by a reaction mixture, a raw material, and a charge ratio, and can be produced as a mixture of various compounds, and is presumed to be a triphenazine oxazine represented by the following chemical formula (I) or (II). A mixture of a azine compound such as phenazine and a compound in which an alkyl substituent is introduced, as shown in the above formulas (III) to (VI).

The aniline black which is a raw material of the organic dye in the present invention can be used, for example, as C.I. in COLOR INDEX, for example, as a methazine condensate described in Acid Black 2, C.I. Solvent Black 5, Solvent Black 7. Mixture. Among them, a metal salt-salt dye containing Solvent Black 5 and Solvent Black 7 having the chemical structural formula shown below is also preferred.

(Solvent Black 5)

(Solvent Black 7)

The amount of the specific color material used in the (B) of the present invention is preferably 0.05 to 80% by mass, more preferably 0.1 to 70% by mass, and preferably 0.5 to 50% by mass based on the composition (solid content). For better. When the blending amount of the (B) specific color material is within the above range, particularly in the visible light region, a desired higher OD value can be obtained.

[(C) thermosetting component]

The (C) thermosetting component to be used in the present invention is intended to impart heat resistance to the composition, and particularly preferably has two or more cyclic ether groups and cyclic thioether groups in the molecule (hereinafter referred to as (C) a thermosetting component which is at least one of a cyclic (thio)ether group). Using heat hardening In the case of a sexual component, not only heat resistance but also adhesion to a substrate can be improved. Here, in the second embodiment of the present invention, (C) a thermosetting component is essential, but in the first embodiment of the present invention, it is preferable to add (C) a thermosetting component. Thereby, a curable resin composition having both photocurability and thermosetting property can be obtained.

The (C) thermosetting component having two or more cyclic (thio)ether groups in the molecule is a cyclic ether group or a cyclic thio group having two or more 3, 4 or 5 membered rings in the molecule. The compound of either or both of the ether groups may, for example, be a compound having at least two or more epoxy groups in the molecule, that is, a polyfunctional epoxy compound having at least two or more oxetanyl groups in the molecule. The compound, that is, a polyfunctional oxetane compound, a compound having two or more thioether groups in the molecule, that is, an episulfide resin or the like.

Examples of the polyfunctional epoxy compound include EPICOAT 828, EPICOAT 834, EPICOAT 1001, EPICOAT 1004 manufactured by Mitsubishi Chemical Corporation, EPICLON 840 manufactured by DIC Corporation, EPICLON 850, EPICLON 1050, EPICLON 2055, and Epotohto YD-011, YD-013, YD manufactured by Tosho Kasei Co., Ltd. -127, YD-128, DER317, DER331, DER661, DER664, manufactured by Dow Chemical Co., Ltd., Suomi-Epoxy ESA-011, ESA-014, ELA-115, ELA- manufactured by Sumitomo Chemical Industries, Ltd. 128. Aceiba A, AER331, AER661, AER664, etc. (both are trade names) bisphenol A type epoxy resin manufactured by Asahi Kasei Industrial Co., Ltd.; EPICOATYL903 manufactured by Mitsubishi Chemical Corporation, manufactured by DIC Corporation EPICLON 152, EPICLON 165, Epotohto YDB-400, YDB-500, manufactured by Tosho Kasei Co., Ltd., DER542 manufactured by Dow Chemical Co., Ltd., Suomi-Epoxy ESB-400, ESB-700, manufactured by Sumitomo Chemical Industries, Ltd., manufactured by Asahi Kasei Kogyo Co., Ltd. Brominated epoxy resin such as AER711, AER714, etc. (both trade names); EPICOAT152, EPICOAT154 manufactured by Mitsubishi Chemical Corporation, DEN431, DEN438 manufactured by The Dow Chemical Co., Ltd., EPICLONN-730, EPICLONN manufactured by DIC Corporation 770, EPICLONN-865, Epotohto YDCN-701, YDCN-704 manufactured by Dongdu Chemical Co., Ltd., EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, manufactured by Nippon Kayaku Co., Ltd., manufactured by Sumitomo Chemical Industries Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220, AERECN-235, ECN-299, etc. (all trade names) made of Asahi Kasei Kogyo Co., Ltd. (all are brand name) novolac type epoxy resin; DIC company's EPICLON830, Mitsubishi Chemical EPICOAT807 manufactured by the company, Epotohto YDF-170, YDF-175, YDF-2004, etc. (both trade names) made of bisphenol F-type epoxy resin, EpotohtoST-2004, ST-2007, manufactured by Dongdu Chemical Co., Ltd. Hydrogenated bisphenol A type epoxy such as ST-3000 (trade name) Lipid; EPICOAT604 manufactured by Mitsubishi Chemical Corporation, EpotohtoYH-434 manufactured by Tosho Chemical Co., Ltd., and Sumi-Epoxy ELM-120 manufactured by Sumitomo Chemical Industries Co., Ltd. (all are trade names) of glycidylamine epoxy resin; Internal ureia type epoxy resin; alicyclic epoxy resin of CELLOXIDE 2021 (all trade name) manufactured by Daicel Chemical Industry Co., Ltd.; YL-933 manufactured by Mitsubishi Chemical Corporation, TEN manufactured by Dow Chemical Co., Ltd., EPPN- 501, EPPN-502, etc. (all are trade names) Phenyl phenylmethane type epoxy resin; bis-xylenol type or bisphenol type epoxy resin or a mixture thereof such as YL-6056, YX-4000, YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation; Japan EBPS-200 manufactured by Chemicals Co., Ltd., EPX-30 manufactured by Asahi Kasei Kogyo Co., Ltd., bisphenol S-type epoxy resin such as EXA-1514 (trade name) manufactured by DIC Corporation, and bisphenol such as EPICOAT157S (trade name) manufactured by Mitsubishi Chemical Corporation A novolac type epoxy resin; a tetraphenol ethane type epoxy resin such as EPICOATYL-931 manufactured by Mitsubishi Chemical Corporation (all are trade names); a heterocyclic ring of TEPIC (all are trade names) manufactured by Nissan Chemical Industries Co., Ltd. Epoxy resin; diglycidyl phthalate resin such as BLEMMERDGT manufactured by Nippon Oil & Fats Co., Ltd.; tetraglycidyl xylene decyl ethane resin such as ZX-1063 manufactured by Dongdu Chemical Co., Ltd.; Nippon Steel Chemical Co., Ltd. Ethylene-based epoxy resin such as ESN-190, ESN-360, HP-4032, EXA-4750, and EXA-4700 manufactured by DIC Corporation; HP-7200 and HP-7200H manufactured by DIC Corporation have dicyclopentylene Epoxy resin of olefin skeleton; copolymerization of glycidyl methacrylate such as CP-50S and CP-50M manufactured by Nippon Oil Co., Ltd. Epoxy resin; further, a copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; an epoxy-modified polybutadiene rubber derivative (for example, manufactured by Daicel Chemical Industry Co., Ltd.) PB-3600, etc., CTBN modified epoxy resin (for example, YR-102, YR-450, manufactured by Tosho Kasei Co., Ltd.), epoxy resin containing biphenyl skeleton, etc., such as NC3000 manufactured by Nippon Kayaku Co., Ltd. Not limited to this. These epoxy resins may be used alone or in combination of two or more. Among them, a novolak type epoxy resin, a heterocyclic epoxy resin, a bisphenol A type epoxy resin or a mixture thereof is used. good.

