JP6423215B2 - Photocurable composition - Google Patents

Description

  The present invention relates to a photocurable composition containing an epoxy compound containing a nitrogen atom in its structure and an unsaturated compound having a specific structure.

  The photocurable composition usually contains an unsaturated compound having an ethylenically unsaturated bond and a photopolymerization initiator. Since this photocurable composition can be rapidly polymerized and cured by irradiation with ultraviolet rays or an electron beam, it is useful in various applications. Such a photocurable composition is required to have chemical resistance to obtain a high-definition pattern, and transparency to be used for clear applications such as a display. In addition, when the photocurable composition uses a colorant, particularly a black pigment, ultraviolet rays and electron beams are absorbed and reflected by these colorants. There is a demand for high sensitivity to electron beams.

  Furthermore, in the manufacturing process of a black matrix using a black pigment as a colorant, it is required to improve the light shielding property for the purpose of improving the contrast. In general, although carbon black has higher light shielding properties than other organic pigments, it has conductivity. If the carbon black concentration in the composition is increased in order to increase the light shielding property, the formed black matrix itself also has conductivity. On the other hand, if the carbon black content is decreased, the conductivity is lowered, but in order to increase the light shielding rate, it is necessary to increase the thickness of the light shielding film, resulting in color unevenness and display quality deterioration. Development of a black matrix having high resistance while being excellent in light shielding properties and a color filter excellent in display quality is desired.

  The following Patent Documents 1 and 2 disclose colored alkali-developable photosensitive resin compositions that achieve both high light-shielding properties and ultrafine wire formation, and the following Patent Documents 3 and 4 disclose epoxy compounds containing nitrogen atoms. ing.

JP 2007-072196 A JP 2007-264433 A JP-A-56-122313 JP 2014-019826 A

However, in Patent Documents 1 to 4, no consideration has been given to combining chemical resistance, transparency, good sensitivity, light-shielding properties, and high resistance, and the techniques described in these documents are in this respect. It was insufficient.
Accordingly, an object of the present invention is to provide a photocurable composition having transparency and high chemical resistance with high sensitivity to ultraviolet rays and electron beams, which does not impair the curability even when a colorant is added. There is to do. Another object of the present invention is to provide a photocurable composition having high light shielding properties and high resistance.

  As a result of intensive studies, the present inventors have determined that the epoxy compound (A) containing a group selected from the group represented by the following formula (a), (b) or (c) in the structure, the following general formula (I The unsaturated compound (B), which is a reaction product obtained by esterification reaction of an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by) and a polybasic acid anhydride, and The present inventors have found that the photocurable composition containing the photopolymerization initiator (C) is excellent in sensitivity, has a high light shielding property and is suitable for a high resistance photocurable composition, and have reached the present invention.

（式中、Ｍは直接結合、炭素原子数１〜６の炭化水素基、炭素原子数３〜２０の脂環式炭化水素基、−Ｏ−、−Ｓ−、−ＳＯ₂−、−ＳＳ−、−ＳＯ−、−ＣＯ−、−ＯＣＯ−又は下記式（ｄ）、（ｅ）、（ｆ）或いは（ｇ）で表される群から選ばれる置換基を表し、該炭化水素基はハロゲン原子で置換されていてもよく、Ｒ^１、Ｒ^２、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８はそれぞれ独立に、水素原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、又はハロゲン原子を表し、ｎは０〜１０の数である。）

(Wherein, M is a direct bond, a hydrocarbon group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, -O -, - S -, - SO 2 -, - SS- , -SO-, -CO-, -OCO- or a substituent selected from the group represented by the following formula (d), (e), (f) or (g), wherein the hydrocarbon group is a halogen atom R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, carbon Represents an alkoxy group having 1 to 10 atoms or a halogen atom, and n is a number from 0 to 10.

（式中、Ｒ^９は炭素原子数１〜３のアルキル基或いは炭素原子数５〜１０のシクロアルキル基を表す。Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１８、Ｒ^１９、Ｒ^２０、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２５、Ｒ^２６、Ｒ^２７、Ｒ^２８、Ｒ^２９、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４、Ｒ^３５、Ｒ^３６、Ｒ^３７及びＲ^３８は、それぞれ独立に、水素原子、炭素原子数１〜１０のアルキル基、炭素原子数１〜１０のアルコキシ基、炭素原子数６〜２０のアリール基、炭素原子数７〜２０のアリールアルキル基、炭素原子数２〜２０の複素環基、又はハロゲン原子を表し、上記アルキル基およびアリールアルキル基中のアルキレン部分は、不飽和結合、−Ｏ−又は−Ｓ−で中断されてもよく、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２５、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４、Ｒ^３５、Ｒ^３６、Ｒ^３７及びＲ^３８は、隣接するＲ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１３、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^２２、Ｒ^２３、Ｒ^２４、Ｒ^２５、Ｒ^３０、Ｒ^３１、Ｒ^３２、Ｒ^３３、Ｒ^３４、Ｒ^３５、Ｒ^３６、Ｒ^３７ 及びＲ^３８同士で環を形成してもよい。）

(In the formula, R ⁹ represents an alkyl group having 1 to 3 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms. R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. 20 represents an aryl group, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a halogen atom, and the alkylene moiety in the alkyl group and arylalkyl group is an unsaturated bond, -O- or It may be interrupted by ^{S-, R 10, R 11,} R 12, R 13, R 14, R 15, R 16, R 17, R 22, R 23, R 24, R 25, R 30, R 31 , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are adjacent to R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ may form a ring.

  Moreover, this invention provides the black matrix and color filter which added the black pigment as a coloring agent to the said photocurable composition.

  According to the present invention, a highly sensitive photocurable composition having transparency and chemical resistance and suitable as a pixel of a color filter for a display device, a liquid crystal display panel, and a color filter of an organic EL display panel is provided. Can do. Moreover, the photocurable composition which is excellent in the light shielding property suitable for black matrix formation which uses the carbon black which is a black pigment for the said photocurable composition, and has a high resistance value can be provided.

  Hereinafter, the photocurable composition of the present invention will be described based on preferred embodiments.

  The photocurable composition of the present invention includes an epoxy compound (A), an unsaturated compound (B), and light containing a group selected from the group represented by the above formula (a), (b) or (c) in the structure. Contains a polymerization initiator (C). Hereinafter, each component will be described in order.

<Epoxy compound (A)>
The epoxy compound (A) used for the photocurable composition of the present invention has a structure containing a group selected from the group represented by the formula (a), (b) or (c). One group selected from the group represented by the formula (a), (b) or (c) may be contained in the epoxy compound, or two or more groups may be contained. Moreover, when two or more are included, the plurality of the groups may be the same or different.
As a group selected from the group represented by the above formula (a), (b) or (c), as a group corresponding to (a), a group represented by (a-1) or (a-2), The group represented by (b-1), (b-2) or (b-3) as corresponding to (b), and the group represented by (c-1) as corresponding to (c) Can be mentioned.

