KR20150035420A - Curable resin composition, dry film, cured product, and display member - Google Patents

Abstract

The present invention provides a curable resin composition which can maintain high light shielding property, increase insulation property, and have excellent photocurable property. The present invention relates to a curable resin composition comprising: (A) a near-infrared ray absorbent; (B) a coloring material having the minimum absorption value in 380 to 500 nm and the maximum absorption value in 500 to 780 nm in a visible ray region of 380 to 780 nm; (C) a thermosetting resin composition; and additionally (F) a photosensitive (meth)acrylate compound, to a dry film using the same, to a cured product thereof, and to a display member.

Description

TECHNICAL FIELD [0001] The present invention relates to a curable resin composition, a dry film, a cured product and a display member,

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

In a product having a liquid crystal display portion such as a cellular phone or a display, a material for forming a so-called bezel (frame region) that surrounds the display region to hide the touch panel has high light shielding property, that is, high OD value A black resin composition containing a carbon black pigment has conventionally been used (Patent Documents 1, 2, and 3). However, in the case of a carbon black-based pigment, in order to achieve a high OD value, a composition added at a high concentration tends to have poor insulating properties. Therefore, for example, depending on the construction method of the touch panel, It is not suitable for use for directly forming a conductive film. From the viewpoint of the photosensitive material, since the carbon black pigment exhibits absorption in a wide wavelength range from the ultraviolet region to the infrared region, the problem that the exposure at the time of photo-curing is absorbed by the pigment, .

Patent Document 4 discloses a black photosensitive resin composition containing a pigment containing a specific titanium black particle as a main component. However, since titanium black is likely to precipitate in a low viscosity composition due to the addition of a high concentration, there is a limit to the addition amount even if it is desired to obtain a high OD value alone.

As described above, various resin compositions having black have been proposed so far. However, along with recent technological development, it has been desired to provide a black resin composition having high light-shielding property, high insulating property, It is required to realize a material that can be used.

Japanese Patent Application Laid-Open No. H04-190362 (claims) Japanese Patent Application Laid-Open No. 2010-519592 (claims and the like) WO2012 / 133148 A1 (claims) Japanese Patent Application Laid-Open No. 2002-275343 (claims)

An object of the present invention is to provide a curable resin composition which can increase insulation while maintaining high light shielding property, and can provide particularly good photo curability.

As a result of intensive studies, the inventors of the present invention have found that the above problems can be solved by combining a near infrared absorber and a coloring material having a maximum absorption value and a minimum absorption value in a specific wavelength range to complete the present invention It came.

That is, the curable resin composition of the present invention is a curable resin composition comprising: (A) a near infrared absorbing agent; (B) a colorant having a minimum absorption value at 380 to 500 nm and a maximum absorption value at 500 to 780 nm in a visible light region of 380 to 780 nm; (C) a thermosetting component. The curable resin composition of the present invention preferably further contains (D) an alkali-soluble resin and (E) a photopolymerization initiator. It is also preferable that the curable resin composition of the present invention further contains (F) a photosensitive (meth) acrylate compound.

(B) a colorant having a minimum absorption value at 380 to 500 nm and a maximum absorption value at 500 to 780 nm in a visible light region of 380 to 780 nm, and (F) a photosensitive (meth) acrylate compound.

In the curable resin composition of the present invention, it is preferable that the maximum absorption wavelength of the near infrared absorbing agent (A) is 500 to 1000 nm. As the near infrared absorbing agent (A), at least one selected from metal complex dyes and condensed polycyclic dyes can be suitably used. The curable resin composition of the present invention preferably exhibits black color and can be suitably used for forming an insulating film.

The curable resin composition of the present invention has a minimum absorption value at 380 to 500 nm in the visible light region (380 to 780 nm) and a maximum absorption at 500 to 780 nm (B) It is also possible to use a coloring material other than a coloring material having a value.

Further, the dry film of the present invention is obtained by applying the curable resin composition of the present invention on a carrier film and drying it.

The cured product of the present invention can be obtained by applying a dry film obtained by applying and drying the curable resin composition of the present invention onto a substrate or by applying the curable resin composition onto a carrier film and drying the dried film to laminate on the substrate And curing the resulting coating film.

Further, the light-shielding member of the present invention is characterized by comprising the cured product of the present invention.

Further, the display member of the present invention is characterized by comprising the cured product of the present invention.

INDUSTRIAL APPLICABILITY According to the present invention, it becomes possible to realize a curable resin composition capable of maintaining high light-shielding property while improving the insulating property, and particularly having good photo-curability.

Hereinafter, embodiments of the present invention will be described in detail.

The curable resin composition of the present invention is a curable resin composition comprising (A) a near infrared absorbing agent, and (B) a colorant having a minimum absorption value at 380 to 500 nm and a maximum absorption value at 500 to 780 nm in a visible light region of 380 to 780 nm (C) a thermosetting component or (F) a photosensitive (meth) acrylate compound as an essential component.

(C) a thermosetting component as an essential component, together with a colorant having a minimum absorption value at 380 to 500 nm and a maximum absorption value at 500 to 780 nm at a visible light region of 380 to 780 nm; The curable resin composition according to the second embodiment of the present invention can obtain a high light shielding property, a thermosetting property and an insulating property. (A) a near-infrared absorbing agent, and (B) a coloring material having a minimum absorption value at 380 to 500 nm and a maximum absorption value at 500 to 780 nm in a visible light region of 380 to 780 nm, (F) According to the curable resin composition of the first embodiment of the present invention containing an acrylate compound as an essential component, high light shielding property, photo-curability and insulating property can be obtained.

That is, according to the present invention, there is provided a resin composition comprising (A) a near infrared absorber and (B) a coloring material having a minimum absorption value in the range of 380 to 500 nm and a maximum absorption value in the range of 500 to 780 nm (Also referred to as "(B) specific coloring material"), it is possible to realize good light-shielding property and photosensitivity without causing problems of dispersion such as sedimentation even when a coloring material is added at a high concentration. The composition of the present invention has an OD value of preferably at least 3, more preferably from 3 to 5, particularly preferably from 5 to 7, particularly in the visible light region. The curable resin composition of the present invention preferably exhibits black when it is blended.

In particular, according to the curable resin composition of the present invention, a similar color tone can be obtained when a carbon black pigment is added. As described above, there is a problem that the resistance value and the photosensitivity are lowered when a high OD value is obtained by blending the carbon black pigment. According to the present invention using the components (A) and (B) Both the OD value and the resistance value can be achieved. The present invention is useful for a touch panel member requiring a higher OD value and shielding property.

[(A) Near infrared ray absorbent]

As the near infrared absorbing agent (A) used in the present invention, a dye having an absorption maximum at 500 to 1000 nm can be used, and a dye having a maximum absorption wavelength of 700 to 1000 nm, more preferably 800 to 1000 nm is used . As the dye, metal complex dyes and condensed polycyclic dyes can be used. Specific examples thereof include phthalocyanine dyes, porphyrin dyes, cyanine dyes, quaternary dyes, squarylium dyes, azo dyes, , Anthraquinone type, diimonium type, naphthalocyanine type dye, nickel complex dye, copper ion dye, dithiol metal complex, heterocyclic compound and the like. Among them, it is preferable that absorption occurs in a visible light region such as a heterocyclic compound, a quaternary dye, a phthalocyanine, or a naphthalocyanine dye. Examples of the products include SDO-C8 and SDO-C33 (manufactured by Arimoto Chemical Industry Co., Ltd.), Lumogen IR 765 and Lumogen IR 788 (manufactured by BASF Japan) . A dye having an absorption maximum within the wavelength range and having a metal complex which absorbs light efficiently and has a sensitizing action is preferable. One or more of these may be used.