The polyfunctional oxetane compound may, for example, be bis[(3-methyl-3-oxetanylmethoxy)methyl]ether or bis[(3-ethyl-3-oxa) Cyclobutane methoxy)methyl]ether, 1,4-bis[(3-methyl-3-oxetanylmethoxy)methyl]benzene, 1,4-bis[(3) -ethyl-3-oxetanylmethoxy)methyl]benzene, (3-methyl-3-oxetanyl)methacrylate, (3-ethyl-3-oxo Heterocyclobutane)methacrylate, (3-methyl-3-oxetanyl)methyl methacrylate, (3-ethyl-3-oxetanyl)methyl Examples of the methacrylate or the polyfunctional oxetane such as these oligomers or copolymers include oxetane and novolac resins, poly(p-hydroxystyrene), and ether ketones. An ether compound such as a bisphenol, a calixarene, a resorcinol calixarene or a sesquioxane or a resin having a hydroxyl group. Other examples thereof include a copolymer of an oxetane ring-containing unsaturated monomer and an alkyl (meth) acrylate.

Examples of the compound having two or more cyclic thioether groups in the molecule include bisphenol A type episulfide resin YL7000 manufactured by Nippon Epoxy Co., Ltd., and the like. Further, an episulfide resin or the like in which an oxygen atom of an epoxy group of a novolac type epoxy resin is replaced by a sulfur atom can be used by the same synthesis method.

The amount of the thermosetting component (C) is preferably 0.6 to 2.8 equivalents, preferably 0.8 to 2.5 equivalents, per 100 parts by mass of the resin component. When the amount of the (C) thermosetting component is within the above range, good heat resistance can be imparted to the composition.

[(D) alkali soluble resin]

In the composition of the present invention, (D) an alkali-soluble resin can be added as a resin component. As the (D) alkali-soluble resin, a carboxyl group-containing resin or a phenol resin is preferably used. When a carboxyl group-containing resin is particularly used, it is more preferable from the viewpoint of development.

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

In the present invention, in particular, the non-photosensitive carboxyl group-containing resin having no ethylenically unsaturated double bond in the molecule is preferably improved in flexibility, reduced in hardening shrinkage, and improved in adhesion.

Specific examples of the non-photosensitive carboxyl group-containing resin include the following compounds (both oligomers and polymers).

(1) A diol compound containing a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate or an aromatic diisocyanate, or a carboxyl group such as dimethylolpropionic acid or dimethylolbutanoic acid. A polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, a bisphenol A-based epoxide adduct diol, a phenolic hydroxyl group, and an alcoholic hydroxyl group. A carboxyl group-containing urethane resin which is subjected to a polyaddition reaction of a diol compound.

(2) A carboxyl group-containing urethane resin which is reacted by polyaddition of a diisocyanate and a carboxyl group-containing diol compound.

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

(4) reacting a bifunctional epoxy resin or a bifunctional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid to form an phthalic acid in the resulting hydroxyl group A carboxyl group-containing polyester resin of two alkali anhydrides such as an acid anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride.

(5) A carboxyl group-containing resin obtained by subjecting an epoxy resin or an oxetane resin to ring-opening and reacting the resulting hydroxyl group with a polybasic acid anhydride.

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

Further, in the present specification, the (meth) acrylate means an acrylate, a methacrylate, and a mixture thereof.

As the non-photosensitive carboxyl group-containing resin, it is preferred to use the above (1), (2), and (6) as compared with the case where chlorine is not used. Among them, the above (6) is also preferable in that it has a good balance of all the characteristics from the viewpoint of having an aromatic ring and having excellent thermal cycling, and using a combination hardening shrinkage.

Further, specific examples of the photosensitive carboxyl group-containing resin include the following compounds (oligomers and polymers). Further, the ethylenically unsaturated double bond in the carboxyl group-containing resin is preferably acrylic acid or methacrylic acid or a derivative derived therefrom.

(7) Containing aliphatic diisocyanate, branched aliphatic a diisocyanate such as an isocyanate, an alicyclic diisocyanate or an aromatic diisocyanate; a diol compound having a carboxyl group such as dimethylolpropionic acid or dimethylolbutanoic acid; and a polycarbonate-based polyol or a polyether-based polyol Polyaddition reaction of diol compounds such as alcohol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A epoxide adduct diol, phenolic hydroxyl group and alcoholic hydroxyl group The obtained carboxyl group-containing photosensitive urethane resin was obtained.

(8) Diisocyanate, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisxylenol epoxy resin, double A (meth) acrylate having a bifunctional epoxy resin such as a phenol epoxy resin or a photosensitive urethane resin containing a carboxyl group obtained by a polyaddition reaction of the acid anhydride-modified compound with the carboxyl group-containing diol compound.

(9) In the synthesis of the resin of the above (7) or (8), the addition of a hydroxyalkyl (meth) acrylate is equivalent to a compound having one hydroxyl group and one or more (meth) acryl fluorenyl groups in the molecule. A terminal (meth) acrylated carboxyl group-containing photosensitive urethane resin.

(10) In the synthesis of the resin of the above (8) or (9), a molar reactant such as isophorone diisocyanate and pentaerythritol triacrylate is added to have one isocyanate group and one or more (methyl group) in the molecule. A compound containing a carboxy group, which is a terminal (meth) acrylated carboxyl group-containing photosensitive urethane resin.

(11) A bifunctional or higher polyfunctional (solid) epoxy resin is reacted with (meth)acrylic acid to form a hydroxyl group present in the side chain. A photosensitive resin containing a carboxyl group as a base acid anhydride.

(12) A polyfunctional epoxy resin obtained by further epoxidizing a hydroxyl group of a bifunctional (solid) epoxy resin with epichlorohydrin is reacted with (meth)acrylic acid to form a hydroxyl group-added 2 alkali anhydride. A photosensitive resin of a carboxyl group.

(13) reacting a bifunctional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid or hexahydrophthalic acid to form phthalic anhydride at the first-order hydroxyl group formed, A carboxyl group-containing polyester photosensitive resin of two alkali anhydrides such as tetrahydrophthalic anhydride or hexahydrophthalic anhydride.

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

(15) A compound having a plurality of phenolic hydroxyl groups in one molecule is reacted with a cyclic carbonate compound such as ethyl acrylate or propyl carbonate to obtain a reaction product, which is combined with an unsaturated group-containing monocarboxylic acid. The reaction product is obtained to obtain a reaction product, and a carboxyl group-containing photosensitive resin obtained by reacting the polybasic acid anhydride with the polybasic acid anhydride is obtained.

(16) A resin containing a carboxyl group which is obtained by further adding a resin having one epoxy group to one or more (meth)acryl fluorenyl groups in one molecule to the resin of the above (7) to (15).

These photosensitive carboxyl group-containing resins may be used alone or in combination of plural kinds, as described in (7) to (16). Particularly, a resin having an aromatic ring among the carboxyl group-containing resins is preferred because of excellent resolution.