Specifically, as the epoxy compound (A) containing in the structure a group selected from the group represented by the above formula (a), (b) or (c),
As an epoxy compound containing a group represented by (a) in its structure, 6-methyl-2-nitro-3- (2-oxiranylmethoxy) pyridine, N, N-dibutyl-5- [2- (4-nitro Phenyl) diazenyl] -4- [4- (2-oxiranylmethoxy) phenyl] -2-thiazolamine, 2-methyl-6- (2-oxiranylmethoxy) -1H-benzimidazole, 2- [4 -(3-Butyl-2-oxiranylmethoxy) phenyl] -5-octylpyrimidine, 3,6-bis [4-2-2-oxiranylmethoxy) phenyl] -1,2,4-triazine, 3-methyl -5-[[2- (2-oxiranylmethoxy) phenoxy] methyl] -1,2,4-oxadiazole, 2- [4- (2-oxiranylmethoxy) phenyl] -1H-imidazole, 4- [4- (2-oxira Rumetokishi) 1,2,5-thiadiazol-3-yl] morpholine, and the like,
N- [3- (2-oxiranylmethoxy) phenyl] urea, 5-[[4- (2-oxiranylmethoxy) phenyl] methylene] as an epoxy compound containing a group represented by (b) in the structure -2,4,6 (1H, 3H, 5H) -pyrimidinetrione, 1,3-dihydro-1-methyl-3- (2-oxiranylmethyl) -2H-imidazol-2-one, 2- (2 -Oxiranylmethyl) -1,2,4-triazolo [4,3-a] pyrazin-3 (2H) -one, 5-bromo-4,6-dimethyl-1- (2-oxiranylmethyl) -2 (1H) -pyrimidinone, 2,4-dihydro-4- (1-methylethyl) -5-[[(2-methyl-2-oxiranyl) methyl] thio] -3H-1,2,4-thiazole -3-one, 1-methyl-3- (2-oxiranylmethyl) -2, 4,5-imidazolidinetrione, 3- (2-oxiranylmethyl) -2,4-imidazolidinedione, 1-methyl-3- (2-oxiranylmethyl) -2-imidazolidinone, 1, 1,3,5-tris (2-oxiranylmethyl) 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,3-dihydro-4- (2-oxy) Ranylmethoxy) -2H-benzimidazol-2-one, 1,3-dimethyl-6-[(2-phenyl-2-oxiranyl) methyl] -2,4 (1H, 3H) -pyrimidinedione, bis (oxy Ranylmethyl) carbamic azide, 1,4-dihydro-1,4-bis (2-oxiranylmethyl) -5H-tetraazol-5-one, 4-methyl-4- (2-oxiranyl) -1-phenyl -1,3-diazetidine 2-one, 1,2,4-tris (2-oxiranylmethyl) -1,2,4-triazolidine-3,5-dione, 2- (4,4,6-trimethyl-7-oxa Bicyclo [4.1.0] hept-2-ylidene-hydrazinecarboxysamide, 3,7-dihydro-3,7-dimethyl-1- (2-oxiranylmethyl) -1H-purine-2,6- Dione, 1,3,4,6-tetrakis (2-oxiranylmethyl) tetrahydroimidazo [4,5-d] imidazole-2,5 (1H, 3H) dione, diglycidyl dimethylhydantoin, etc.
3- (2-oxiranylmethyl) -oxazolo [4,5-b] -2 (3H) -one, octahydro-4H-oxyleno [f] as an epoxy compound containing a group represented by (c) in the structure ] T-butyl isoindole-4-carboxylate, azidocarboxylic acid (3-methyloxiranyl) methyl, phenylcarbamate, N- (glycosyloxycarbonyl) aniline and the like.
As the epoxy compound (A) containing in the structure a group selected from the group represented by the above formula (a), (b) or (c), a commercially available one can be used. For example, the TEPIC (shown below) Nissan Chemical Industries, Ltd.), TG-G, DG-DMH (manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like.

  In the photocurable composition of the present invention, the epoxy compound (A) preferably has two or more epoxy groups. In addition, it is preferable that a group represented by the following formula (Q) is bonded to one or more nitrogen atoms in the above formula (a), (b) or (c), and two or more nitrogen atoms in each of these formulas Those having a group represented by the following formula (Q) bonded to an atom are more preferred. Moreover, it is preferable that an epoxy compound (A) does not have a reactive group with big cure shrinkage, such as an acryloyl group, from a viewpoint of obtaining hardened | cured material of high resistance.

（式中、Ｒ^ｍは水素原子又は炭素原子数１〜４のアルキル基を表す。）

(In the formula, R ^m represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

  In the photocurable composition of the present invention, the content of the epoxy compound (A) is 100 parts by mass of the total value of the epoxy compound (A), the unsaturated compound (B), and the photopolymerization initiator (C). Preferably it is 1-50 mass parts, More preferably, 5-30 mass parts is preferable. If the content of the epoxy compound (A) is less than 1 part by mass, sufficient insulation may not be obtained for a cured product obtained by blending and curing carbon black. When used, sufficient fine line adhesion during development may not be obtained.

<Unsaturated compound (B)>
The unsaturated compound (B) used in the photocurable composition of the present invention includes an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to the epoxy compound represented by the general formula (I), and a polybasic It is a reaction product obtained by an esterification reaction with an acid anhydride.

In the general formula ^{(I), R 1, R 2, R 3} , R 4, R 5, R 6, an alkyl group having 1 to 10 carbon atoms represented by R ⁷ and R ^8, methyl, ethyl Propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl, hexyl, heptyl, isoheptyl, t-heptyl, n-octyl, isooctyl, t-octyl , 2-ethylhexyl, n-nonyl, n-decyl, trifluoromethyl, difluoromethyl, monofluoromethyl, pentafluoroethyl, tetrafluoroethyl, trifluoroethyl, difluoroethyl, heptafluoropropyl, hexafluoropropyl, pentafluoropropyl , Tetrafluoropropyl, trifluoropropyl, perful Robuchiru, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl and the like,
Examples of the alkoxy group having 1 to 10 carbon atoms represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ include methyloxy, ethyloxy, iso-propyloxy, propyl Oxy, butyloxy, pentyloxy, iso-pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and the like,
Examples of the halogen atom represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ and R ^{10 to} R ³⁸ described later include fluorine, chlorine, bromine and iodine. .

Examples of the hydrocarbon group having 1 to 6 carbon atoms represented by M in the general formula (I) include a linear, branched or cyclic aliphatic hydrocarbon group. Specifically, Examples include methanediyl, 1,1-ethanediyl, 2,2-propanediyl, 2-2butanediyl, and cyclohexanediyl.
In the substituent selected from the group represented by the above formula (d), (e), (f) or (g), the alkyl group having 1 to 3 carbon atoms represented by R ⁹ or 5 carbon atoms Among the examples of the alkyl group having 1 to 10 carbon atoms represented by the above R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and ⁸ , Respectively, those having 1 to 3 carbon atoms and cyclic aliphatic groups having 5 to 10 carbon atoms,
R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ (also referred to herein as R ^{10 to} R ³⁸ ) As the alkyl group having 1 to 10 carbon atoms and the alkoxy group having 1 to 10 carbon atoms, represented by R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ^The ones exemplified in ⁸ are listed,
Examples of the aryl group having 6 to 20 carbon atoms represented by R ^{10 to} R ³⁸ include phenyl, naphthyl, anthracen-1-yl, phenanthren-1-yl, o-tolyl, m-tolyl, p-tolyl, 4 -Vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-t-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4- (2 -Ethylhexyl) phenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4 -Di-t-butylphenyl, 2,5-di-t-butylphenyl, 2,6-di-t-butylphenyl 2,4-di-t-pentylphenyl, 2,5-di-t-amylphenyl, cyclohexylphenyl, biphenyl, 2,4,5-trimethylphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4- And trichlorophenyl, 4-trifluorophenyl, perfluorophenyl, etc.
Examples of the arylalkyl group having 7 to 20 carbon atoms represented by R ^{10 to} R ³⁸ include benzyl, phenethyl, 2-phenylpropyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, 4-chlorophenylmethyl and the like. ,
Examples of the heterocyclic group represented by R ^{10 to} R ³⁸ include pyrrolyl, pyridyl, pyrimidyl, pyridazyl, piperazyl, piperidyl, pyranyl, pyrazolyl, triazyl, pyrrolidyl, quinolyl, isoquinolyl, imidazolyl, benzimidazolyl, triazolyl, furyl, furanyl, benzofuranyl , Thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazolyl, oxazolyl, benzoxazolyl, isothiazolyl, isoxazolyl, indolyl, urolidyl, morpholinyl, thiomorpholinyl, 2-pyrrolidinon-1-yl, 2-piperidone-1 -Yl, 2,4-dioxyimidazolidin-3-yl, 2,4-dioxyoxazolidine-3-yl and the like.