The content of the near infrared absorbing agent (A) in the curable resin composition (solid content) is preferably from 0.001 to 50 mass%, more preferably from 0.005 to 30 mass%, and even more preferably from 0.005 to 20 mass%. (A) By using a near infrared absorbing agent in combination with (B) a specific coloring material in the above range, a desired high OD value can be obtained particularly in a visible light region. In addition, absorption of a required visible wavelength portion can be further increased.

[(B) Specific coloring material]

The specific coloring material (B) to be used in the present invention may be any coloring material having a minimum absorption value in the range of 380 to 500 nm and a maximum absorption value in the range of 500 to 780 nm in the visible light region of 380 to 780 nm. The coloring material includes an organic coloring material and an inorganic coloring material. In the present invention, an organic coloring material is preferably used. Examples of the specific coloring material (B) used in the present invention include pigments and dyes, which are chemically synthesized in addition to those present naturally, and organic (synthetic) dyes include anthraquinone-based synthetic dyes, There are known organic (synthetic) dyes for known dyes of the group consisting of dyes, methine dyes, quinoline dyes, perylene dyes, and azine dyes, and these dyes are excellent in light shielding properties. Specifically, , A nigrosine including a compound having a phenazine skeleton. In particular, the color index (COLOR INDEX) C.I. Acid Black 2, Solvent Black 5, Solvent Black 7, Solvent Black 22, Solvent Black 27, Solvent Black 29 and Solvent Black 34, and in particular, there are chromium, cobalt, nickel, copper , Iron, and the like are preferred from the viewpoint of tinting strength and heat resistance. Organic pigments include organic pigments for publicly known pigments having a minimum absorption value in the range of 380 to 500 nm and a maximum absorption value in the range of 500 to 780 nm in the visible light region of 380 to 780 nm. Among them, photocuring properties, coloring properties, A phthalocyanine type, a dioxazine type, and a perylene type which are excellent in the shielding property of the region are preferable. Specifically, for example, in the case of the phthalocyanine type, Pigment Blue 15: 3, 15: 4, 15: 6, perylene-based Lumogen Black FK 4280, Lumogen Black FK 4281, Pigment Violet 23, and Pigment Violet 37 are preferred, and one of these may be used singly or two or more of them may be appropriately mixed. Examples of the inorganic colorant include cobalt tetraoxide and titanium black. One of them may be used singly or two or more of them may be appropriately mixed.

As a result of intensive studies, the present inventor has found the following points. That is, the coloring materials include pigments and dyes. Herein, they are chemically synthesized other than those present naturally. They have various choices of saturation, absorption wavelength and coloring property, and commercial properties as a composition , It is found that the photosensitive composition having a high OD value is produced in a balanced manner.

Particularly, in the case of the specific coloring material (B) used in the present invention, a high OD value is attained with a small addition amount of carbon black by an excellent tinting strength, and the desired absorption property is obtained, . Among the specific coloring materials (B) used in the present invention, especially organic dyes have been found to be suitable for a curable resin composition for shielding because they have excellent balance of light curability, coloring property and dispersibility.

Therefore, among the specific colorants (B), an organic dye is preferable in that a high OD value can be obtained with a small addition amount. Among them, a nigrosine compound having a phenazine skeleton condensed with aniline-nitrobenzene is more preferable in that a higher OD value can be obtained. This is a black condensate mixture obtained by dehydration, deammonia, or oxidation-reduction condensation reaction (Redox Condensation) in which hydrochloric acid of aniline or aniline and hydrochloric acid are added to nitrobenzene under a catalyst such as copper or iron, Phenazine skeleton. ≪ / RTI > Nigrosine is produced as a mixture of various different compounds depending on the reaction time, the feedstock and the feed ratio, and is a tripenaxane photograph represented by the following formula (I) or (II) , And azine compounds such as phenazineazine, which are represented by the following formula, and compounds in which alkyl substituents are introduced into them.

Nigrosine as a raw material of the organic dyes in the present invention is a color index C.I. For example, a black azine condensation mixture described as Acid Black 2, CI Solvent Black 5, and Solvent Black 7 can be used. Among them, a metal complex dye of Solvent Black 5 and Solvent Black 7 containing the following chemical structural formula is more preferable.

(Solvent Black 5)

(Solvent black 7)

The blending amount of the specific coloring material (B) used in the present invention is preferably from 0.05 to 80 mass%, more preferably from 0.1 to 70 mass%, and even more preferably from 0.5 to 50 mass%, in the composition (solid content). By setting the blending amount of the specific coloring material (B) within the above range, a desired high OD value can be obtained particularly in the visible light region.

[(C) Thermosetting component]

The thermosetting component (C) used in the present invention is contained in order to impart heat resistance to the composition. Particularly preferably, the thermosetting component (C) used in the present invention contains two or more cyclic ether groups and cyclic thioether groups (C) a thermosetting component having at least any one of the following components: It was confirmed that the use of the thermosetting component improves not only the heat resistance but also the adhesion to the base. Here, in the second embodiment of the present invention, the thermosetting component (C) is essential. In the first embodiment of the present invention, it is also preferable that the thermosetting component (C) is blended, whereby the thermosetting component A curable resin composition can be obtained.

The thermosetting component (C) having at least two cyclic (thio) ether groups in the molecule is a compound having at least two or more cyclic ether groups or cyclic thioether groups of 3, 4 or 5-membered rings in the molecule, For example, a compound having at least two epoxy groups in the molecule, that is, a polyfunctional epoxy compound, a compound having at least two oxetanyl groups in the molecule, that is, a polyfunctional oxetane compound, a compound having two or more thioether groups Compounds, i.e., episulfide resins, and the like.