Among them, the carboxyl group-containing resin synthesized by using a phenol compound as a starting material such as a carboxyl group-containing resin (14) or (15) is excellent in insulating property because it does not contain chlorine.

The above-mentioned carboxyl group-containing resin can be explained as follows, regardless of whether it is photosensitive or non-photosensitive. That is, the side chain of the backbone ‧ polymer can be visualized in a dilute aqueous alkali solution because it has a plurality of carboxyl groups.

Further, the acid value of the carboxyl group-containing resin is suitably in the range of 40 to 200 mgKOH/g, preferably in the range of 45 to 120 mgKOH/g. When the acid value of the carboxyl group-containing resin is less than 40 mgKOH/g, the alkali development becomes difficult. On the other hand, when it exceeds 200 mgKOH/g, since the exposure portion is dissolved by the developing solution, the line is tapered to If necessary, depending on the case, the exposed portion and the unexposed portion may cause dissolution and separation of the developing liquid, and the drawing of the normal resist pattern may be difficult.

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

The amount of the carboxyl group-containing resin is such that the curable resin The composition is preferably in the range of 20 to 60% by mass, preferably 30 to 50% by mass. When the amount of the carboxyl group-containing resin is less than 20% by mass, the strength of the film is lowered, which is not preferable. On the other hand, when the amount is more than 60% by mass, the viscosity of the curable resin composition becomes high, or the coatability to the carrier film or the like is lowered, which is not preferable.

Further, in the present invention, as the alkali-soluble resin, one of a photosensitive carboxyl group-containing resin and a carboxyl group-containing resin having no photosensitivity may be used, or a mixture thereof may be used, but a mixed photosensitive carboxyl group-containing resin may be used. It is preferable to use a photosensitive carboxyl group-containing resin, and the content ratio (photosensitive carboxyl group-containing resin: carboxyl group-containing resin having no photosensitivity) is (1:9) to (9:1) based on the mass of the solid component. Preferably, it is preferably (2:8)~(8:2), more preferably (5:5)~(7:3). When it is in this range, in particular, it is possible to obtain a cured product of a resin composition excellent in both resolution and adhesion, and a printed circuit board having the same, while avoiding an increase in exposure amount.

The photosensitive carboxyl group-containing resin and the carboxyl group-containing resin having no photosensitivity may be used alone or in combination of two or more. Among the carboxyl group-containing resins, a resin having an aromatic ring is preferable because of its high refractive index and excellent resolution, and a resin having a novolac structure is excellent in resolution, PCT resistance, and crack resistance.

As the phenol resin, a compound having a phenolic hydroxyl group can be used, for example, a compound having a biphenyl skeleton or a phenylene skeleton or a skeleton thereof, or a phenolic hydroxy compound can be used, and for example, phenol or o-cresol can be used. P-cresol, m-cresol, 2,3-xylenol, 2,4-dimethyl Phenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methyl hydrogen A phenolic resin having various skeletons synthesized by ruthenium, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, and phloroglucinol.

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

These can be used individually or in combination of 2 or more types.

HF1H60 (made by Megumi Kasei Co., Ltd.), PHENOLITETD-2090, PHENOLITETD-2131 (made by Dainippon Printing Co., Ltd.), Besumoru CZ-256-A (made by DIC Corporation), Shiyounoru BRG-555, etc. are mentioned as a commercial item of the phenol resin. Shiyounoru BRG-556 (manufactured by Showa Denko KK), CGR-951 (manufactured by Maruzen Oil Co., Ltd.), or CST70, CST90, S-1P, S-2P (manufactured by Maruzen Oil Co., Ltd.) of polyvinyl phenol. These phenol resins may be used singly or in combination of two or more kinds as appropriate.

In the present invention, as the (D) alkali-soluble resin, either one of a carboxyl group-containing resin and a phenol resin or a mixture thereof can be used.

In the curable resin composition of the present invention, when a material containing no ethylenically unsaturated group is used as the (D) alkali-soluble resin, it is necessary to use one or more molecules in the molecule, and preferably two or more ethyl groups. An unsaturated group of compounds, that is, a photopolymerizable monomer must be used together A photopolymerizable compound such as a substance. The photopolymerizable compound is photocured by irradiation with an active energy ray, and can promote the dissolution of the (D) alkali-soluble resin into an aqueous alkali solution. Further, when a carboxyl group-containing resin is used, a photopolymerizable compound can be used in combination for the purpose of further promoting photocuring.

One type or a plurality of types of photopolymerizable compounds can be used in either case.

[(E) Photopolymerization initiator]

The composition of the present invention may contain (E) a photopolymerization initiator. Examples of the (E) photopolymerization initiator include a benzophenone type, an acetophenone type, an amino acetophenone type, a benzoin ether type, a benzyl ketal type, and a decylphosphinium oxide type. A known compound such as an oxime ether, an oxime ester or a titanocene.

The (E) photopolymerization initiator contains α-aminoacetophenone selected from the group consisting of an oxime ester group having a structural moiety represented by the general formula (I) shown below and containing a structural moiety represented by the general formula (II). It is preferred that one or two or more kinds of the fluorenylphosphinyl oxide system having a structural moiety represented by the general formula (III) and the ferrocene-based compound represented by the general formula (IV) are present.

In the general formula (I), R ¹ represents a hydrogen atom, a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzamidine group. R ² represents a phenyl group, an alkyl group, a cycloalkyl group, an alkano group or a benzyl group.

The phenyl group represented by R ¹ and R ² may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a phenyl group, and a halogen atom.

The alkyl group represented by R ¹ and R ² is preferably an alkyl group having 1 to 20 carbon atoms, and may have one or more oxygen atoms in the alkyl chain. Further, it may be substituted by one or more hydroxyl groups.

The cycloalkyl group represented by R ¹ and R ² is preferably a cycloalkyl group having 5 to 8 carbon atoms.

The alkyl fluorenyl group represented by R ¹ and R ² is preferably an alkyl fluorenyl group having 2 to 20 carbon atoms.

The benzamidine group represented by R ¹ and R ² may have a substituent, and examples of the substituent include an alkyl group having 1 to 6 carbon atoms and a phenyl group.

In the general formula (II), R ³ and R ⁴ each independently represent an alkyl group or an arylalkyl group having 1 to 12 carbon atoms, and R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Or two combinations may form a cyclic alkyl ether group.

In the general formula (III), R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 10 carbon atoms, a cyclohexyl group, a cyclopentyl group, an aryl group or an aryl group which may be substituted by a halogen atom, an alkyl group or an alkoxy group, Or a carbonyl group having 1 to 20 carbon atoms (however, the case where both of them are a carbonyl group having 1 to 20 carbon atoms) is removed.

In the general formula (IV), R ⁹ and R ¹⁰ each independently represent a halogen atom, an aryl group, a halogenated aryl group, and a heterocyclic ring contains a halogenated aryl group.

The oxime ester photopolymerization initiator containing the structural moiety represented by the general formula (I) is exemplified by 1,2-octanedione-1-[4-(phenylthio)-2-(O- Benzamidine), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(O-acetamidine A compound represented by the following formula (I-1), 2-(ethyloxyiminomethyl)thioxanthene-9-one, and a compound represented by the following general formula (I-2).