The unsaturated monobasic acid that acts on the epoxy group of the epoxy compound includes acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate. , Hydroxypropyl acrylate malate, dicyclopentadiene malate and the like.
In addition, the polybasic acid anhydride to be esterified after adding the unsaturated monobasic acid includes biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic acid Anhydride, pyromellitic anhydride, 2,2'-3,3'-benzophenone tetracarboxylic anhydride, ethylene glycol bisanhydro trimellitate, glycerol tris anhydro trimellitate, hexahydrophthalic anhydride, methyl tetrahydro Phthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, trialkyltetrahydro Phthalic - maleic acid adduct, dodecenyl succinic anhydride, and anhydride and methyl high Mick acid.

The reaction molar ratio of the epoxy compound, the unsaturated monobasic acid and the polybasic acid anhydride is preferably as follows.
That is, in the epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy compound, the hydroxyl group of the epoxy adduct is 1 It is preferable that the acid anhydride structure of the polybasic acid anhydride has a ratio of 0.1 to 1.0.
Reaction of the said epoxy compound, the said unsaturated monobasic acid, and the said polybasic acid anhydride can be performed in accordance with a conventional method.

  In the photocurable composition of the present invention, the content of the unsaturated compound (B) is 100 parts by mass with respect to a total value of 100 parts by mass of the epoxy compound (A), the unsaturated compound (B), and the photopolymerization initiator (C). The amount is preferably 30 to 90 parts by mass, and more preferably 40 to 80 parts by mass. If the content of the unsaturated compound (B) is less than 30 parts by mass, sufficient photocurability may not be obtained. If it is greater than 90 parts by mass, sufficient alkali developability is obtained when used as a resist. It may not be possible.

<Photopolymerization initiator (C)>
As the photopolymerization initiator (C) used in the photocurable composition of the present invention, a conventionally known photoradical initiator can be used. The radical photopolymerization initiator is not particularly limited as long as it generates radicals by light irradiation, and a conventionally known compound can be used. For example, acetophenone compounds, benzyl compounds, benzophenone compounds, thioxanthone Examples of preferred compounds include ketone compounds such as benzene compounds and oxime ester compounds.

  Examples of acetophenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methylpropiophenone, 2-hydroxymethyl-2. -Methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tertiarybutyldichloroacetophenone, p-tertiarybutyltrichloroacetophenone, p-azidobenzal Acetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1, benzoy , Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane- 1-one etc. are mentioned.

  Examples of the benzyl compound include benzyl.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4′-bisdiethylaminobenzophenone, 4,4′-dichlorobenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, and the like. .

  Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, and 2,4-diethylthioxanthone.

  Especially as an oxime type compound used for the photocurable composition of this invention, the compound represented by the following general formula (II) is preferable from the point of a sensitivity and heat resistance.

（式中、Ｒ^３９及びＲ^４０は、それぞれ独立に、水素原子、ニトロ基、ハロゲン原子、シアノ基、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環基を表し、
Ｒ^４１及びＲ^４２は、それぞれ独立に、水素原子、ハロゲン原子、ニトロ基、シアノ基、水酸基、カルボキシル基、Ｒ^４３、ＯＲ^４４、ＳＲ^４５、ＮＲ^４６Ｒ^４７、ＣＯＲ^４８、ＳＯＲ^４９、ＳＯ_２Ｒ^５０又はＣＯＮＲ^５１Ｒ^５２を表し、Ｒ^３９及びＲ^４０は、互いに結合して環を形成していてもよく、
Ｒ^４３、Ｒ^４４、Ｒ^４５、Ｒ^４６、Ｒ^４７、Ｒ^４８、Ｒ^４９、Ｒ^５０、Ｒ^５１及びＲ^５２は、それぞれ独立に、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基、炭素原子数７〜３０のアリールアルキル基又は炭素原子数２〜２０の複素環含有基を表し、
Ｘ^１は、酸素原子、硫黄原子、セレン原子、ＣＲ^５３Ｒ^５４、ＣＯ、ＮＲ^５５又はＰＲ^５６を表し、
Ｘ^２は、単結合又はＣＯを表し、
Ｒ^５３、Ｒ^５４、Ｒ^５５及びＲ^５６は、それぞれ独立に、水素原子、炭素原子数１〜２０のアルキル基、炭素原子数６〜３０のアリール基又は炭素原子数７〜３０のアリールアルキル基を表し、
前記のアルキル基又はアリールアルキル基中のメチレン基は、ハロゲン原子、ニトロ基、シアン基、水酸基、カルボキシル基又は複素環基で置換されていてもよく、−Ｏ−で中断されていてもよく、
Ｒ^５３、Ｒ^５４、Ｒ^５５及びＲ^５６は、それぞれ独立に、隣接するどちらかのベンゼン環と一緒になって環を形成していてもよい。
ｈは、０〜４の整数を表し、
ｉは、０〜５の整数を表す。）

(In the formula, R ³⁹ and R ⁴⁰ are each independently a hydrogen atom, a nitro group, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or the number of carbon atoms. Represents a 7-30 arylalkyl group or a C2-C20 heterocyclic group,
R ⁴¹ and R ⁴² each independently represent a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, R ⁴³ , OR ⁴⁴ , SR ⁴⁵ , NR ⁴⁶ R ⁴⁷ , COR ⁴⁸ , SOR ⁴⁹ , SO _2. Represents R ⁵⁰ or CONR ⁵¹ R ⁵² , R ³⁹ and R ⁴⁰ may be bonded to each other to form a ring;
R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁴⁹ , R ⁵⁰ , R ⁵¹ and R ⁵² are each independently an alkyl group having 1 to 20 carbon atoms, or 6 to 6 carbon atoms. Represents an aryl group of 30, an arylalkyl group of 7 to 30 carbon atoms or a heterocyclic ring-containing group of 2 to 20 carbon atoms,
X ¹ represents an oxygen atom, a sulfur atom, a selenium atom, CR ⁵³ R ⁵⁴ , CO, NR ⁵⁵ or PR ⁵⁶ ,
X ² represents a single bond or CO,
R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an arylalkyl group having 7 to 30 carbon atoms. Represents
The methylene group in the alkyl group or arylalkyl group may be substituted with a halogen atom, nitro group, cyan group, hydroxyl group, carboxyl group or heterocyclic group, and may be interrupted with -O-,
R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ may each independently form a ring together with any adjacent benzene ring.
h represents an integer of 0 to 4,
i represents an integer of 0 to 5. )

Examples of the alkyl group, aryl group, arylalkyl group, and heterocyclic group represented by each symbol of the general formula (II) include the alkyl group, aryl group, arylalkyl group represented by the above R ^{10 to} R ³⁸ , The thing similar to the example of a heterocyclic group is mentioned.

  Other photoradical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pyru- 1-yl)] titanocene compounds such as titanium.

  These radical photopolymerization initiators can be used alone or in combination according to the desired performance.

  Commercially available photo radical initiators include N-1414, N-1717, N-1919, PZ-808, NCI-831, NCI-930 (manufactured by ADEKA), IRGACURE 184, IRGACURE 369, IRGACURE 651, IRGACURE 907, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE 784 (manufactured by BASF), TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-314 (manufactured by Troly) and the like.