Examples of the polyfunctional epoxy compound include Epikote 828, Epikote 834, Epikote 1001, Epikote 1004 manufactured by Mitsubishi Chemical Corporation, Epiklon 840 manufactured by DIC Corporation, Epiclon 850, Epiclon 1050, Epiclon YD-013, YD-127, YD-128 manufactured by Tohto Kasei Co., Ltd., DER 317, D.E.R. 331, D.E.R. 661, D.E.R. 664, SUMI EPOXY ESA-011, ESA-014, ELA-115, ELA-128 manufactured by Sumitomo Chemical Co., Ltd., A.E.R. 330, A.E.R. 331, A.E.R. 661, A.E.R. 664 (all trade names), bisphenol A type epoxy resin; Epikoton YL903 manufactured by Mitsubishi Chemical Corporation, Epiclon 152 manufactured by DIC Corporation, Epiclon 165, Epototo YDB-400 manufactured by Dotato Kasei Co., Ltd., YDB-500 manufactured by Dow Chemical Co., and D.E.R. 542, SUMI EPOXY ESB-400, ESB-700 manufactured by Sumitomo Chemical Co., Ltd., and A.E.R. 711, A.E.R. 714 (all trade names), brominated epoxy resin; Epikote 152, Epikote 154, manufactured by Mitsubishi Chemical Corporation, and D.E.N. 431, D.E.N. Epoclon N-770, Epiclon N-865, Epotto YDCN-701 and YDCN-704 manufactured by Dotagasei Co., Ltd., EPPN-201 manufactured by Nihon Kayaku Co., Ltd., EOCN -1025, EOCN-1020, EOCN-104S, RE-306, SUMI EPOXY ESCN-195X, ESCN-220 manufactured by Sumitomo Chemical Co., ECN-235, ECN-299 and the like (all trade names); Bisphenol F type epoxy resins such as Epiclon 830 manufactured by DIC Corporation, Epikote 807 manufactured by Mitsubishi Chemical Corporation, and Epototo YDF-170, YDF-175 and YDF-2004 manufactured by Toto Kasei Co., Hydrogenated bisphenol A type epoxy resins such as Epitoto ST-2004, ST-2007, and ST-3000 (trade name) manufactured by Toyobo Co., Ltd.; Epikote 604 manufactured by Mitsubishi Kagaku Co., Ltd., Epototo YH-434 manufactured by Tohto Kasei Co., Ltd., Sumi Epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (all trade names), glycidylamine type epoxy resin; Hidanto dolphin epoxy resin; Alicyclic epoxy resins such as Celloxide 2021 (all trade names) manufactured by Daicel Chemical Industries, Ltd.; YL-933 manufactured by Mitsubishi Chemical Corporation, T.E.N., EPPN-501 and EPPN-502 manufactured by Dow Chemical Co., Ltd. (all trade names), trihydroxyphenylmethane type epoxy resin; Biscylenol-type or biphenol-type epoxy resins such as YL-6056, YX-4000, and YL-6121 (all trade names) manufactured by Mitsubishi Chemical Corporation or a mixture thereof; Bisphenol S type epoxy resin such as EBPS-200 manufactured by Nihon Kayakazai, EPX-30 manufactured by Asahi Denka Kogyo Co., and EXA-1514 (trade name) manufactured by DIC Corporation; Bisphenol A novolak type epoxy resins such as Epikote 157S (trade name) manufactured by Mitsubishi Chemical Corporation; Tetraphenylol ethane type epoxy resin such as Epikote YL-931 (all trade names) manufactured by Mitsubishi Chemical Corporation; A heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Industries, Ltd. (all trade names); Diglycidyl phthalate resins such as Blenda DGT manufactured by Nippon Yushi Co., Ltd.; Tetraglycidylcylenoyl ethane resins such as ZX-1063 manufactured by Tohto Kasei Co., Ltd.; ESN-190, ESN-360 manufactured by Shin-Nippon Steel Chemical Co., Ltd., HP-4032, EXA-4750 and EXA-4700 manufactured by DIC Corporation; An epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; Glycidyl methacrylate copolymer-based epoxy resins such as CP-50S and CP-50M manufactured by Nihon Yucca; Further, copolymerized epoxy resin of cyclohexylmaleimide and glycidyl methacrylate; Epoxy-modified polybutadiene rubber derivatives (e.g., PB-3600 manufactured by Daicel Chemical Industries, Ltd.), CTBN-modified epoxy resins (such as YR-102 and YR-450 manufactured by Toyobo Co., And biphenyl skeleton-containing epoxy resins such as NC3000 manufactured by Kayaku Co., Ltd., but are not limited thereto. These epoxy resins may be used alone or in combination of two or more. Of these, novolak type epoxy resins, heterocyclic epoxy resins, bisphenol A type epoxy resins and mixtures thereof are particularly preferable.

Examples of the polyfunctional oxetane compound include bis [(3-methyl-3-oxetanylmethoxy) methyl] ether, bis [ Methyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) (3-ethyl-3-oxetanyl) methyl acrylate, (3-methyl-3-oxetanyl) methyl methacrylate, , Poly (p-hydroxystyrene), cardo type bisphenols, calixarene, calix resorcinarene, or a mixture of oxalic alcohol and novolak resin, poly And ether compounds with a hydroxyl group-containing resin such as sesquioxane. Other examples include copolymers of an unsaturated monomer having an oxetane ring 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 Japan Epoxy Resin Co., Ltd., and the like. An episulfide resin in which the oxygen atom of the epoxy group of the novolac epoxy resin is substituted with a sulfur atom can also be used by using the same synthetic method.

The blending amount of the thermosetting component (C) is in the range of 0.6 to 2.8 equivalents, more preferably 0.8 to 2.5 equivalents, per 100 parts by mass of the resin component. By setting the blending amount of the thermosetting component (C) 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 may be blended as a resin component. As the alkali-soluble resin (D), it is preferable to use a carboxyl group-containing resin or a phenol resin. In particular, the use of a carboxyl group-containing resin is more preferable in view of developability.

As the carboxyl group-containing resin, various conventionally known carboxyl group-containing resins having a carboxyl group in the molecule and not having an ethylenically unsaturated double bond (non-photosensitive) or having (photosensitive) thereon can be used.

In the present invention, a non-photosensitive carboxyl group-containing resin having no ethylenically unsaturated double bond in the molecule is particularly preferred in view of improvement in flexibility, reduction in curing shrinkage, and improvement in adhesion.

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

(1) a dialcohol compound containing a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate and a carboxyl group such as dimethylolpropionic acid or dimethylolbutanoic acid, a polycarbonate-based polyol Containing carboxyl groups in a diol compound such as a polyether polyol, a polyester polyol, a polyolefin polyol, a bisphenol A-based alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group Urethane resin.

(2) A urethane resin containing a carboxyl group by the reaction of a diisocyanate and a carboxyl group-containing dialcohol compound with a middle part.

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

(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 react the resulting hydroxyl group with phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride A carboxyl group-containing polyester resin to which a dibasic acid anhydride is added.

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

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

Further, in the present specification, (meth) acrylate means acrylates, methacrylates and mixtures thereof.

As the non-photosensitive carboxyl group-containing resin, the above-mentioned (1), (2), and (6) are preferably used rather than chlorine-free resin. Above all, it is preferable to use the above-mentioned (6), which has an aromatic ring and is excellent in thermal cycle, and has good balance of curing shrinkage and all characteristics.

Specific examples of the photosensitive carboxyl group-containing resin include the following compounds (any of oligomers and polymers). The ethylenically unsaturated double bond in the carboxyl group-containing resin is preferably derived from acrylic acid or methacrylic acid or a derivative thereof.

(7) a dialcohol compound containing a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate and an aromatic diisocyanate and 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, an acrylic-based polyol, a bisphenol A-based alkylene oxide adducted diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group By weight of a carboxyl group-containing photosensitive urethane resin.

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

(9) In the synthesis of the resin of the above-mentioned (7) or (8), a compound having one hydroxyl group and at least one (meth) acryloyl group in the molecule such as hydroxyalkyl (meth) (Meth) acrylated carboxyl group-containing photosensitive urethane resin.

(10) In the synthesis of the resin of the above-mentioned (8) or (9), one isocyanate group and one or more (meth) acryloyl groups in the molecule, such as equimolar reactants of isophorone diisocyanate and pentaerythritol triacrylate, (Meth) acrylate obtained by adding a compound having a carboxyl group to a carboxyl group-containing photosensitive urethane resin.

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

(12) A method for producing a photosensitive resin composition comprising a carboxyl group-containing photosensitive resin (a), which is obtained by reacting a polyfunctional epoxy resin obtained by epoxidizing a hydroxyl group of a bifunctional (epoxy) epoxy resin with epichlorohydrin, .

(13) A process for producing a bifunctional oxetane resin, which comprises reacting a bifunctional oxetane resin with a dicarboxylic acid such as adipic acid, phthalic acid, or hexahydrophthalic acid, reacting the generated primary hydroxyl group with a dibasic acid such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride A carboxyl group-containing polyester photosensitive resin to which an acid anhydride is added.

(14) A reaction product of a polyalcohol resin obtained by reacting a compound having a plurality of phenolic hydroxyl groups in a molecule, that is, a polyphenol compound with an alkylene oxide such as ethylene oxide or propylene oxide, Containing monocarboxylic acid, which is obtained by reacting a polybasic acid anhydride with a reaction product obtained by reacting an unsaturated group-containing monocarboxylic acid with an unsaturated group-containing monocarboxylic acid.

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

(16) A carboxyl group-containing photosensitive resin obtained by further adding a compound having one epoxy group and at least one (meth) acryloyl group in one molecule to the resin of the above-mentioned (7) to (15).