In the general formula (I-2), R ¹¹ is synonymous with R ¹ in the general formula (I), and R ¹² and R ^{14 are} each independently synonymous with R ² in the general formula (I). R ¹³ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclopentyl group, a cyclohexyl group, a phenyl group, a benzyl group, a benzamyl group, an alkyl 2 group having 2 to 12 carbon atoms, and a carbon number of 2 ~12 alkoxycarbonyl group (when the alkyl group number of the alkoxy group is 2 or more, the alkyl group may be substituted by one or more hydroxyl groups, or may have one or more oxygen atoms in the middle of the alkyl chain) or phenoxy Carboxyl group.

Among them, the compound represented by the above formula (I-2) is also preferred.

Such an oxime ester photopolymerization initiator is preferably used for direct imaging, for example, because the composition of the present invention has high sensitivity and excellent resolution.

In particular, in the case where the exposure is h line (405 nm) of a single wavelength, the oxime ester photopolymerization initiator is preferably a dimer.

As the dimeric oxime ester photopolymerization initiator, a compound represented by the following general formula (I-3) is preferred.

In the general formula (I-3), R ²³ represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group or a naphthyl group.

R ²¹ and R ²² each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen group, a phenyl group, a naphthyl group, a fluorenyl group, a pyridyl group, a benzofuranyl group or a benzothienyl group.

Ar represents a single bond, or an alkylene group having 1 to 10 carbon atoms, a benzothienyl group, a phenylene group, a diphenylene group, a pyridyl group, a naphthylene group, a fluorenyl group, a thienyl group, and a furanyl group. 2,5-pyrrole-diyl, 4,4'-fluorenyl-diyl, 4,2'-styrene-diyl.

n represents an integer from 0 to 1.

The alkyl group represented by R ²³ is preferably an alkyl group having 1 to 17 carbon atoms.

The alkoxy group represented by R ²³ is preferably an alkoxy group having 1 to 8 carbon atoms.

The phenyl group represented by R ²³ may have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms), an alkoxy group (preferably having 1 to 8 carbon atoms), and an amine group. And an alkylamino group (preferably having an alkyl group having 1 to 8 carbon atoms) and a dialkylamino group (preferably having an alkyl group having 1 to 8 carbon atoms).

The naphthyl group represented by R ²³ may have a substituent, and examples of the substituent include the same group as the above substituent of the phenyl group represented by R ²³ .

The alkyl group represented by R ²¹ and R ²² is preferably an alkyl group having 1 to 17 carbon atoms.

The alkoxy group represented by R ²¹ and R ²² is preferably an alkoxy group having 1 to 8 carbon atoms.

The phenyl group represented by R ²¹ and R ²² may have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 17 carbon atoms) and an alkoxy group (preferably having 1 to 8 carbon atoms). And an amine group, an alkylamino group (preferably having an alkyl group having 1 to 8 carbon atoms) and a dialkylamino group (preferably having an alkyl group having 1 to 8 carbon atoms).

The naphthyl group represented by R ²¹ and R ²² may have a substituent, and examples of the substituent include the same groups as the above substituents having a phenyl group represented by R ²¹ and R ²² .

And in the general formula (I-3), R ²¹ and R ^{23 are} each independently a methyl group or an ethyl group, R ²² is a methyl group or a phenyl group, and Ar is a single bond or a phenyl group, a naphthylene group or a thienylene group. When n is 0, it is preferable. Among the compounds represented by the general formula (I-3), those represented by the following structural formulas are also preferred.

When such an oxime ester photopolymerization initiator is used, it is preferred to use an α-aminoacetophenone photopolymerization initiator containing a structural moiety represented by the general formula (II), and the like.

The α-aminoacetophenone photopolymerization initiator containing the structural moiety represented by the general formula (II) includes 2-methyl-1-[4-(methylthio)phenyl]-2. -morpholinone-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, etc. .

The fluorenylphosphinic oxide-based photopolymerization initiator containing a structural moiety represented by the general formula (III) includes 2,4,6-trimethylbenzimidyldiphenylphosphinium oxide and a double (2,4,6-trimethylbenzylidene)-phenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethyl-pentyl Phosphine oxide and the like.

As the titanocene photopolymerization initiator represented by the general formula (IV), bis(η ⁵ -2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-) (1H-pyrrol-1-yl)-phenyl)titanium.

The blending ratio of the (E) photopolymerization initiator is preferably from 0.01 to 100 parts by mass, more preferably from 0.5 to 80 parts by mass, per 100 parts by mass of the resin component. (E) When the blending ratio of the photopolymerization initiator is less than 0.01 parts by mass based on 100 parts by mass of the resin component, the photocurability is insufficient, the coating film is peeled off, and the coating properties such as chemical resistance are lowered. Not good. On the other hand, when the blending ratio of the (E) photopolymerization initiator exceeds 100 parts by mass based on 100 parts by mass of the resin component, the deep curing property is lowered by the light absorption of the (E) photopolymerization initiator. The situation is not good.

Further, a photopolymerization initiator or a photoinitiator and a sensitizer other than the above compounds may be used in the curable resin composition of the present invention, and examples thereof include a benzoin compound, an anthraquinone compound, and a thioxanthone compound. A ketone compound, a benzophenone compound, a xanthone compound, and a tertiary amine compound.

Specific examples of the benzoin compound are exemplified by benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Specific examples of acetophenone compounds, such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylphene Ketone, 1,1-dichloroacetophenone. Specific examples of the ruthenium compound are exemplified by 2-methyl hydrazine, 2-ethyl hydrazine, 2-t-butyl hydrazine, and 1-chloro hydrazine. Hey. Specific examples of the thioxanthone compound include, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 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-benzylidene diphenyl sulfide, 4-benzylidene-4'-methyldiphenyl sulfide, 4-Benzylmercapto-4'-ethyldiphenyl sulfide, 4-benzylidene-4'-propyldiphenyl sulfide.

Specific examples of the tertiary amine compound, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, for example, 4,4'-dimethylaminobenzophenone (Nissokyua MABP, manufactured by Nippon Soda Co., Ltd.) , 4,4'-diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.), etc., dialkylaminobenzophenone, 7-(diethylamino)-4-methyl- a dialkylamino group-containing coumarin compound, 4-dimethylamine, such as 2H-1-benzopyran-2-one (7-(diethylamino)-4-methylcoumarin) Kean acid ethyl ester (Kayacure EPA manufactured by Nippon Kayaku Co., Ltd.), 2-dimethylamino benzoic acid ethyl (Quantacure DMB manufactured by International Bio-synthetics), 4-dimethylamino benzoic acid (n-butoxy) Ethyl (International Bio-synthetics Quantacure BEA), p-dimethylamino benzoic acid isoamyl ethyl ester (Kayacure DMBI, manufactured by Nippon Kayaku Co., Ltd.), 4-dimethylamino benzoic acid 2- Ethylhexyl (Esolol 507, manufactured by Van Dyk Co., Ltd.), 4,4'-diethylaminobenzophenone (EAB, manufactured by Hodogaya Chemical Co., Ltd.).