  In the photocurable composition of the present invention, the content of the photopolymerization initiator (C) is 100 parts by mass of the total value of the epoxy compound (A), the unsaturated compound (B), and the photopolymerization initiator (C). On the other hand, 2.0-60 mass parts, especially 10-30 mass parts are preferable. When the content of the photopolymerization initiator is less than 2.0 parts by mass, curing by exposure may be insufficient, and when it is greater than 60 parts by mass, the initiator may be precipitated in the resin composition. .

<Colorant (D)>
As the colorant (D) used in the photocurable composition of the present invention, an inorganic color material or an organic color material can be used, and these can be used alone or in admixture of two or more.
Examples of the inorganic color material or organic color material include nitroso compounds, nitro compounds, azo compounds, diazo compounds, xanthene compounds, quinoline compounds, anthraquinone compounds, coumarin compounds, phthalocyanine compounds, isoindolinone compounds, isoindoline compounds, and quinacridones. Compound, anthanthrone compound, perinone compound, perylene compound, diketopyrrolopyrrole compound, thioindigo compound, dioxazine compound, triphenylmethane compound, quinophthalone compound, naphthalenetetracarboxylic acid, azo dye, metal complex compound of cyanine dye, lake pigment, furnace Carbon black obtained by the method, channel method or thermal method, or carbon black such as acetylene black, ketjen black or lamp black, Carbon black prepared or coated with an epoxy resin, carbon black previously dispersed with a resin in a solvent, 20 to 200 mg / g of resin adsorbed, and carbon black treated with an acidic or alkaline surface Carbon black having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, a carbon black having a total oxygen amount calculated from CO and CO ₂ in a volatile content at 950 ° C. of 9 mg or more per 100 m ^{2 of} surface area, Graphite, graphitized carbon black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene, aniline black, pigment black 7, titanium black, chromium oxide green, miloli blue, cobalt green, cobalt blue, man Cancer series, ferrocyanide, phosphate ultramarine, bitumen, ultramarine, cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, synthetic iron black Organic or inorganic pigments such as amber can be used.

  As the inorganic color material or organic color material, commercially available pigments can also be used. For example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 3, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; pigment violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50, and the like.

  As the inorganic color material or organic color material, known dyes can be used. Known dyes include, for example, azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, Examples thereof include phthalocyanine dyes and cyanine dyes.

  When using the photocurable composition of this invention as a black matrix, a black pigment is used as a coloring agent (D). Of these various pigments, carbon black or titanium black is preferably used as the black pigment in this case.

  In the photocurable composition of the present invention, the content of the colorant (D) is 100 parts by mass of the total value of the epoxy compound (A), the unsaturated compound (B), and the photopolymerization initiator (C). The amount is preferably 0 to 400 parts by mass, more preferably 150 to 300 parts by mass. When the amount exceeds 400 parts by mass, the colorant tends to aggregate and storage stability is deteriorated.

<Silane coupling agent (E)>
A silane coupling agent (E) can further be used in the photocurable composition of the present invention. Examples of the silane coupling agent include dimethyldimethoxysilane, dimethyldiethoxysilane, methylethyldimethoxysilane, methylethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Alkyl-functional alkoxysilanes, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane and other alkenyl-functional alkoxysilanes, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 2-methacryloxypropyltrimethoxysilane (Meth) acrylic acid ester functional alkoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ Epoxy functional alkoxysilanes such as-(3,4-epoxycyclohexyl) propyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ -Amino-functional alkoxysilanes such as aminopropyltrimethoxysilane, mercapto-functional alkoxysilanes such as γ-mercaptopropyltrimethoxysilane, titanium alkoxides such as titanium tetraisopropoxide, titanium tetranormal butoxide, titanium dioxide Titanium chelates such as cutyloxybis (octylene glycolate) and titanium diisopropoxybis (ethyl acetoacetate), zirconium chelates such as zirconium tetraacetylacetonate and zirconium tributoxymonoacetylacetonate, zirconium tributoxy monostearate, etc. Zirconium acylates, isocyanate silanes such as methyl triisocyanate silane, etc. can be used, and alkyl functional alkoxy silanes, epoxy functional alkoxy silanes, and isocyanate silanes are particularly preferable because of high adhesion in a moist heat resistance test. .

  Although the usage-amount of the said silane coupling agent is not specifically limited, Preferably, it is 0 with respect to 100 mass parts of total values of an epoxy compound (A), an unsaturated compound (B), and a photoinitiator (C). The range is 10 parts by mass.

  In the photocurable composition of the present invention, a polymerizable compound having an ethylenically unsaturated bond can be further used. The polymerizable compound having an ethylenically unsaturated bond is not particularly limited, and those conventionally used in photosensitive compositions can be used. For example, ethylene, propylene, butylene, isobutylene, vinyl chloride can be used. , Unsaturated aliphatic hydrocarbons such as vinylidene chloride, vinylidene fluoride, tetrafluoroethylene; (meth) acrylic acid, α-chloroacrylic acid, itaconic acid, maleic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, Isocrotonic acid, vinyl acetate, allyl acetate, cinnamic acid, sorbic acid, mesaconic acid, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω- A carboxypolycaprolactone mono (meth) acrylate, etc. having a carboxy group and a hydroxyl group at both ends Mer mono (meth) acrylates; having hydroxyethyl (meth) acrylate malate, hydroxypropyl (meth) acrylate malate, dicyclopentadiene malate or one carboxyl group and two or more (meth) acryloyl groups Unsaturated monobasic acids such as polyfunctional (meth) acrylates; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, the following compound No. A1-No. A4, methyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, (t-butyl) (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, ( Isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, dimethyl (meth) acrylate Aminoethyl, aminopropyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, ethoxyethyl (meth) acrylate, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, (meta ) Ethylhexyl acrylate, (meth) acrylic acid Phenoxyethyl, tetrahydrofuryl (meth) acrylate, vinyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol Unsaturated monobasic acids such as tra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecane dimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomers and the like Esters of polyhydric alcohols or polyphenols; metal salts of unsaturated polybasic acids such as zinc (meth) acrylate and magnesium (meth) acrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, methyl Tetrahydrophthalic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trialkyltetrahydro Phthalic anhydride-anhydrous Acid anhydrides of unsaturated polybasic acids such as rain acid adducts, dodecenyl succinic anhydride, methyl hymic anhydride; (meth) acrylamide, methylene bis- (meth) acrylamide, diethylenetriamine tris (meth) acrylamide, xylylene bis (meth) Unsaturated monobasic acids such as acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide and amides of polyvalent amines; unsaturated aldehydes such as acrolein; (meth) acrylonitrile, α-chloroacrylonitrile, cyanide Unsaturated nitriles such as vinylidene and allyl cyanide; styrene, 4-methylstyrene, 4-ethylstyrene, 4-methoxystyrene, 4-hydroxystyrene, 4-chlorostyrene, divinylbenzene, vinyltoluene, vinylbenzoic acid, vinyl Unsaturated aromatic compounds such as ruphenol, vinyl sulfonic acid, 4-vinylbenzene sulfonic acid, vinyl benzyl methyl ether, vinyl benzyl glycidyl ether; unsaturated ketones such as methyl vinyl ketone; vinyl amine, allyl amine, N-vinyl pyrrolidone, vinyl Unsaturated amine compounds such as piperidine; vinyl alcohols such as allyl alcohol and crotyl alcohol; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, n-butyl vinyl ether, isobutyl vinyl ether, allyl glycidyl ether; maleimide, N-phenylmaleimide, N -Unsaturated imides such as cyclohexylmaleimide; Indenes such as indene and 1-methylindene; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene Macromolecules having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, etc .; vinyl chloride, vinylidene chloride, divinyls Cuccinate, diallyl phthalate, triallyl phosphate, triallyl isocyanurate, vinyl thioether, vinyl imidazole, vinyl oxazoline, vinyl carbazole, vinyl pyrrolidone, vinyl pyridine, hydroxyl group-containing vinyl monomers and vinyl isocyanate compounds of polyisocyanate compounds, hydroxyl groups Examples thereof include vinyl monomers containing vinyl monomers and polyepoxy compounds.