These photosensitive carboxyl group-containing resins other than those described in (7) to (16) may be used either singly or in combination. Of the carboxyl group-containing resins in particular, resins having an aromatic ring are preferred because of their excellent resolution.

Among them, a carboxyl group-containing resin synthesized using a phenol compound as a starting material, such as the carboxyl group-containing resins (14) and (15), can be suitably used because it has excellent insulating properties .

The above-mentioned carboxyl group-containing resin, whether photosensitive or non-photosensitive, can be mentioned as follows. That is, since a large number of carboxyl groups are present in the side chain of the backbone polymer, development with a dilute alkaline aqueous solution becomes possible.

The acid value of the carboxyl group-containing resin is suitably in the range of 40 to 200 mg KOH / g, more preferably in the range of 45 to 120 mg KOH / g. If 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 the acid value exceeds 200 mgKOH / g, dissolution of the exposed portion by the developer proceeds, The resist is dissolved and peeled off as a developing solution without distinction between the light portion and the unexposed portion, which makes it difficult to draw a normal resist pattern.

The weight-average molecular weight of the above-mentioned carboxyl group-containing resin varies depending on the resin skeleton, but is generally in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. If the weight-average molecular weight is less than 2,000, the tack free performance may deteriorate, and the developability of the coated film after exposure may not be obtained, and the resolution may be significantly lowered. On the other hand, if the weight average molecular weight exceeds 150,000, the developability may be remarkably deteriorated.

The amount of such a carboxyl group-containing resin is suitably in the range of 20 to 60 mass%, preferably 30 to 50 mass%, in the curable resin composition. If the blending amount of the carboxyl group-containing resin is less than 20% by mass, the film strength may be lowered, which is not preferable. On the other hand, if it is more than 60% by mass, the viscosity of the curable resin composition becomes high or the coatability to the carrier film becomes low, which is not preferable.

In the present invention, either the photosensitive resin containing a photosensitive carboxyl group or the resin containing a carboxyl group having no photosensitive property may be used as the alkali-soluble resin, or a mixture thereof may be used. However, the photosensitive resin containing a photosensitive carboxyl group- (Containing a photosensitive carboxyl group: a carboxyl group-containing resin having no photosensitivity) is preferably used in a ratio of (1: 9) to (9: 1) Is in the range of (2: 8) to (8: 2), more preferably in the range of (5: 5) to (7: 3). Within this range, it is possible to obtain a cured product of a resin composition and a printed wiring board having the cured product, both of which are excellent in both resolution and adhesion, while avoiding an increase in exposure dose.

The photosensitive carboxyl group-containing resin and the photosensitive group-containing carboxyl group-containing resin other than those described above may be used alone or in combination of two or more. Among the carboxyl group-containing resins, resins having an aromatic ring are particularly preferable because they have a high refractive index and excellent resolution, and further, they have a novolak structure because they are excellent in terms of resolution, PCT resistance and crack resistance .

As the phenol resin, a compound having a phenolic hydroxyl group, for example, a compound having a skeleton of a biphenyl skeleton or a phenylene skeleton or both, or a compound containing a phenolic hydroxyl group, such as phenol, orthocresol, Xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol , Phenol resins having various skeletons synthesized by using catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, and fluoroglucinol may be used.

Examples thereof include phenol novolak resins, alkylphenol novolac resins, bisphenol A novolak resins, dicyclopentadiene type phenol resins, xylok type phenol resins, terpene modified phenol resins, polyvinyl phenols, bisphenol F, Phenol resins such as bisphenol S type phenol resin, poly-p-hydroxystyrene, condensates of naphthol and aldehydes, condensation products of dihydroxynaphthalene and aldehydes, and the like can be used.

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

Examples of commercially available products of such phenol resins include HF1H60 (manufactured by Meiwa Kasei Co.), phenolite TD-2090, phenolite TD-2131 (manufactured by Dainippon Printing Co.), Bethmol CZ-256-A CST90, S-1P, S-2P (manufactured by Maruzen Kogyo Co., Ltd.) of polyvinyl phenol, etc., . These phenolic resins may be used alone or in combination of two or more.

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

In the curable resin composition of the present invention, when a material that does not contain an ethylenic unsaturated group is used as the alkali-soluble resin (D), a compound having at least one, preferably at least two ethylenically unsaturated groups in the molecule That is, a photopolymerizable compound such as a photopolymerizable monomer and an oligomer must be used in combination. The photopolymerizable compound is photo-cured by irradiation with active energy rays, and (D) dissolves the alkali-soluble resin in an aqueous alkali solution. In addition, even when a carboxyl group-containing resin is used, a photopolymerizable compound can be used in combination for the purpose of further promoting photo-curing.

In either case, one kind or plural kinds of photopolymerizable compounds can be used.

[(E) Photopolymerization initiator]

The composition of the present invention may contain (E) a photopolymerization initiator. Examples of the photopolymerization initiator (E) include photopolymerization initiators such as benzophenone, acetophenone, aminoacetophenone, benzoin ether, benzyl ketal, acylphosphine oxide, oxime ether, oxime ester and titanocene Compounds.

Examples of the photopolymerization initiator (E) as the photopolymerization initiator include oxime ester-based photopolymerization initiators including structural moieties represented by the following general formula (I),? -Amino acetophenone based moieties represented by the general formula (II) (III), and a titanocene-based compound represented by the general formula (IV). In the present invention,

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 benzoyl group. R ² represents a phenyl group, an alkyl group, a cycloalkyl group, an alkanoyl group or a benzoyl group.

The phenyl 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, a phenyl group, a halogen atom and the like.

The alkyl group represented by R ¹ and R ² is preferably an alkyl group having 1 to 20 carbon atoms, and may contain at least one oxygen atom in the alkyl chain. It may also be substituted with one or more hydroxyl groups.

As the cycloalkyl group represented by R ¹ and R ² , a cycloalkyl group having 5 to 8 carbon atoms is preferable.

As the alkanoyl group represented by R ¹ and R ² , an alkanoyl group having 2 to 20 carbon atoms is preferable.

The benzoyl 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, a phenyl group, and the like.

In the 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 of them may combine to 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 substituted with a halogen atom, an alkyl group or an alkoxy group, Represents a carbonyl group having 1 to 20 carbon atoms (provided that both are a carbonyl group having 1 to 20 carbon atoms).

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

Examples of the oxime ester-based photopolymerization initiator containing the structural moiety represented by the general formula (I) include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], A compound represented by the following formula (I-1), a compound represented by the following formula (I-1), 2- (Acetyloxyiminomethyl) thioxanthen-9-one, and compounds represented by the following general formula (I-2).

In the general formula (I-2), R ¹¹ is the same as R ¹ in the general formula (I), and R ¹² and R ¹⁴ are each independently the same as 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 benzoyl group, an alkanoyl group having 2 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms When the number of carbon atoms in the alkyl group constituting the actual group is 2 or more, the alkyl group may be substituted with at least one hydroxyl group or may have at least one oxygen atom in the middle of the alkyl chain) or a phenoxycarb group.

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

Such an oxime ester-based photopolymerization initiator is preferable because, for example, the sensitivity of the composition of the present invention can be increased with respect to exposure for direct imaging, and the resolution is excellent.

In particular, when the exposure is an h-line (405 nm) of a single wavelength, the oxime ester-based photopolymerization initiator is preferably a dimer.

As the oxime ester-based photopolymerization initiator of the dimer, it is more preferable to be a compound represented by the following general formula (I-3).

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, an anthryl group, a pyridyl group, a benzofuryl group or a benzothienyl group.