As a tertiary amine compound, having a dialkylamine benzene knot The compound is preferably a dialkylaminobenzophenone compound, and a coumarin compound having a dialkylamine group having a maximum absorption wavelength of 350 to 410 nm is particularly preferred. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferred because it has a low toxicity. The maximum absorption wavelength of the dialkylamine-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm is in the ultraviolet region, so that a coloring film which uses a coloring agent and reflects the color of the coloring agent itself can be provided. Particularly, 7-(diethylamino)-4-methyl-2H-1-benzopyran-2-one is preferred because it exhibits an excellent sensitizing effect on laser light having a wavelength of 400 to 410 nm.

[(F) Photosensitive (meth) acrylate compound]

The (F) photosensitive (meth) acrylate compound used in the present invention is photocured by irradiation with an active energy ray, and the resin component is insolubilized in an aqueous alkali solution or helps to insolubilize it. As such a compound, conventionally known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, epoxy can be used. Specific examples of the (meth) acrylate and the like include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; ethylene glycol, methoxytetraethylene glycol, and polyethyl b. a diacrylate of glycol such as diol or propylene glycol; propylene such as N,N-dimethylpropenyl, N-methylolpropenyl or N,N-dimethylaminopropylpropenyl Mercapto group; amine alkyl acrylates such as N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl acrylate; hexane, trimethylolpropane , pentaerythritol, dipentaerythritol, cis-hydroxyethyl isocyanurate a polyvalent alcohol or a polyvalent acrylate such as an ethylene oxide adduct, a propylene oxide adduct, or an ε-caprolactone adduct; a phenoxy acrylate, a bisphenol A diacrylate, And polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether And a polyvalent acrylate such as a glycidyl ether such as triglycidyl isocyanurate; and not limited to the above, examples thereof include polyether polyol, polycarbonate diol, hydroxyl terminal polybutadiene, and poly Polyols such as ester polyols which are directly acrylated or acrylated with urethane via diisocyanate, melamine acrylate, nano cerium oxide modified acrylate or isocyanate acrylate The functional acrylate and at least any one of the methacrylates corresponding to the above acrylate.

Further, an epoxy acrylate resin in which a polyfunctional epoxy resin such as a cresol novolac type epoxy resin is reacted with acrylic acid, or a hydroxyl group such as a hydroxyl group of the epoxy acrylate resin and pentaerythritol triacrylate may be mentioned. An epoxy urethane acrylate compound obtained by reacting a semi-carbamate compound of a diisocyanate such as isophorone diisocyanate. Such an epoxy acrylate-based resin can improve the photocurability without lowering the dryness of the touch.

(F) The amount of the photosensitive (meth) acrylate compound is preferably from 1 to 150 parts by mass, more preferably from 5 to 120 parts by mass, per 100 parts by mass of the resin component. When the amount of the (F) photosensitive (meth) acrylate compound is within the above range, good photocurability is obtained, which is preferable.

[other color materials]

In order to further adjust the color tone or the like, the composition of the present invention may be used in addition to (B) a specific color material, or (B) a known conventional color material other than the specific color material, an organic pigment, an inorganic pigment, an organic dye, a natural dye, or the like. Any of the pigments. Specific examples thereof include a black colorant, a red colorant, a blue colorant, a yellow colorant, a green colorant, a purple colorant, an orange colorant, a brown colorant, a white colorant, and the like. Among them, a black colorant, a blue colorant, a blue green colorant, and a purple colorant have a higher OD value.

(black colorant)

Examples of the black coloring agent include carbon black pigments such as CIPigment black 6, 7, 9, and 18, black lead pigments such as CIPigment black 8 and 10, and CIPigment black 11, 12, and 27, and Pigment Brown 35. An iron oxide-based pigment; for example, iron oxide of KN-370 manufactured by Putian Industrial Co., Ltd., an anthraquinone pigment such as CIPigment black 20, a cobalt oxide pigment such as CIPigment black 13, 25, 29, or CIPigment black 15, 28 such as copper oxide pigment, manganese dye such as CIPigment black 14, 26, cerium oxide pigment such as CIPigment black 23, nickel oxide pigment such as CIPigment black 30, CIPigment black 31, 32, BASFJAPAN Lumeng Black FK4280's lanthanide pigment (excluding (B) specific color material), Pigment Black 1 aniline pigment and molybdenum sulfide or strontium sulfide It can also be exemplified as a suitable pigment. These pigments can be used singly or in combination as appropriate.

(red colorant)

Examples of the red coloring agent include a monoazo type, a bisazo type, an AZO LAKE (azo dye) type, a benzimidazolone type, an anthraquinone type, a diketopyrrolopyrrole type, a condensed azo type, and an anthracene. The quinacridone system or the like is specifically exemplified by a color index number as follows.

Monoazo system: Pigment Red 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114,146,147 ,151,170,184,187,188,193,210,245,253,258,266,267,268,269; bisazo system: Pigment Red 37,38,41;MONO AZO LAKE (azo dye) Department: 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: Pigment Red 171,175,176,185,208; lanthanide: Solvent Red 135,179, Pigment Red 123 , 149, 166, 178, 179, 190, 194, 224; diketopyrrolopyrrole: Pigment Red 254, 255, 264, 270, 272; condensed azo system: Pigment Red 144, 166, 214, 220, 221,242; 蒽醌: Pigment Red 168, 177, 216, Solvent Red 149, 150, 52, 207; quinacridone: Pigment Red 122, 202, 206, 207, 209

(blue colorant)

As a blue coloring agent, it is classified into a phthalocyanine system (excluding (B) specific color material), an anthraquinone system, a dioxin-based system (excluding (B) specific color material), and a cobalt-based pigment. The compound is a pigment, a dye is a solvent, and the like, and specifically, a color index number as described below is attached. Further, in addition to these, a metal-substituted or unsubstituted phthalocyanine compound (excluding the (B) specific color material) may be used.

Pigment system: Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60; dye system: Solvent Blue 35, 45, 63, 67, 68, 70, 83, 87,94,97,104,122,136

(yellow colorant)

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

Monoazo system: Pigment Yellow 1,2,3,4,5,6,9,10,12,61,62,62:1,65,73,74,75,97,100,101,104,105 , 111, 116, 167, 168, 169, 182, 183; bisazo system: Pigment Yellow 12,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188,198; condensed azo Line: Pigment Yellow 93,94,95,128,155,166,180;benzimidazolone: Pigment Yellow 120,151,154,156,175,181;isoporphyrin system:Pigment Yellow 109,110, 139, 179, 185; lanthanide: Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202;

(green colorant)

As the green coloring agent, there are a phthalocyanine system (excluding the (B) specific color material) and a lanthanoid system, and specifically, Pigment Green 7, 36, Solvent Green 3, 5, 20, 28 and the like can be used. A metal-substituted or unsubstituted phthalocyanine compound may also be used in addition to the above.

(purple colorant)

Specific examples of the purple coloring agent include Pigment Violet 19, 29, 32, 36, 38, 42; Solvent Violet 13, 36; Pigment Black 1, Pigment Black 7, Pigment Brown 25 and the like.

(orange colorant)

Specific examples of the orange coloring agent include Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71. 73 et al.

(tea coloring agent)

Specific examples of the brown coloring agent include Pigment brown 23, 25 and the like.