  In addition, as the polymerizable compound having an ethylenically unsaturated bond, an acrylic ester copolymer, a phenol and / or cresol novolac epoxy resin, or a polyphenylmethane type epoxy resin having a polyfunctional epoxy group may be used. it can.

  When the photocurable composition of the present invention further contains a polymerizable compound having an ethylenically unsaturated bond, in addition to the components (A) to (E), the amount thereof is the epoxy compound (A), unsaturated. The amount is preferably 1 to 80 parts by mass and more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the total value of the compound (B) and the photopolymerization initiator (C).

Among the polymerizable compounds having an ethylenically unsaturated bond, when a compound having an acid value is used, alkali developability can be imparted to the photocurable composition of the present invention. When using the compound which has the said acid value, the usage-amount will be 30-90 mass parts with respect to 100 mass parts of total values of an epoxy compound (A), an unsaturated compound (B), and a photoinitiator (C). It is preferable to do so.
The compound having an acid value can be used after adjusting the acid value by further reacting with a monofunctional or polyfunctional epoxy compound. The alkali developability of the photosensitive resin can be improved by adjusting the acid value of the compound having an acid value. The compound having an acid value (that is, a polymerizable compound having an ethylenically unsaturated bond imparting alkali developability) preferably has a solid content acid value in the range of 5 to 120 mgKOH / g, and is monofunctional or polyfunctional. The amount of the functional epoxy compound used is preferably selected so as to satisfy the acid value.

  Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, heptyl. Glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidylate , Propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether, benzyl glycidyl Ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy-4-vinyl Cyclohexane, styrene oxide, pinene oxide, methyl styrene oxide, cyclohexene oxide, propylene oxide, the above-mentioned compound no. A2, No. A3 etc. are mentioned.

As the polyfunctional epoxy compound, it is preferable to use one or more compounds selected from the group consisting of bisphenol-type epoxy compounds and glycidyl ethers because a colored photosensitive resin composition with better characteristics can be obtained.
As the bisphenol type epoxy compound, an epoxy compound represented by the above general formula (I) can be used, and for example, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used.
Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,8-octanediol diglycidyl ether, 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl Ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-to (Glycidyloxymethyl) ethane, 1,1,1-tri (glycidyloxymethyl) methane, 1,1,1,1- tetra (glycidyloxymethyl) can be used such as methane.
Other novolac epoxy compounds such as phenol novolac epoxy compounds, biphenyl novolac epoxy compounds, cresol novolac epoxy compounds, bisphenol A novolac epoxy compounds, dicyclopentadiene novolac epoxy compounds; 3,4-epoxy-6-methyl Cycloaliphatic epoxies such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compound: Glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, glycidyl dimer, tetraglycidyl diamino Glycidylamines such as phenylmethane, triglycidyl P-aminophenol and N, N-diglycidylaniline; heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; Dioxide compounds such as pentadiene dioxide; naphthalene type epoxy compounds; triphenylmethane type epoxy compounds; dicyclopentadiene type epoxy compounds can also be used.

  In addition, the photocurable composition of the present invention may contain a compound that does not have an ethylenically unsaturated bond and imparts alkali developability. The compound is not particularly limited as long as it is a compound that is soluble in an aqueous solution, but a typical example is an alkali-soluble novolak resin (hereinafter simply referred to as “novolak resin”). The novolak resin is obtained by polycondensation of phenols and aldehydes in the presence of an acid catalyst.

  Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2, 3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, p-phenylphenol, hydroquinone, catechol, resorcinol, 2- Methyl resorcinol, pyrogallol, α-naphthol, bisphenol A, dihydroxybenzoic acid ester, gallic acid ester and the like are used. Among these phenols, phenol, o-cresol, m-cresol, p-cresol, 2,5-xy Nord, 3,5-xylenol, 2,3,5-trimethylphenol, resorcinol, 2-methyl resorcinol and bisphenol A are preferred. These phenols are used alone or in combination.

  Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o -Chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde, m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde, p N-butylbenzaldehyde and the like are used, and among these compounds, formal Dehydr, acetaldehyde and benzaldehyde are preferred. These aldehydes may be used alone or in combination of two or more. Aldehydes are preferably used in a proportion of 0.7 to 3 mol, particularly preferably 0.7 to 2 mol, per mol of phenol.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, or organic acids such as formic acid, oxalic acid, and acetic acid. The amount of these acid catalysts used is preferably 1 × 10 ^{−4 to} 5 × 10 ⁻¹ mol per mol of phenols. In the condensation reaction, water is usually used as a reaction medium. However, if the phenols used in the condensation reaction do not dissolve in an aqueous solution of aldehydes and become heterogeneous from the beginning of the reaction, the reaction medium is hydrophilic. A solvent can also be used. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol and butanol, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of these reaction media used is usually 200 to 2000 parts by mass with respect to 100 parts by mass of the solid content of the photocurable composition. Although the reaction temperature of a condensation reaction can be suitably adjusted according to the reactivity of a reaction raw material, it is 10-200 degreeC normally, Preferably it is 70-150 degreeC. After completion of the condensation reaction, in order to remove unreacted raw materials, acid catalyst and reaction medium present in the system, the internal temperature is generally raised to 130 to 230 ° C., and the volatile component is distilled off under reduced pressure. Next, the melted novolac resin is collected on a steel belt or the like.
After completion of the condensation reaction, the reaction mixture is dissolved in the hydrophilic solvent and added to a precipitating agent such as water, n-hexane or n-heptane to precipitate a novolak resin, and the precipitate is separated and dried by heating. It can also be recovered by doing so.

  Examples other than the novolak resin include polyhydroxystyrene or a derivative thereof, a styrene-maleic anhydride copolymer, polyvinylhydroxybenzoate, and the like.

  A solvent can be further added to the photocurable composition of the present invention. As the solvent, each of the above components (epoxy compound (A), unsaturated compound (B), photopolymerization initiator (C), colorant (D), silane coupling agent (E) is usually used as necessary. Solvents that can dissolve or disperse such as ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone; ethyl ether, dioxane, tetrahydrofuran, 1, 2 -Ether solvents such as dimethoxyethane, 1,2-diethoxyethane, dipropylene glycol dimethyl ether; methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, succinic acid Ester solvents such as dimethyl and texanol; Cellosolve solvents such as tylene glycol monomethyl ether and ethylene glycol monoethyl ether; alcohol solvents such as methanol, ethanol, iso- or n-propanol, iso- or n-butanol, amyl alcohol; ethylene glycol monomethyl acetate, ethylene glycol mono Ether ester solvents such as ethyl acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate; benzene, toluene, xylene, etc. BTX solvents; aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpenes such as terpine oil, D-limonene and pinene Hydrocarbon oil; paraffinic solvents such as mineral spirit, swazol # 310 (manufactured by Cosmo Matsuyama Petroleum), Solvesso # 100 (manufactured by Exxon Chemical); carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane, etc. Halogenated aliphatic hydrocarbon solvents such as chlorobenzene, halogenated aromatic hydrocarbon solvents such as chlorobenzene, carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, and the like can be used, and these solvents can be used as one or two or more mixed solvents, among which ketones, ether ester solvents, and the like. , Especially propylene glycol-1-mono Methyl ether-2-acetate (PGMEA), cyclohexanone, and the like are preferable because the coloring composition has good compatibility between the resist and the photopolymerization initiator.