Ar is a single bond or a single bond or an alkylene group having 1 to 10 carbon atoms, a vinylene group, a phenylene group, a biphenylene group, a pyridylene group, a naphthylene group, an anthrylene group, a thienylene group, a furylene group, A 4,4'-stilbene-diyl group, and a 4,2'-styrene-diyl group.

and n represents an integer of 0 to 1.

As the alkyl group represented by R ²³ , an alkyl group having 1 to 17 carbon atoms is preferable.

As the alkoxy group represented by R ²³ , an alkoxy group having 1 to 8 carbon atoms is preferable.

The phenyl group represented by R ²³ may have a substituent, and 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), an amino group, (Preferably 1 to 8 carbon atoms of the alkyl group) and a dialkylamino group (preferably 1 to 8 carbon atoms of the alkyl group).

Naphthyl group represented by R ²³ as may be have a substituent, the substituent may be a group of the same as those of the substituent in a phenyl group may have to be represented by R ^23.

As the alkyl group represented by R ²¹ and R ²² , an alkyl group having 1 to 17 carbon atoms is preferable.

As the alkoxy group represented by R ²¹ and R ²² , an alkoxy group having 1 to 8 carbon atoms is preferable.

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), an alkoxy group (preferably having 1 to 8 carbon atoms) , An alkylamino group (preferably having 1 to 8 carbon atoms in the alkyl group) and a dialkylamino group (preferably having 1 to 8 carbon atoms in the alkyl group).

R may be have a naphthyl group substituents represented by ²¹ and R ^22, may be the substituent, R ²¹ and R ²² to a group of the same as those of the substituent in a phenyl group may have to be represented by.

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, Ar is a single bond, a phenylene group, a naphthylene group or a thienylene group, n is preferably 0. Of the compounds represented by the general formula (I-3), those represented by the following structural formulas are more preferable.

When such an oxime ester-based photopolymerization initiator is used, it is preferably used in combination with an? -Amino acetophenone-based photopolymerization initiator or the like containing the structural moiety represented by the general formula (II) in order to improve the sensitivity to exposure.

Examples of the? -Amino acetophenone-based photopolymerization initiator containing the structural moiety represented by the general formula (II) include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoprofenon- 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- -Morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone, and the like.

Examples of the acylphosphine oxide photopolymerization initiator containing the structural moiety represented by the general formula (III) include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, and the like.

Examples of the titanocene photopolymerization initiator represented by the general formula (IV) include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro- -Yl) -phenyl) titanium. ≪ / RTI >

The blending ratio of the (E) photopolymerization initiator is preferably 0.01 to 100 parts by mass, more preferably 0.5 to 80 parts by mass based on 100 parts by mass of the resin component. If the blending ratio of the (E) photopolymerization initiator is less than 0.01 part by mass based on 100 parts by mass of the resin component, the photocuring property is insufficient and the coating film may peel off or the coating film properties such as chemical resistance may deteriorate. On the other hand, when the blending ratio of the (E) photopolymerization initiator is more than 100 parts by mass based on 100 parts by mass of the resin component, the deep curing property may be lowered due to the light absorption of the (E) photopolymerization initiator.

The curable resin composition of the present invention may contain a photopolymerization initiator other than the above-mentioned compounds, a photoinitiator, and a sensitizer, and examples thereof include benzoin compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, Benzophenone compounds, xanthone compounds, and tertiary amine compounds.

Specific examples of the benzoin compound are, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether. Concrete examples of the acetophenone compound are, for example, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone . Specific examples of the anthraquinone compound are, for example, 2-methyl anthraquinone, 2-ethyl anthraquinone, 2-t-butyl anthraquinone and 1-chloro anthraquinone. Specific examples of the thioxanthone compound include, for example, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone to be. Specific examples of the ketal compound include, for example, acetophenone dimethyl ketal and benzyl dimethyl ketal. Specific examples of the benzophenone compound include, for example, benzophenone, 4-benzoyldiphenylsulfide, 4-benzoyl-4'-methyldiphenylsulfide, 4-benzoyl- Benzoyl-4'-propyldiphenylsulfide.

Specific examples of the tertiary amine compound include, for example, an ethanolamine compound, a compound having a dialkylaminobenzene structure, for example, 4,4'-dimethylaminobenzophenone (Nissokyure MABP manufactured by Nippon Soda Co., Ltd.) Dialkylaminobenzophenone such as 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.), 7- (diethylamino) -4-methyl-2H-1-benzopyran- Dimethylaminobenzoate (Kaya Cure EPA, manufactured by Nippon Kayaku Co., Ltd.), ethyl 2-dimethylaminobenzoate (manufactured by Nippon Kayaku Co., Ltd.) (International Bio-Synthesis (Quantacure DMB manufactured by Nippon Kayaku Co., Ltd.), 4-dimethylaminobenzoic acid (n-butoxy) ethyl (Quantacure BEA manufactured by International Bio-Synthesis Inc.), p-dimethylaminobenzoic acid isoamylethyl ester Kayacure DMBI), 2-ethylhexyl 4-dimethylaminobenzoate (manufactured by Van Dyk) Esolol 507), and 4,4'-diethylaminobenzophenone (EAB manufactured by Hodogaya Chemical Co., Ltd.).

As the tertiary amine compound, a compound having a dialkylaminobenzene structure is preferable, and a dialkylaminobenzophenone compound and a dialkylamino group-containing coumarin compound having a maximum absorption wavelength of 350 to 410 nm are particularly preferable. As the dialkylaminobenzophenone compound, 4,4'-diethylaminobenzophenone is preferable because it has low toxicity. A coumarin compound having a dialkylamino group having a maximum absorption wavelength of 350 to 410 nm can provide a colored film reflecting the color of the coloring agent itself using a coloring agent since the maximum absorption wavelength is in the ultraviolet region. Particularly, 7- (diethylamino) -4-methyl-2H-1-benzopyran-2-one is preferable because it exhibits an excellent increase / decrease effect with respect to a laser beam having a wavelength of 400 to 410 nm.

[(F) Photosensitive (meth) acrylate compound]

The photosensitive (meth) acrylate compound (F) used in the present invention is photo-cured by irradiation with active energy rays to insolubilize or insolubilize the resin component in an aqueous alkali solution. Examples of such compounds include polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate and epoxy Specific examples thereof include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; Diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; Acrylamides such as N, N-dimethyl acrylamide, N-methylol acrylamide and N, N-dimethylaminopropylacrylamide; Aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate and N, N-dimethylaminopropyl acrylate; Polyhydric alcohols such as hexanediol, trimethylol propane, pentaerythritol, dipentaerythritol, and tris-hydroxyethylisocyanurate, or ethylene oxide adducts thereof, propylene oxide adducts, or? -Caprolactone adducts Polyhydric acrylates such as water; Phenoxy acrylate, bisphenol A diacrylate, and polyhydric acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; Polyhydric acrylates of glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylol propane triglycidyl ether and triglycidyl isocyanurate; The present invention is not limited to the above, and may be exemplified by acrylates obtained by directly acrylating a polyol such as a polyether polyol, a polycarbonate diol, a hydroxyl-terminated polybutadiene, or a polyester polyol, or acrylates and melamine acrylates obtained by urethane acrylating through a diisocyanate , Functional acrylates such as nano silica-modified acrylate and isocyanate acrylate, and at least one of the respective methacrylates corresponding to the acrylate.

In addition, epoxy acrylate resins obtained by reacting polyfunctional epoxy resins such as cresol novolak type epoxy resins with acrylic acid, or epoxy acrylate resins obtained by reacting hydroxy acrylates such as pentaerythritol triacrylate with isophorone And an epoxy urethane acrylate compound obtained by further reacting a half urethane compound of diisocyanate such as diisocyanate. Such an epoxy acrylate resin can improve photo-curability without deteriorating the touch-dry composition.