(white colorant)

Examples of the white colorant include zinc acid represented by Pigment white 4, titanium oxide represented by Pigment white 6, and zinc sulfide represented by Pigment white 7. From the viewpoint of coloring power and non-toxicity, titanium oxide is particularly used. For example, TR-600, TR-700, TR-750, TR-840, and R-550, R-580, R-630, R-820, and CR-50 manufactured by Fujitsu Industries Co., Ltd. CR-60, CR-90, rutile type titanium oxide such as KR-270, KR-310, KR-380, etc., TA-100, TA-200, TA-300, TA-made by Fuji Titanium Industry Co., Ltd. 500. A100, A220 manufactured by Ishihara Sangyo Co., Ltd., anatase type titanium oxide such as KA-15, KA-20, KA-35, and KA-90 manufactured by Titanium Industry Co., Ltd. Under a small amount of a white coloring agent, for example, when the composition is added only to 0.1 to 3% by mass, it is expected to improve the concealing effect.

As the color material other than the specific color material (B), at least one of the above may be used, but a black colorant, a blue colorant, and a green color may be used. It is preferable that at least one of a coloring agent and a purple coloring agent is preferable, whereby an advantage of being able to obtain a high OD value while adjusting a slight color sensation can be obtained. Further, in the case of 500 to 900 nm, in particular, 500 to 800 nm has a maximum absorption wavelength, and when the absorption of 380 to 500 nm is lower than this, it is preferable because it has no influence on the OD value or photocurability. In the above, as the color material other than the specific color material (B), it is preferable to contain titanium black, cobalt tetraoxide, or a synthetic inorganic pigment which exhibits black color, whereby the OD value or photocurability can be maintained. Improve heat resistance.

(B) the blending amount of the color material other than the specific color material is the ratio of the color material other than (A): (A) to the ratio of the specific color material used in (B) of the present invention: 99:1 to 10:90 The range is better, preferably in the range of 99:1 to 30:70, preferably in the range of 99:1 to 50:50, and especially in the range of 99:1 to 51:49. . When the blending amount of the color material other than the specific color material (B) is within the above range, a curable resin composition having a good balance can be obtained particularly for the OD value, the photocurability, and the light resistance.

[thermosetting catalyst]

It is preferable that the curable resin composition of the present invention further contains a thermosetting catalyst. Examples of the thermosetting catalyst include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, and 1-cyanoquinone. Imidazole derivatives such as ethyl ethyl-2-phenylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyanodiamide, benzyldimethylamine, 4-(Dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy An amine compound such as benzyl-N,N-dimethylbenzylamine or 4-methyl-N,N-dimethylbenzylamine, anthracene compound such as diammonium adipate or diterpene sebacate a phosphorus compound such as triphenylphosphinium or the like. In addition, as a commercially available product, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ (all are imidazole-based compounds) manufactured by Shikoku Chemicals Co., Ltd., and U manufactured by San-apro Co., Ltd. -CAT3503N, U-CAT3502T (all trade names of block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (all of which are bicyclic guanidine compounds and salts thereof). Further, it is not limited thereto, and can be used only for a thermosetting catalyst capable of promoting an epoxy resin or an oxetane compound, or a reaction of an epoxy group and/or an oxetane group with a carboxyl group. These can be used individually or in mixture of 2 or more types. Further, guanamine, acetamide, benzoguanamine, melamine, 2,4-diamino-6-methylpropenyloxyethyl-S-triazine, 2-vinyl-2,4 can be used. -diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine ‧ isocyanuric acid adduct, 2,4-diamino-6-methyl propylene hydride An S-triazine derivative such as an oxyethyl-S-triazine ‧ isocyanuric acid addition product is preferably used in combination with a thermosetting catalyst which is a function of the adhesion imparting agent.

The amount of the thermosetting catalyst to be used is generally sufficient, for example, 0.1 to 20 parts by mass, more preferably 0.5 to 15.0 parts by mass, per 100 parts by mass of the resin component or (C) thermosetting component. .

[Other ingredients]

Moreover, in the composition of the present invention, the hardness of the cured product can be further improved An inorganic filler is added for the purpose of properties such as properties, mechanical strength, and linear expansion coefficient. As such an inorganic filler, for example, barium sulfate, barium titanate, cerium oxide powder, fine powdered cerium oxide, amorphous cerium oxide, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, mica can be used. A well-known inorganic filler such as powder.

In the composition of the present invention, a known conventional polymerization inhibitor, such as hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, pyrogallol, phenothiazine, or the like, may be further added. At least one of a known tackifier, a polyfluorene-based, a fluorine-based, a polymer-based antifoaming agent, and a coating agent, such as an isocyanate or an imidazole, etc., such as an anthracene, an organic bentonite, or a montmorillonite. A well-known and customary additive such as a thiazole coupling agent such as a thiazole system or a triazole system, an antioxidant, a photopolymerization sensitizer, a photostabilizer, a dispersant, a hardening accelerator, a flame retardant, and a flame retardant auxiliary.

The composition of the present invention may contain an organic solvent used in the preparation of the composition for adjustment or viscosity adjustment. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; cellosolve, methyl cellosolve, and butyl cellosolve. Glycol ethers such as carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (DPM), dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether Ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate Esters such as esters, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, naphtha, and solvent brain oil. These organic solvents can Used alone or in combination of two or more types.

The curable resin composition of the present invention which is formed of the above-mentioned compounding component has a maximum absorption value at 500 to 780 nm in the visible light region of 380 to 780 nm, and has a minimum absorption value at 380 to 500 nm. It is preferable from the viewpoint of obtaining a photosensitive composition having a high OD value, and it is preferable to exhibit a black color. It is preferable that the L* value of the cured product is 30 or less by the SCI method by the colorimeter displaying the blackness. Also, the a* value is -5 to 5, and the b* value is preferably -5 to 5. Preferably, the a* value is -2 to 2, and the b* value is -2 to 2.

Since the curable resin composition of the present invention has high OD value and high insulating property, it is useful as a material for forming an insulating film. Moreover, the curable resin composition of the present invention is also useful as a member for light shielding. Further, since the curable resin composition of the present invention has high OD value and excellent photosensitivity, a high-quality display member can be obtained by using the curable resin composition of the present invention. The curable resin composition of the present invention can be used for other printing inks, inkjet inks, mask manufacturing materials, moisture-proof paper making materials for printing, etching resists, solder resists, and plasma display panels (PDP). The electric pattern, the electrode (conductor loop) pattern, the wiring pattern of the electronic component, the conductive paste, the conductive film, the shading image such as a black matrix, etc., and the curable resin composition of the present invention can be used for improving the use. When the display characteristics of a color filter such as a color liquid crystal display device are provided, a light-shielding image (including a black matrix) is provided for the spacer portion, the peripheral portion, and the light side of the TFT, and thus the touch panel can be applied to the touch. The board uses a light-shielding film. Especially suitable for liquid crystal display Display device, plasma display display device, EL display device with inorganic EL, CRT display device, black edge (formed with a baffle) provided on the periphery of a display device having a touch panel, or as a red, blue, and green color painting The grid-like or striped black portion between the elements is preferably used for a black matrix such as a dot-like or linear black pattern when the TFT is shielded from light.