  In the photocurable composition of the present invention, the amount of the solvent used is preferably such that the concentration of the composition other than the solvent is 5 to 30% by mass, and if it is less than 5% by mass, the film thickness may be increased. It is difficult and is not preferable because it cannot sufficiently absorb light of a desired wavelength. When it exceeds 30% by mass, the storage stability of the composition due to the precipitation of the composition is reduced, and the handling is reduced because the viscosity is improved. It is not preferable.

  A dispersant can be further used in the photocurable composition of the present invention. As the dispersant, any dispersant can be used as long as it can disperse and stabilize the colorant (D). Commercially available dispersants such as BYK series manufactured by Big Chemie can be used, and polyester having a basic functional group. , A polymer dispersant made of polyether or polyurethane, having a nitrogen atom as a basic functional group, the functional group having a nitrogen atom is an amine and / or a quaternary salt thereof, and an amine value of 1 to 100 mgKOH / g Are preferably used.

  The photocurable composition of the present invention can further contain an inorganic compound. Examples of the inorganic compound include metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, silica, and alumina; lamellar clay mineral, miloli blue, calcium carbonate, Magnesium carbonate, cobalt, manganese, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper Among these, titanium oxide, silica, layered clay mineral, silver and the like are preferable. In the photocurable composition of the present invention, the content of the inorganic compound is preferably 0.00 with respect to the total value of 100 parts by mass of the epoxy compound (A), the unsaturated compound (B), and the photopolymerization initiator (C). It is 5-100 mass parts, More preferably, it is 2.0-50 mass parts, and these inorganic compounds can use 1 type (s) or 2 or more types.

By containing an inorganic compound in the photocurable composition of the present invention, it can be used as a photosensitive paste composition. The photosensitive paste composition is used to form a fired product pattern such as a partition pattern, a dielectric pattern, an electrode pattern, and a black matrix pattern of a plasma display panel.
These inorganic compounds are also suitably used as, for example, fillers, antireflection agents, conductive agents, stabilizers, flame retardants, mechanical strength improvers, special wavelength absorbers, ink repellents, and the like.

  In addition, the photocurable composition of the present invention includes, if necessary, a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; a plasticizer; an adhesion promoter; a filler; Conventional additives such as an antifoaming agent, a leveling agent, a surface conditioner, an antioxidant, an ultraviolet absorber, a dispersion aid, a coagulation inhibitor, a catalyst, an effect promoter, a crosslinking agent, and a thickener can be added. .

  In the photocurable composition of the present invention, an ethylenically unsaturated bond excluding an epoxy compound (A), an unsaturated compound (B), a photopolymerization initiator (C), a colorant (D), and an unsaturated compound (B) The content of an optional component other than the polymerizable compound having a solvent and a solvent is appropriately selected according to the purpose of use and is not particularly limited, but is preferably an epoxy compound (A), an unsaturated compound (B), a photopolymerization initiator. The total value of (C) is 50 parts by mass or less with respect to 100 parts by mass.

  In the photocurable composition of the present invention, a chain transfer agent, a sensitizer, a surfactant, melamine and the like can be further used in combination.

  As the chain transfer agent and sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- ( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-me Captoethylamine, 2-mercaptoimidazole, 2-mercaptobenzimidazole, 2-mercapto-3-pyridinol, 2-mercaptobenzothiazole, mercaptoacetic acid, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3- Mercapto compounds such as mercaptopropionate), disulfide compounds obtained by oxidizing the mercapto compounds, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc. Alkyl compound, trimethylolpropane tris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decanedithiol, 1,4- Methyl mercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate , Trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, the following compound no. C1, Karenz PE1, NR1 manufactured by Showa Denko KK and the like.

  Examples of the surfactant include fluorine surfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates, anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates, and alkyl sulfates, and higher amines. Cationic surfactants such as halogenates and quaternary ammonium salts, nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters and fatty acid monoglycerides, amphoteric surfactants, silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

Examples of the melamine compound include all or part of active methylol groups (CH ₂ OH groups) in nitrogen compounds such as (poly) methylol melamine, (poly) methylol glycoluril, (poly) methylol benzoguanamine, and (poly) methylol urea. Mention may be made of compounds in which (at least two) are alkyl etherified. Here, examples of the alkyl group constituting the alkyl ether include a methyl group, an ethyl group, and a butyl group, which may be the same as or different from each other. Moreover, the methylol group which is not alkyletherified may be self-condensed within one molecule, or may be condensed between two molecules, and as a result, an oligomer component may be formed. Specifically, hexamethoxymethyl melamine, hexabutoxymethyl melamine, tetramethoxymethyl glycoluril, tetrabutoxymethyl glycoluril and the like can be used. Among these, alkyl etherified melamines such as hexamethoxymethyl melamine and hexabutoxymethyl melamine are preferable.

In the cured product of the photocurable composition of the present invention containing carbon black as a colorant, the volume resistivity is 1 × 10 ¹² Ω · cm or more, and preferably 1 × 10 ¹³ from the viewpoint of non-conductivity. Ω · cm or more. The surface resistivity is 1 × 10 ¹³ Ω · cm or more, and is preferably 1 × 10 ¹⁴ Ω · cm or more from the viewpoint of non-conductivity.

  The photocurable composition of the present invention is a known method such as spin coater, roll coater, bar coater, die coater, curtain coater, various printing, dipping, soda glass, quartz glass, semiconductor substrate, metal, paper, It can be applied on a supporting substrate such as plastic. Moreover, after once applying on support bases, such as a film, it can also transfer on another support base | substrate, There is no restriction | limiting in the application method.

  Moreover, as the light source of the active light used when curing the photocurable composition of the present invention, one that emits light having a wavelength of 300 to 450 nm can be used, for example, ultrahigh pressure mercury, mercury vapor arc, Carbon arc, xenon arc, etc. can be used.

  Furthermore, by using laser light as the exposure light source, the laser direct drawing method that directly forms an image from digital information such as a computer without using a mask improves not only productivity but also resolution and positional accuracy. As the laser light, light having a wavelength of 340 to 430 nm is preferably used, but an argon ion laser, a helium neon laser, a YAG laser, a semiconductor laser, etc. are visible to infrared region. Those that emit light are also used. When these lasers are used, a sensitizing dye that absorbs the region from visible to infrared is added.

  The photocurable composition of the present invention (or a cured product thereof) is a photocurable paint or varnish, a photocurable adhesive, a printed circuit board, a color television, a PC monitor, a portable information terminal, a digital camera or the like. Color filters for LCD panels, color filters for CCD image sensors, touch panels, electrode materials for plasma display panels, powder coatings, printing inks, printing plates, adhesives, gel coats, photoresists for electronics, electroplating resists, etching For manufacturing resists, liquid and dry films, solder resists, insulating films, color filters for various display applications, or for forming structures in the manufacturing process of plasma display panels, electroluminescent display devices, and LCDs Composition, solder for encapsulating resist, electrical and electronic components Resist, magnetic recording materials, micromechanical components, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, materials for manufacturing 3D objects by stereolithography Holographic recording material, image recording material, fine electronic circuit, decoloring material, decoloring material for image recording material, decoloring material for image recording material using microcapsules, photoresist material for printed wiring board, UV and visible It can be used for various applications such as a photoresist material for a laser direct image system, a photoresist material used for forming a dielectric layer in the sequential lamination of printed circuit boards, or a protective film, and the application is not particularly limited.

  The photocurable composition of the present invention is used for the purpose of forming a black matrix when a black pigment is used, and the black matrix is particularly useful for a color filter for a display device for an image display device such as a liquid crystal display panel. It is.