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

[Other color]

The composition of the present invention may further contain a known coloring material other than the specific coloring material (B) in addition to the specific coloring material (B) for color tone adjustment or the like, and may further contain an organic pigment, an inorganic pigment, Any of the pigments may be used. Specific examples include black coloring agents, red coloring agents, blue coloring agents, yellow coloring agents, green coloring agents, purple coloring agents, orange coloring agents, brown coloring agents and white coloring agents. Among them, a black coloring agent, a blue coloring agent, a green coloring agent with a blue color, and a purple coloring agent are preferable because the OD value is increased.

(Black coloring agent)

Examples of the black colorant include carbon black based pigments such as CI Pigment Black 6, 7, 9 and 18, black pigments such as CI Pigment Black 8 and 10, CI Pigment Black 11, 12 and 27, Pigment Brown (Pigment Brown) 35; For example, pigments of anthraquinone pigments such as iron oxide of CI Pigment Black 20, pigments of cobalt oxide such as CI Pigment Black 13, 25, 29, CI Pigment Black 15, 28, and the like, manganese-based pigments such as CI Pigment Black 14 and 26, antimony oxide pigments such as CI Pigment Black 23, nickel oxide pigments such as CI Pigment Black 30, CI Pigment Black 31 and 32, and Rumogen Black FK4280 manufactured by BASF Japan Ltd. (except those corresponding to the specific colorant (B)), aniline pigments of Pigment Black 1 and molybdenum sulfide and bismuth sulfide Can be exemplified as suitable pigments. These pigments may be used alone or in appropriate combination.

(Red colorant)

Examples of the red colorant include monoazo, disazo, azo lake, benzimidazolone, perylene, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone. A color index number as shown below is given.

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

Disazo system: Pigment Red 37, 38, 41;

48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 53: 2, 57: 1, 58: 4, 63: 1, 63: 2, 64: 1, 68;

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

Perylene system: Solvent Red 135, 179, Pigment Red 123, 149, 166, 178, 179, 190, 194, 224;

Diketopyrrolopyrrole-based pigments: Pigment Red 254, 255, 264, 270, 272;

Condensation azo pigments: Pigment Red 144, 166, 214, 220, 221, 242;

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

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

(Blue coloring agent)

Examples of the blue colorant include pigments such as phthalocyanine type pigments (except those corresponding to the specific coloring material (B)), anthraquinone type pigments, dioxazine type pigments (excluding those corresponding to the specific coloring material (B) (Pigment), and the dye system is classified as a solvent. Specific examples include those having the following color index numbers. In addition to these, metal-substituted or unsubstituted phthalocyanine compounds (excluding those corresponding to the specific coloring material (B)) may also 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 colorant include a monoazo system, a disazo system, a condensed azo system, a benzimidazolone system, an isoindolinone system, and an anthraquinone system, and specific examples include the following colorants.

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;

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

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

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

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

Anthraquinone-based solvents: Solvent Yellow 163, Pigment Yellow 24, 108, 193, 147, 199, 202;

(Green colorant)

Examples of the green colorant include a phthalocyanine series (except those corresponding to the specific colorant (B)) and anthraquinone series, and specifically, Pigment Green 7, 36, Solvent Green 3, , 20, 28, etc. can be used. In addition to the above, metal substituted or unsubstituted phthalocyanine compounds may also be used.

(Purple coloring agent)

Specific examples of the purple colorant 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 colorant include Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64 , 71, 73, and the like.

(browning)

Specific examples of the brown colorant include Pigment Brown 23, 25 and the like.

(White colorant)

Examples of the white colorant include zinc oxide represented by Pigment white 4, titanium oxide represented by Pigment White 6, and zinc sulfide represented by Pigment White 7, and titanium oxide is particularly preferred from the viewpoint of tinting power and non-toxicity R-550, R-580, R-630, R-820 and CR-50 manufactured by Fuji Titanium Kogyo Co., Ltd., TR-600, TR-700, TR- TA-100, TA-200, TA-300, and TA-300 manufactured by Fuji Titanium Corporation, such as CR-60, CR-90, KR-270, KR- 500, anatase type titanium oxide such as KA-15, KA-20, KA-35 and KA-90 manufactured by Titan Kogyo Co., When the white colorant is added in a small amount, for example, in an amount of 0.1 to 3% by mass in the composition, an effect of increasing the hiding power can be expected.

As the coloring material other than the specific coloring material (B), at least one of the above-mentioned coloring materials may be used, and it preferably contains at least one of a black coloring agent, a blue coloring agent, a green coloring agent and a purple coloring agent, And a subtle color feeling can be adjusted. Among them, it is preferable that it has a maximum absorption wavelength in the range of 500 to 900 nm, particularly 500 to 800 nm, and the absorption in the range of 380 to 500 nm is lower than the OD value and the photocurability. As the coloring material other than the specific coloring material (B) among the above, it is preferable to specifically include, for example, titanium black, cobalt trioxide, or a synthetic inorganic pigment showing black color, whereby OD value and photo- And the heat resistance can be improved while keeping it.

The amount of the coloring material other than the specific coloring material (B) is preferably in the range of 99: 1 to 10: 90, and the coloring material other than the (B) :( B) More preferably in the range of 99: 1 to 30:70, further preferably in the range of 99: 1 to 50:50, and particularly preferably in the range of 99: 1 to 51:49. By setting the blending amount of the coloring material other than the specific coloring material (B) within the above range, it is possible to obtain a curable resin composition having a good balance in OD value, photo-curability and light resistance.

[Thermal curing catalyst]

The curable resin composition of the present invention preferably further contains a thermosetting catalyst. As the thermosetting catalyst, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, Imidazole derivatives such as 1-cyanoethyl-2-phenylimidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; Amines such as dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine and 4- Compounds, hydrazine compounds such as adipic acid dihydrazide and sebacic acid dihydrazide; And phosphorus compounds such as triphenylphosphine. 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (all trade names of imidazole compounds) manufactured by Shikoku Chemical Industry Co., Ltd., U- CAT3503N, U-CAT3502T (all of the block isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102 and U-CAT5002 (both bicyclic amidine compounds and salts thereof). However, the present invention is not limited thereto, and any of them may be used as long as it accelerates a reaction between a thermosetting catalyst of an epoxy resin or an oxetane compound or a carboxyl group with an epoxy group and / or an oxetanyl group, Can be used. Further, it is also possible to use at least one selected from the group consisting of guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, Azine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid And S-triazine derivatives such as adducts may be used. Preferably, a compound that also functions as such an adhesion-imparting agent is used in combination with a thermosetting catalyst.

The blending amount of the thermosetting catalyst is usually sufficient. For example, it is preferably 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) to be.

[Other ingredients]

Further, an inorganic filler may be further added to the composition of the present invention for the purpose of improving properties such as adhesion, mechanical strength and linear expansion coefficient of a cured product. Examples of such an inorganic filler include known inorganic fillers such as barium sulfate, barium titanate, silicon oxide, fine powdery silicon oxide, amorphous silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, Of inorganic fillers can be used.

The composition of the present invention may contain, if necessary, a conventionally known polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, t-butyl catechol, pyrogallol, phenothiazine and the like, a known tolerance such as fine silica, organic bentonite and montmorillonite A silane coupling agent such as an isocyanate-based, imidazole-based, thiazole-based or triazole-based silane coupling agent, an antioxidant, a photopolymerization sensitizer, a light stabilizer, a dispersant, Additives such as a curing accelerator, a flame retardant, a flame retardant, and the like can be further blended.