The composition of the present invention may be in the form of a dry film obtained by coating on a carrier film (support) and drying it. When the dry film formation is carried out, the composition of the present invention is diluted with the above organic solvent to adjust to a moderate viscosity, and then a notch wheel coater, a knife coater, a lip coater, a rod coater, and a squeeze Press coater, reverse coater, transfer roll coater, gravure coater, spray coater, etc. are applied to the carrier film to a uniform thickness, and are generally dried at a temperature of 50 to 130 ° C for 1 to 30 minutes. Can be used as a dry coating film. The coating film thickness is not particularly limited, but is generally preferably 0.1 to 100 μm after drying, and is preferably selected from the range of 0.5 to 50 μm.

As the carrier film, a plastic film is used, and a polyester film such as polyethylene terephthalate, a polyimide film, a polyimide film, a polypropylene film, a polystyrene film, or the like is used. A quality film is preferred. The thickness of the carrier film is not particularly limited, but is preferably selected from the range of 0.1 to 150 μm.

In this case, after the film is formed on the carrier film, it is preferable to further laminate the peelable cover film on the surface of the coating film for the purpose of preventing dust from adhering to the surface of the coating film. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, and a watch can be used. When the cover film is peeled off, the adhesion between the coating film and the cover film may be smaller than the adhesion between the coating film and the carrier film.

Further, the composition of the present invention is adjusted to have a preferred viscosity of the above-mentioned organic solvent in the coating method, and then subjected to dip coating, flow coating, roll coating, bar coating, and wire mesh on the substrate. Coating by a printing method, a curtain coating method, a die coating method, etc., and the organic solvent contained in the composition is volatilized and dried (false drying) at a temperature of about 50 ° C to 90 ° C to form a non-stick property. Dry the film. Further, when the composition of the present invention is applied onto a carrier film and dried to form a film as a dry film, the film is bonded to the substrate by a laminate or the like to bring the coating film of the composition into contact with the substrate. By peeling off the carrier film, a layer of the coating film can be formed on the substrate.

These coating films are photohardened by, for example, irradiation with an active energy ray, or heated at a temperature of from 100 ° C to 250 ° C to be thermally cured to obtain a cured product.

Examples of the substrate include a printed circuit board or a flexible printed circuit board in which a circuit is formed first, and paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth/ All materials such as non-fibrous epoxy, glass cloth/paper epoxy, synthetic fiber epoxy, fluororesin, polyethylene, polyphenylene ether, cyanate ester resin, etc. For the copper-clad laminate of the grade (FR-4, etc.), other examples include a polyimide film, a PET film, a glass substrate, a ceramic substrate, and a wafer plate.

The volatilization drying carried out after coating the composition of the present invention can be carried out using a hot air circulating drying furnace, an IR furnace, a heating plate, a convection oven, etc. A heat source for the air heating method of steam is used to bring the hot air in the dryer into contact with the flow, and a method in which the support can be blown by the nozzle.

As an exposure machine for active energy ray irradiation, only a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short-arc lamp, or the like can be disposed, and a device that can irradiate ultraviolet rays in a range of 350 to 450 nm can be used, and can also be used directly. A drawing device (for example, a device that directly images an image by directly irradiating an active energy line from CAD data of a computer). As the light source of the direct drawing machine, only light having a maximum wavelength in the range of 350 to 410 nm can be used. The amount of exposure used for image formation differs depending on the film thickness and the like, but is generally in the range of 20 to 1000 mJ/cm ² , preferably 20 to 800 mJ/cm ² .

Further, as a developing method, it can be completed by a dipping method, a shower method, a spray method, a combing method, or the like, and potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, or barium can be used as the developing solution. An aqueous alkali solution such as sodium, ammonia or amine.

[Examples]

Hereinafter, the present invention will be described in more detail using an embodiment.

According to the mixing shown in the following Tables 1 and 2, each component was added, stirred, and dispersed by three rolls to prepare each composition. And the compounding quantity in Table 1, 2 shows the mass part.

[Synthesis Example 1]

An o-cresol novolac type epoxy resin (EPICLON (EPICLON) N-695, manufactured by DIC Corporation, softening point 95 ° C, epoxy equivalent 214, average functional group) was placed in 700 g of diethylene glycol monoethyl ether acetate. Base 7.6) 1070 g (glycidyl group (total number of aromatic rings): 5.0 mol), 360 g of acrylic acid (5.0 mol), and 1.5 g of hydroquinone were uniformly dissolved by heating and stirring at 100 °C.

Next, 4.3 g of triphenylphosphinane was charged, and after heating at 110 ° C for 2 hours, 1.6 g of triphenylphosphinylphosphine was further added thereto, and the mixture was heated to 120 ° C, and further reacted for 12 hours. Into the obtained reaction liquid, 562 g of an aromatic hydrocarbon (SOLVESSO 150) and 684 g (4.5 mol) of tetrahydrophthalic anhydride were charged, and the reaction was carried out at 110 ° C for 4 hours. Further, 142.0 g (1.0 mol) of glycidyl methacrylate was placed in the obtained reaction liquid, and the reaction was carried out at 115 ° C for 4 hours to obtain a photosensitive carboxyl group-containing resin solution. The solid content of the resin solution thus obtained was 65%, and the acid value of the solid content was 87 mgKOH/g.

*3) HO (manufactured by Mitsubishi Soap Co., Ltd.) *4) N870 (modified novolac epoxy resin manufactured by DIC Corporation) *5) 1001 (bisphenol epoxy resin manufactured by Nippon Epoxy Co., Ltd.)*6) HF-1 (phenol resin manufactured by Minghe Chemical Co., Ltd.)*7)828 (bisphenol epoxy resin manufactured by Nippon Epoxy Co., Ltd.)*8) NC3000H (epoxy resin manufactured by Nippon Kayaku Co., Ltd.)*9) SB7 ( Orient Chemical Industry Co., Ltd. organic dye) (maximum absorption value 595nm, minimum absorption value 408nm) *10) PV37 (organic pigment CTROMOPHTAL VIOLET D5700 made by BASFJAPAN)*11) Cobalt trioxide (synthetic inorganic pigment)*12) BYK-LPD20950 (made by BYK‧JAPAN)*13) BYK-354 (BYK‧JAPAN company *14) Polyflow No.99C (acrylic polymer defoamer manufactured by Kyoei Chemical Co., Ltd.)*15) Lumogen S0795 (manufactured by BASFJAPAN Co., Ltd.)*16) Carbon black (inorganic pigment)*17) Compound (A) ) *18) Compound B (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one)*19) SDO-C33 (with this chemical industry) Company made heterocyclic compound) *20) SIR-132 (manufactured by Mitsui Chemicals, Inc.) *21) YKR-5010 (manufactured by Yamamoto Kasei Co., Ltd.) *22) Lumogen IR765 (manufactured by BASF JAPAN Co., Ltd.) *23) IRG-022 (Nippon Chemical Co., Ltd.) Company system)*24) AEROSIL 380 (hydrophilic gas phase cerium oxide manufactured by Nippon Aerosil Co., Ltd.)

The composition of each of the obtained Examples and Comparative Examples was evaluated in accordance with the following. The results are shown in Tables 3 and 4 below.