The black matrix comprises (1) a step of forming a coating film of the photocurable composition of the present invention on a substrate, and (2) a step of irradiating the coating film with active light through a mask having a predetermined pattern shape. (3) The step of developing the exposed film with a developer (particularly an alkali developer) and (4) the step of heating the film after development are preferably formed. The colored composition of the present invention is also useful as an ink jet composition without a development process.
Manufacture of color filters for use in liquid crystal display panels, etc. is made by repeating the above steps (1) to (4) using the present invention or other colored compositions and combining patterns of two or more colors. Can do.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

[Production Example 1] Photopolymerizable unsaturated compound No. 1 Preparation of 1 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane 43 g, acrylic acid 11 g, 2,6-di-tert-butyl-p-cresol 0.05 g, tetrabutylammonium acetate 0.11 g and PGMEA 23 g were charged and stirred at 120 ° C. for 16 hours. After cooling to room temperature, 35 g of PGMEA and 9.4 g of biphenyltetracarboxylic dianhydride were added and stirred at 120 ° C. for 8 hours. Further, 6.0 g of tetrahydrophthalic anhydride was added and stirred at 120 ° C. for 4 hours, 100 ° C. for 3 hours, 80 ° C. for 4 hours, 60 ° C. for 6 hours, and 40 ° C. for 11 hours, and then PGMEA 27 g was added to prepare a PGMEA solution As the photopolymerizable unsaturated compound no. 1 was obtained (Mw = 4000, Mn = 2100, acid value (solid content) 86 mgKOH / g).

[Production Example 2] Photopolymerizable unsaturated compound No. 1 Production of 2 9,9-bis (4-glycidyloxyphenyl) fluorene 75.0 g, acrylic acid 23.8 g, 2,6-di-t-butyl-p-cresol 0.273 g, tetrabutylammonium chloride 0.585 g And PGMEA 65.9 g, and stirred at 90 ° C. for 1 hour, 100 ° C. for 1 hour, 110 ° C. for 1 hour and 120 ° C. for 14 hours. After cooling to room temperature, 25.9 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride, and 1.37 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 90.0 g of 9,9-bis (4-glycidyloxyphenyl) fluorene, 0.269 g of 2,6-di-t-butyl-p-cresol and 1.50 g of PGMEA were added, and 90 minutes at 90 ° C. After stirring at 120 ° C. for 4 hours, 93.4 g of PGMEA was added, and the photopolymerizable unsaturated compound No. 1 as the target product as a PGMEA solution was added. 2 (Mw = 4190, Mn = 2170, acid value (solid content) 52 mg · KOH / g).

[Examples 1-5 and Comparative Examples 1-3] Preparation of Photocurable Composition
Each component was mixed according to the mixing | blending of [Table 1], and the photocurable composition (Examples 1-5 and Comparative Examples 1-3) was obtained. In addition, the number of the line of A-1 to F-2 in Table 1 represents a mass part.

A-1 TEPIC (isocyanurate skeleton epoxy compound; manufactured by Nissan Chemical Co., Ltd.)
A-2 TG-G (glycoluril skeleton epoxy compound; manufactured by Shikoku Kasei Kogyo Co., Ltd.)
A-3 DG-DMH (hydantoin skeleton epoxy compound; manufactured by Shikoku Kasei Kogyo Co., Ltd.)
A′-4 EP-4100L (bisphenol A skeleton epoxy compound; manufactured by ADEKA)
A′-5 EP-4088L (alicyclic skeleton; epoxy compound manufactured by ADEKA)
A′-6 N-660 (cresol novolac skeleton epoxy compound; manufactured by DIC)
B-1 Photopolymerizable unsaturated compound No. 1
B-2 Photopolymerizable unsaturated compound No. 2
C-1 NCI-831 (made by ADEKA)
C-2 TR-PBG-304 (manufactured by Troly)
E-1 KBM403 (alkoxysilane coupling agent; manufactured by Shin-Etsu Chemical Co., Ltd.)
F-1 Kayalad DPHA (dipentaerythritol hexaacrylate; manufactured by Nippon Kayaku Co., Ltd.)
F-2 PGMEA

[Evaluation Examples 1 to 5 and Comparative Evaluation Examples 1 to 3]
After spin coating γ-glycidoxypropylmethylethoxysilane on the substrate and spin drying well, the photocurable compositions No. 1 obtained in Examples 1 to 5 were used. 1-No. 5 and Comparative Photocurable Composition Nos. Obtained in Comparative Examples 1-3. 1-No. 3 was spin-coated (1300 rpm, 50 seconds) and dried. After prebaking at 70 ° C. for 20 minutes, a 5% by weight aqueous solution of polyvinyl alcohol was coated to form an oxygen barrier film. After drying at 70 ° C. for 20 minutes, using a predetermined mask, using an ultra-high pressure mercury lamp as a light source, exposure, and then developing by immersing in a 2.5% by weight sodium carbonate aqueous solution at 25 ° C. for 30 seconds, thoroughly washing with water did. After washing with water and drying, the pattern was fixed by baking at 230 ° C. for 1 hour. The sensitivity was evaluated by changing the exposure amount to the exposure amount described in the following (sensitivity) evaluation method during this exposure. Moreover, photocurable composition No. obtained in Examples 1-5. 1-No. 5 and Comparative Photocurable Composition Nos. Obtained in Comparative Examples 1-3. 1-No. With respect to 3, the transparency, chemical resistance test, and volume resistivity were measured by the following evaluation methods. The results are shown in [Table 1].

[Evaluation method]
(transparency)
The photocurable composition No. obtained in Examples 1-5. 1-No. 5 and Comparative Photocurable Composition Nos. Obtained in Comparative Examples 1-3. 1-No. 3 is spin-coated so that the film thickness of the clear film is 2 μm, pre-baked at 110 ° C. for 2 minutes, exposed at 100 mJ / cm ^{2 with a} high pressure mercury lamp, and post-baked at 230 ° C. for 20 minutes. Of the clear film obtained in this manner, a film having a transmittance of 400 nm of 90% or more was rated as “○”, and a value of 90% or less as “×”.
(Chemical resistance test)
The photocurable composition No. obtained in Examples 1-5. 1-No. 5 and Comparative Photocurable Composition Nos. Obtained in Comparative Examples 1-3. 1-No. 3 is spin-coated so that the film thickness of the clear film is 2 μm, pre-baked at 110 ° C. for 2 minutes, exposed at 100 mJ / cm ^{2 with a} high pressure mercury lamp, and post-baked at 230 ° C. for 20 minutes. Then, a cured film was prepared. The obtained clear film was 5 minutes in 50 ° C. aqua regia, 5 minutes in 4.5% KOH aqueous solution at 40 ° C., and 45 ° C. Al acid aqueous solution (mass ratio: phosphoric acid 70%, nitric acid 10%, acetic acid 20 %) For 5 minutes, 80 ° C. resist stripping solution N-300 (manufactured by Nagase ChemteX) 20 minutes (5 minutes × 4 times) in sequence, followed by the test method of JIS K5600-5-6, A cross cut was applied to the coating film in the shape of a base, a chemical resistance test was performed, a peeling test was performed with a cellophane tape, and the state of peeling of the base was confirmed with a microscope. The ones that were not peeled off 100 squares were marked with ○, and the ones that were peeled off even a little were marked with ×.
(Volume resistivity)
The photocurable composition No. obtained in Examples 1 to 5 on a 100 mm × 100 mm, 0.7 mm thick glass substrate on which aluminum was vapor-deposited for electrodes. 1-No. 5 and Comparative Photocurable Composition Nos. Obtained in Comparative Examples 1-3. 1-No. 3 was applied using a spin coater to a film thickness of 2.50 μm to obtain a coated substrate. Next, after drying under reduced pressure, the coated substrate is heated at 230 ° C. for 210 minutes and allowed to cool, and aluminum for an electrode having an area of 1 cm ² is deposited on the obtained cured coating film, and the black coating film is sandwiched between the aluminum electrodes. A sample was made. The volume resistivity (Ω · cm) of the coating film was measured with a minute current measuring instrument (“R8340A type” manufactured by ADVANTEST).
(sensitivity)
When the exposure amount was 40 mJ / cm ² and the pattern was sufficiently fixed after development, 40 mJ and 40 mJ / cm ² the pattern was not sufficiently fixed, and when exposed at 80 mJ / cm ² , the exposure was 80 mJ.