The composition of the present invention may contain an organic solvent used for preparation of the composition and viscosity adjustment. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; Methylcellosolve, butylcellosolve, carbitol, methylcarbitol, butylcarbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (DPM), dipropylene glycol diethyl ether, tripropylene glycol Glycol ethers such as monomethyl ether; Esters such as ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate and propylene carbonate; Aliphatic hydrocarbons such as octane and decane; Petroleum ether such as petroleum ether, petroleum naphtha, and solvent naphtha may be used. These organic solvents may be used alone or in combination of two or more.

The curable resin composition of the present invention containing the above-mentioned compounding ingredients has a maximum absorption value at 500 to 780 nm and a minimum absorption value at 380 to 500 nm in the visible light region of 380 to 780 nm as the composition, It is preferable that the photosensitive composition exhibits a black color. It is preferable that the L * value of the cured product thereof measured by a colorimetric system, which is a reference indicating blackness, is 30 or less in SCI system. The a * value is preferably -5 to 5, and the b * value is preferably -5 to 5. More 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 a high OD value and a high dielectric constant, it is useful as a material for forming an insulating film. The curable resin composition of the present invention is also useful for light-shielding members. 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 applied to various applications such as printing ink, ink jet ink, photomask producing material, printing proof fabrication material, etching resist, solder resist, barrier rib of a plasma display panel (PDP) A wiring pattern of an electronic component, a conductive paste, a conductive film, a shielded image such as a black matrix, and the like. Particularly, the curable resin composition of the present invention is used for improving the display characteristics of a color filter used for a color liquid crystal display device or the like Shielding film for a touch panel, for providing a light-shielding image (including a black matrix) on a color pattern spacing, a peripheral portion, and an external light side of a TFT, or for a light-shielding film for a touch panel. Particularly preferably, a black frame (bezel formation) provided on the periphery of a liquid crystal display device, a plasma display display device, an EL display device with inorganic EL, a CRT display device, and a display device including a touch panel, Is preferably used as a black matrix such as a lattice image between green coloring pixels or a black portion on a stripe, more preferably a dot image for TFT shielding or a black pattern on a line.

The composition of the present invention may be in the form of a dry film obtained by coating and drying on a carrier film (support). In the case of dry film formation, the composition of the present invention is diluted with the above-mentioned organic solvent and adjusted to an appropriate viscosity, and the composition is applied to a substrate by using a comma coater, blade coater, lip coater, rod coater, squeeze coater, reverse coater, transfer roll coater, Coater or the like to a uniform thickness on the carrier film and dried at a temperature of usually 50 to 130 DEG C for 1 to 30 minutes to obtain a dried coating film. The thickness of the coating film is not particularly limited, but is generally appropriately selected in the range of 0.1 to 100 占 퐉, preferably 0.5 to 50 占 퐉 in the film thickness after drying.

As the carrier film, a plastic film is used, and it is preferable to use a plastic film such as a polyester film such as polyethylene terephthalate, a polyimide film, a polyamideimide film, a polypropylene film, and a polystyrene film. The thickness of the carrier film is not particularly limited, but is generally appropriately selected in the range of 0.1 to 150 mu m.

In this case, it is preferable to further laminate a peelable cover film on the surface of the coating film for the purpose of preventing the adhesion of dust to the surface of the coating film after forming the coating film on the carrier film. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper and the like can be used. When the cover film is peeled off, May be smaller than the adhesion force of the carrier film.

After the composition of the present invention is adjusted to a viscosity suitable for the application method using the above-mentioned organic solvent, a dip coating method, a flow coating method, a roll coating method, a bar coater method, a screen printing method, , A die coater method and the like, and the organic solvent contained in the composition is volatilized and dried (dried) at a temperature of about 50 캜 to 90 캜 to form a dry film without tackiness. When the composition of the present invention is coated on a carrier film, and the film is dried and wound as a film, it is laminated on a substrate so that the coating film of the composition comes into contact with the substrate with a laminator or the like, A layer of a coating film can be formed on a substrate.

The coating film is cured by, for example, irradiation of active energy rays, or by heating at a temperature of 100 to 250 DEG C to thermally cure the cured product.

As the above substrate, it is possible to use a substrate such as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / nonwoven epoxy, glass cloth / paper epoxy, synthetic fiber epoxy, fluororesin, polyethylene (FR-4 or the like), other polyimide film, PET film, glass substrate, ceramic substrate, or the like using a material such as a copper clad laminate for a high frequency circuit using a polyphenylene ether, a cyanate ester resin, , A wafer plate, and the like.

The volatile drying performed after application of the composition of the present invention can be carried out by using hot air circulating drying furnace, IR, a hot plate, a convection oven, or the like, , And a method of spraying onto a support from a nozzle can be used.

Examples of the exposure apparatus used for irradiation with active energy rays include a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., and irradiating ultraviolet rays in the range of 350 to 450 nm. A direct imaging device that draws an image by directly irradiating an active energy ray by CAD data from a computer) can also be used. As a light source of a direct game, any light source having a maximum wavelength in the range of 350 to 410 nm may be used. Light exposure for image formation film varies, depending upon the thickness, but in general can be within the 20 to 1000mJ / cm ^2, preferably in the range of 20 to a range of 800mJ / cm ^2.

Examples of the developing method include a dipping method, a shower method, a spraying method, a brushing method and the like. As the developing solution, an alkali aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, Can be used.

[Example]

Hereinafter, the present invention will be described in more detail with reference to examples.

The components were mixed, stirred, and dispersed in a three-roll mill according to the formulation shown in Tables 1 and 2 below to prepare compositions, respectively. The blending amounts in Tables 1 and 2 represent parts by mass.

[Synthesis Example 1]

To 700 g of diethylene glycol monoethyl ether acetate were added 1070 g of an orthocresol novolac epoxy resin (EPICLON N-695, manufactured by DIC Corporation, softening point 95 캜, epoxy equivalent 214, average functional group number 7.6) (glycidyl group number (The total number of aromatic rings): 5.0 moles), 360 g (5.0 mols) of acrylic acid and 1.5 g of hydroquinone were charged and stirred at 100 DEG C to dissolve uniformly.

Subsequently, 4.3 g of triphenylphosphine was added, and the mixture was heated to 110 DEG C and reacted for 2 hours. Then, 1.6 g of triphenylphosphine was further added, the temperature was raised to 120 DEG C and the reaction was further performed for 12 hours. To the obtained reaction solution, 562 g of aromatic hydrocarbon (Solvesso 150) and 684 g (4.5 mol) of tetrahydrophthalic anhydride were added and reacted at 110 DEG C for 4 hours. Further, 142.0 g (1.0 mol) of glycidyl methacrylate was added to the obtained reaction solution, and the reaction was carried out at 115 캜 for 4 hours to obtain a photosensitive resin solution containing a carboxyl group. The resin solution thus obtained had a solid content of 65% and an acid value of solid content of 87 mgKOH / g.

* 1) Acrylic oligomer (MRX-401 manufactured by Mitsubishi Materials Corporation)

* 2) Laromer LR8863 (BASF Japan)

* 3) HO (manufactured by Mitsubishi Rayon Co., Ltd.)

* 4) N870 (modified novolac epoxy resin, manufactured by DIC Corporation)

* 5) 1001 (bisphenol epoxy resin, manufactured by Japan Epoxy Resins Co., Ltd.)

* 6) HF-1 (phenol resin, manufactured by Meiwa Kasei Co., Ltd.)

* 7) 828 (bisphenol epoxy resin, manufactured by Japan Epoxy Resins Co., Ltd.)

* 8) NC3000H (epoxy resin, manufactured by Nippon Kayaku Co., Ltd.)

* 9) S.B.7 (organic dye manufactured by Orient Chemical Co., Ltd.)