(OD value (optical density))

Example 1 and Comparative Examples 3 and 4 were carried out at 160 ° C for 30 minutes in a hot air circulating drying oven, and Example 2 and Comparative Examples 1 and 2 were placed at 1000 mJ/cm ² under a high pressure mercury lamp UV transfer furnace of an 80 W3 lamp. Example 3 ~9 and Comparative Examples 5 to 8 were dried in a hot air circulating drying oven at 80 ° C for 10 minutes to form a dried coating film, and secondly by an exposure machine equipped with a metal halide lamp manufactured by Oak Co., Ltd., to become a sensitivity 7 The exposure amount of the segment is exposed. Thereafter, development was carried out by a 1 wt% Na ₂ CO ₃ aqueous solution at a spray pressure of 0.1 MPa for 1 minute, followed by a hot air circulating drying oven at 150 ° C for 60 minutes, and then hardened to a thickness of 10 μm on the glass. The coating film was measured by a transmission densitometer (X-Rite Co., Ltd. 361T). The device detects the full wavelength of 400 to 900 nm and calculates the OD value. The OD value is calculated from the transmitted light amount T according to the following formula. The higher the OD value, the better the opacity of the coating film. The composition was adjusted to be above OD3.

OD value = -Log ₁₀ (T/100)

(surface resistance value)

The glass of each of the compositions was washed by screen printing and dried to a thickness of 10 μm, and Example 1 and Comparative Examples 3 and 4 were subjected to a hot air circulating drying oven at 160 ° C for 30 minutes. Example 2 And Comparative Examples 1 and 2 were 1000 mJ/cm ^{2 in a} high-pressure mercury lamp UV transfer furnace of 80 W3 lamps, and Examples 3 to 9 and Comparative Examples 5 to 8 were dried in a hot air circulating drying oven at 80 ° C for 10 minutes to form each. The coating film was dried, and then exposed by an exposure machine equipped with a metal halide lamp manufactured by Oak Co., Ltd. to obtain an exposure amount of 7 degrees of sensitivity. Thereafter, development was carried out by a 1 wt% Na ₂ CO ₃ aqueous solution at a spray pressure of 0.1 MPa for 1 minute, and then a hot air circulation type drying oven was used, and a heat-curing treatment was performed at 150 ° C for 60 minutes to obtain a cured coating film. The surface resistance value of the curable resin composition of each of the examples and the comparative examples was measured in accordance with JIS K6911.

(Spectrophotometer)

For the hardened coating film obtained by the evaluation of the surface resistance value, a spectrophotometer (CM-2600d, manufactured by Konica Minolta Co., Ltd.) was used, and the value of the L*a*b* color system on the coating film was determined in accordance with JIS Z 8729. The measurement indicates that the L*a*b* value of the brightness index is evaluated as an indicator of blackness. The smaller the L* value is, the closer the a* and b* values are to 0, the better the blackness of the watch.

(Sensitivity)

The curable resin compositions of Examples 3 to 9 and Comparative Examples 5 to 8 were dried on a cleaned glass by screen printing, and dried to 10 μm, and dried in a hot air circulating drying oven at 80 ° C for 10 minutes. . On the coating film, a Step tablet (21-stage) manufactured by Kodak Co., Ltd. was exposed by an exposure machine equipped with a metal halide lamp manufactured by Oak Co., Ltd. at an exposure amount of 300 mJ/cm ² by 1 wt% Na ₂ CO _{3 .} The aqueous solution was developed for 1 minute at a spray pressure of 0.1 MPa, and the number of remaining segments was examined. The more the number of remaining segments, the better the sensitivity and the better.

( 100μm drawing)

The curable resin compositions of Examples 3 to 9 and Comparative Examples 5 to 8 were uniformly coated on the cleaned glass to a dry coating film of 10 μm, and dried in a hot air circulating drying oven at 80 ° C for 10 minutes. On the coating film, the opening is A negative film of 100 μm was exposed by exposure to a metal halide lamp manufactured by Oak Co., Ltd., and exposed to a sensitivity of 7 stages, and a 1 wt% Na ₂ CO ₃ aqueous solution was sprayed at 0.1 MPa for 1 minute. The accuracy of the opening is evaluated as follows. The evaluation criteria are as follows.

○: Sharp resolution.

△: Although not sharp, it has a negative size. .

×: Resolution cannot be obtained by halation and undercutting.

As a result of the above table, the composition of each example was confirmed, and compared with each comparative example, the high OD value was obtained, and the blackness was also excellent. Further, in the compositions of the respective examples, the surface resistance value was also excellent, and the precipitation problem caused by the lapse of time was not caused. In particular, in the case of a composition having both photocurability and thermosetting properties, it was confirmed that good sensitivity and good patterning property were obtained. On the other hand, in the comparative example which did not contain (B) a specific color material, the high OD value was not acquired, and the color tone differs greatly.

Claims (11)

A curable resin composition characterized by comprising (A) a near-infrared absorbing agent having a maximum absorption wavelength of 800 to 1000 nm, and (B) a minimum absorption value at 380 to 500 nm in a visible light region of 380 to 780 nm, at 500~ a color material having a maximum absorption value at 780 nm, (C) a thermosetting component, and (D) an alkali-soluble resin; (A) a content of the near-infrared absorbing agent is 0.001 to 50% by mass in the composition (solid content) (B) The amount of the specific color material is 0.05 to 80% by mass in the composition (solid content), and the amount of the (C) thermosetting component is 0.6 to 2.8 equivalents based on 100 parts by mass of the resin component. The curable resin composition of claim 1, which further comprises (E) a photopolymerization initiator. The curable resin composition of claim 2, which further contains (F) a photosensitive (meth) acrylate compound. A curable resin composition characterized by comprising (A) a near-infrared absorbing agent having a maximum absorption wavelength of 800 to 1000 nm, and (B) a minimum absorption value at 380 to 500 nm in a visible light region of 380 to 780 nm, at 500~ a color material having a maximum absorption value at 780 nm, and (F) a photosensitive (meth) acrylate compound; (A) a content ratio of the near-infrared ray absorbing agent is 0.001 to 50% by mass in the composition (solid content), ( B) The amount of the specific color material is in the composition (solid content) The amount of the photosensitive (meth) acrylate compound is from 1 to 150 parts by mass based on 100 parts by mass of the resin component, in an amount of from 0.05 to 80% by mass. The curable resin composition according to any one of claims 1 to 4, wherein the (A) near-infrared ray absorbing agent is at least one selected from the group consisting of a metal complex dye and a condensed polycyclic dye. The curable resin composition according to any one of claims 1 to 4, which is black. The curable resin composition according to any one of claims 1 to 4, which is used for forming an insulating film. A dry film obtained by applying the curable resin composition according to any one of claims 1 to 7 to a carrier film and drying it. A cured product, which is characterized in that the curable resin composition according to any one of claims 1 to 7 is applied onto a substrate, dried to obtain a dried coating film, or the curable resin composition is coated. The dry film obtained by drying on a carrier film is laminated on a coating film formed of a substrate, and is obtained by hardening. A light-shielding member characterized by comprising the cured product of claim 9. A member for a display characterized by having a cured product as claimed in claim 9.