  From the above results, the photocurable composition of the present invention containing the epoxy compound (A) is more transparent, chemical resistant and volume resistant than the photocurable composition containing a general epoxy compound. It shows good results in rate and sensitivity. Therefore, the photocurable composition of the present invention is useful for various applications.

[Examples 6 to 11 and Comparative Examples 4 to 7] Preparation of photocurable compositions
Each component was mixed according to the mixing | blending of [Table 2], and the photocurable black composition (Examples 6-11 and Comparative Examples 4-7) containing carbon black as a coloring agent (D) was obtained. In Table 2, the numbers in the rows A-1 to F-3 represent parts by mass.

A-1 TEPIC (isocyanurate skeleton epoxy compound; manufactured by Nissan Chemical Co., Ltd.)
A-2 TG-G (glycoluril skeleton epoxy compound; manufactured by Shikoku Kasei Kogyo Co., Ltd.)
A-3 DG-DMH (hydantoin skeleton epoxy compound; manufactured by Shikoku Kasei Kogyo Co., Ltd.)
A′-4 EP-4100L (bisphenol A skeleton epoxy compound; manufactured by ADEKA)
A′-5 EP-4088L (alicyclic skeleton; epoxy compound manufactured by ADEKA)
A′-6 N-660 (cresol novolac skeleton epoxy compound; manufactured by DIC)
B-1 Photopolymerizable unsaturated compound No. 1
B-2 Photopolymerizable unsaturated compound No. 2
C-1 NCI-831 (made by ADEKA)
C-2 TR-PBG-304 (manufactured by Troly)
D-1 Surface-treated carbon black dispersion D-1 (carbon black 20%, PGMEA 75%)
D-2 Surface-treated carbon black dispersion D-2 (carbon black 20%, PGMEA 76.5%)
E-1 KBM403 (alkoxysilane coupling agent; manufactured by Shin-Etsu Chemical Co., Ltd.)
F-1 Kayalad DPHA (dipentaerythritol hexaacrylate; manufactured by Nippon Kayaku Co., Ltd.)
F-2 PGMEA
F-3 Cyclohexanone

[Evaluation Examples 6 to 11 and Comparative Evaluation Examples 4 to 7]
After spin coating γ-glycidoxypropylmethylethoxysilane on the substrate and spin drying well, the photocurable black composition Nos. Obtained in Examples 6 to 11 were used. 6-No. 11 and comparative photocurable black composition Nos. Obtained in Comparative Examples 4-7. 4-No. 7 was spin-coated (1300 rpm, 50 seconds) and dried. After prebaking at 70 ° C. for 20 minutes, a 5% by weight aqueous solution of polyvinyl alcohol was coated to form an oxygen barrier film. After drying at 70 ° C. for 20 minutes, after exposure at 100 mJ / cm ² using an ultra-high pressure mercury lamp as a light source using a predetermined mask, it was immersed in a 2.5% by weight aqueous sodium carbonate solution at 25 ° C. for 30 seconds. Developed and washed well with water. After washing with water and drying, the pattern was fixed by baking at 230 ° C. for 1 hour. In this exposure, the sensitivity was evaluated by changing the exposure amount to the exposure amount described in the above (sensitivity) evaluation method. Moreover, photocurable black composition No. obtained in Examples 6-11. 6-No. 11 and comparative photocurable black composition Nos. Obtained in Comparative Examples 4-7. 4-No. For 7, the volume resistivity was measured by the above method, and the OD value was measured by the following evaluation method. The results are shown in [Table 2].

(OD value)
Photocurable black composition No. obtained in Examples 6-11. 6-No. 11 and Comparative Example No. Spin coating was applied to 4 to 7 to a film thickness of 2 μm, baked at 110 ° C. for 2 minutes as a pre-bake, exposed at 100 mJ / cm ^{2 with a} high-pressure mercury lamp, and baked at 230 ° C. as a post-bake for 20 minutes. Thus, a film was obtained. The OD value of the obtained film was measured using a Macbeth transmission densitometer, and the OD value per unit film thickness was calculated by dividing the OD value by the film thickness after post-baking.

From the above results, it is clear that the photocurable black composition of the present invention containing the epoxy compound (A) is excellent in volume resistivity and sensitivity while maintaining the OD value, and has high light shielding properties. High resistance. Therefore, the photocurable black composition of the present invention is useful for a black matrix.

Claims (9)

An epoxy compound (A) containing in its structure a group selected from the group represented by the following formula (a), (b) or (c);
Unsaturation which is a reaction product obtained by esterification reaction of an epoxy addition compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the following general formula (I) and a polybasic acid anhydride A photocurable composition containing a compound (B) and a photopolymerization initiator (C) ,
The epoxy compound (A) has two or more epoxy groups,
When M in the following general formula (I) is a group represented by the following formula (g), the polybasic acid anhydride is tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, Photo-curing only hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, dodecenyl succinic anhydride or methyl hymic anhydride Composition.

(In the formula, M represents —O—, —S—, —SO ₂ —, —SS—, —SO—, —CO—, —OCO— or the following formula (d), (e), (f) or ( g) represents a substituent selected from the group represented by: R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, carbon number 1 Represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom, and n is a number from 0 to 10).

(In the formula, R ⁹ represents an alkyl group having 1 to 3 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms. R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 6 to 6 carbon atoms. 20 represents an aryl group, an arylalkyl group having 7 to 20 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, or a halogen atom, and the alkylene moiety in the alkyl group and arylalkyl group is an unsaturated bond, -O- or It may be interrupted by ^{S-, R 10, R 11,} R 12, R 13, R 14, R 15, R 16, R 17, R 22, R 23, R 24, R 25, R 30, R 31 , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ are adjacent to R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ and R ³⁸ may form a ring. The epoxy compound (A) has a group represented by the following formula (a-1) or (a-2) as a structure containing the formula (a), or a structure containing the formula (b) (B-1) having a group represented by (b-2) or (b-3), or having a group represented by the following formula (c-1) as a structure containing the above formula (c) The photocurable composition according to claim 1, comprising:

The epoxy compound (A) contains in its structure a group selected from the group represented by the formula (b) or (c),
The photocurable composition according to claim 1 or 2, wherein * in the formulas (b) and (c) represents a bond bonded to a carbon atom. When M in the general formula (I) is a group represented by the following formula (g), the polybasic acid anhydride is succinic anhydride, maleic anhydride, trimellitic anhydride, hexahydrophthalic anhydride, Either of methyltetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, dodecenyl succinic anhydride, or methyl hymic anhydride is provided. Item 1. The photocurable composition according to item 1. Furthermore, the photocurable composition of any one of Claims 1-4 containing a coloring agent (D). The photocurable composition according to claim 5 , wherein the colorant (D) is a black pigment. Furthermore, the photocurable composition of any one of Claims 1-6 containing a silane coupling agent (E). The black matrix using the photocurable composition of Claim 6 or 7 . A color filter having a black matrix according to claim 8 .