(Maximum absorption value: 595 nm, minimum absorption value: 408 nm)

* 10) P. V.37 (CTROMOPHTAL VIOLET D5700, manufactured by BASF Japan Co., Ltd.)

* 11) Cobalt trioxide (synthetic inorganic pigment)

* 12) BYK-LPD20950 (manufactured by Big Chem Japan)

* 13) BYK-354 (manufactured by Big Chem Japan)

* 14) Polyflow No. 99C (Acrylic Polymerization System Defoamer, manufactured by Kyoeisha Chemical Co., Ltd.)

* 15) Lumogen S0795 (manufactured by BASF Japan)

* 16) Carbon black (inorganic pigment)

* 17) Compound (A)

* 18) Compound (B) (2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl)

* 19) SDO-C33 (heterocyclic compound manufactured by Arimoto Chemical Co., Ltd.)

* 20) SIR-132 (manufactured by Mitsui Chemical Industry Co., Ltd.)

* 21) YKR-5010 (manufactured by Yamamoto Kasei Co., Ltd.)

* 22) Lumogen IR765 (manufactured by BASF Japan)

* 23) IRG-022 (manufactured by Nihon Kaya Co., Ltd.)

* 24) AEROSIL 380 (manufactured by Nihon Aerosil Co., hydrophilic fumed silica)

The compositions of each of the obtained examples and comparative examples were evaluated as follows. The results are shown in Tables 3 and 4.

(OD value (optical density))

Example 1 and Comparative Examples 3 and 4 were carried out in a hot air circulating type drying furnace at 160 ° C for 30 minutes and in Example 2 and Comparative Examples 1 and 2 at a pressure of 1000 mJ / cm ² in a high pressure mercury lamp UV conveyor such as 80W 3, To 9 and Comparative Examples 5 to 8 were dried in a hot air circulating type drying furnace at 80 DEG C for 10 minutes to form a dry film and subsequently exposed to light having an exposure amount of 7 stages by means of an exposure machine equipped with a metal halide lamp manufactured by OAK INDUSTRIES, Lt; / RTI > Thereafter, the substrate was developed with a 1 wt% Na ₂ CO ₃ aqueous solution at a spray pressure of 0.1 MPa for 1 minute, and then subjected to a heat curing treatment at 150 ° C for 60 minutes using a hot air circulation type drying furnace, , And measurement was carried out with a transmission densitometer (X-Rite Corp. 361T). This apparatus detects the entire wavelength of 400 to 900 nm and calculates an OD value. The OD value was calculated from the amount of transmitted light (T) based on the following equation. The higher the OD value, the better the light shielding property of the coating film is. The composition was adjusted to OD 3 or higher.

OD value = -Log ₁₀ (T / 100)

(Surface resistance value)

Each of the compositions was dried on a glass screen by screen printing and then applied on the entire surface to a thickness of 10 μm. Example 1 and Comparative Examples 3 and 4 were carried out in a hot-air circulating type drying oven at 160 ° C. for 30 minutes, Examples 1 and 2 were dried at 80 mW / cm ² in a high-pressure mercury lamp UV conveyor such as 80 W 3, at 1000 mJ / cm ² , and in Examples 3 to 9 and Comparative Examples 5 to 8, Followed by exposure at an exposure dose of 7 stages in sensitivity by an exposure machine equipped with a metal halide lamp manufactured by OAK INDUSTRIES, LTD. Thereafter, the film was developed with a 1 wt% Na ₂ CO ₃ aqueous solution at a spray pressure of 0.1 MPa for 1 minute, and then subjected to a heat curing treatment at 150 ° C for 60 minutes using a hot air circulation type drying furnace to obtain a cured coating film. The surface resistance values of the curable resin compositions of each of the examples and comparative examples were measured in accordance with JIS K6911.

(Spectral side colorimeter)

The value of the L * a * b * colorimetric system on the coating film was measured according to JIS Z 8729 using a spectroscopic colorimetric system (CM-2600d, manufactured by Konica Minolta Co., Ltd.) for the cured coating film obtained in the evaluation of the surface resistance value, Was evaluated as an index of blackness. ≪ tb > < TABLE > The smaller the L * value and the closer to 0 all the a * and b * values are, the better the blackness is.

(Sensitivity)

The curable resin compositions of Examples 3 to 9 and Comparative Examples 5 to 8 were dried by screen printing on cleaned glass and then applied to the entire surface to a thickness of 10 탆 and dried in a hot air circulation type drying oven at 80 캜 for 10 minutes. A step tablet (21 steps) manufactured by Kodak Co., Ltd. was placed on this coating film and exposed with an exposure amount of 300 mJ / cm ^{2 using} an exposure machine equipped with a metal halide lamp manufactured by Orkmanufacturing Co., Ltd., and sprayed with a 1 wt% Na ₂ CO ₃ aqueous solution And the remaining number of steps after development at 0.1 MPa for 1 minute was examined. The greater the number of the remaining monomers, the better the sensitivity is.

(patterning of? 100 탆)

The curable resin compositions of Examples 3 to 9 and Comparative Examples 5 to 8 were applied on a cleaned glass surface by screen printing to cover the whole surface to a thickness of 10 μm and dried in a hot air circulating type drying oven at 80 ° C for 10 minutes . Place the negative film to the opening φ100㎛ on this coating film, exposure sensitivity in the exposure amount that is 7 by the exposure device equipped with a metal halide lamp of oak production Sosa prepared, and 1wt% Na ₂ CO ₃ aqueous solution by the spray pressure 0.1 MPa for 1 minute. The evaluation criteria are as follows.

○: Sharp resolution.

[Delta]: φ of a negative dimension is obtained although it is not sharp.

X: Resolution is not obtained due to halation or undercut.

From the results in the above table, it was confirmed that a high OD value was obtained in the compositions of the respective Examples as compared with Comparative Examples, and that the blackness was excellent. In the compositions of the respective examples, good performance was also obtained with respect to the surface resistance value, and the problem of sedimentation with time did not occur. Particularly, in the case of a composition having both photo-curability and thermosetting property, it was also confirmed that good sensitivity and patternability were obtained. On the other hand, in the comparative example (B) containing no specific coloring material, a high OD value was not obtained and the color tone was greatly different.

Claims (12)

(B) a coloring material having a minimum absorption value at 380 to 500 nm and a maximum absorption value at 500 to 780 nm in a visible light region of 380 to 780 nm, and (C) a thermosetting component . The curable resin composition according to claim 1, further comprising (D) an alkali-soluble resin, and (E) a photopolymerization initiator. The curable resin composition according to claim 2, further comprising (F) a photosensitive (meth) acrylate compound. (B) a colorant having a minimum absorption value at 380 to 500 nm and a maximum absorption value at 500 to 780 nm in a visible light region of 380 to 780 nm, and (F) a colorant having a maximum absorption value at 500 to 780 nm, By weight of the curable resin composition. The curable resin composition according to any one of claims 1 to 4, wherein the maximum absorption wavelength of the near infrared absorbing agent (A) is 500 to 1000 nm. The curable resin composition according to any one of claims 1 to 4, wherein (A) the near infrared absorbing agent is at least one selected from metal complex dyes and condensed polycyclic dyes. The curable resin composition according to any one of claims 1 to 4, which exhibits black color. The curable resin composition according to claim 1 or 4, which is for forming an insulating film. A dry film obtained by applying the curable resin composition according to any one of claims 1 to 4 on a carrier film and drying it. A dry film obtained by applying the curable resin composition according to any one of claims 1 to 4 on a substrate and drying the film or a dry film obtained by applying the curable resin composition onto a carrier film and drying the film, By weight. A light-shielding member comprising the cured product according to claim 10. A member for a display, comprising the cured product according to claim 10.