JP2015007729A - Photocurable black composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable black composition that exhibits excellent sensibility, excellent adhesion, high light shielding effect and high resistance and is useful as a black matrix.SOLUTION: A photocurable black composition contains: a photopolymerizable unsaturated compound (A) having a structure obtained by an esterification reaction between a polybasic acid anhydride and an epoxy addition compound that has a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the general formula (I) in the figure; a photoinitiator (B); and titanium black (C).

Description

  The present invention relates to a photocurable black composition containing a photopolymerizable unsaturated compound having a specific structure and titanium black.

  The photocurable black composition contains a black pigment, a photopolymerizable unsaturated compound, and a photopolymerization initiator. Since this photocurable black composition can be polymerized and cured by irradiation with ultraviolet rays or electron beams, the boundary between the R, G, and B colored layers of the color filter is particularly enhanced in order to enhance display contrast and coloring effect. It is useful as a black matrix provided in the part.

  In recent years, with higher image quality of liquid crystal display elements, higher performance is also required for the black matrix, and in order to achieve this purpose, a black matrix having excellent sensitivity, light shielding properties and high resistance is required. ing.

  In the following Patent Document 1, a polymer compound (A), titanium black (B), a dispersion aid (C), a solvent (D), a photopolymerizable compound having at least one ethylenically unsaturated double bond ( E), a black radiation sensitive resin composition containing a radical photopolymerization initiator (F) and a tertiary amine compound (G) is disclosed. Patent Document 2 listed below discloses an acrylic resin-based binder polymer, A black photosensitive resin composition containing a photopolymerizable compound having an ethylenically unsaturated bond, a photopolymerization initiator, and a black pigment is disclosed. Patent Document 3 below discloses a light shielding material containing a colorant, and a specific structure. A photosensitive resin composition for BM (black matrix) is disclosed that includes a resin binder having a polyfunctional monomer having an ethylenically unsaturated double bond, a photopolymerization initiator, and a remaining amount of a solvent.

Japanese Patent No. 3230800 International Publication No. 2008-032675 Japanese Patent No. 4804777

  Accordingly, an object of the present invention is to provide a photocurable black composition that is excellent in sensitivity and adhesion, has high light shielding properties, and has high resistance.

  As a result of intensive studies, the present inventors have obtained 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 black composition containing a photopolymerizable unsaturated compound (A) having a structure obtained by an esterification reaction, a photopolymerization initiator (B) and titanium black (C) is suitable for the black matrix. The present invention has been found.

（式中、Ｘ¹は下記式（イ）又は（ロ）で表される置換基を表し、Ｒ¹、Ｒ²、Ｒ³及びＲ⁴は、それぞれ独立に、水素原子、炭素原子数１〜５のアルキル基、炭素原子数１〜８のアルコキシ基、炭素原子数２〜５のアルケニル基又はハロゲン原子を表し、ｍは０〜１０の整数を表す。）

(In the formula, X ¹ represents a substituent represented by the following formula (A) or (B), and R ¹ , R ² , R ^3, and R ⁴ are each independently a hydrogen atom, a carbon atom number of 1 to 5 represents an alkyl group, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a halogen atom, and m represents an integer of 0 to 10).

（式中、Ｙ¹は、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、炭素原子数７〜３０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、上記アルキル基及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−で中断されていてもよく、Ｙ¹は、隣接するＹ¹同士で環を形成していてもよく、ｎは０〜４の整数を表す。）

(In the formula, Y ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a complex having 2 to 20 carbon atoms. A cyclic group or a halogen atom is represented, and the alkylene part in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, and Y ¹ is adjacent to Y ^1. And may form a ring, and n represents an integer of 0 to 4.)

（式中、Ｙ²及びＺ²は、それぞれ独立して、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、炭素原子数７〜３０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、上記アルキル基及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−で中断されていてもよく、Ｚ²は、隣接するＺ²同士で環を形成していてもよく、ｐは０〜４の整数を表し、ｑは０〜８の整数を表し、ｒは０〜４の整数を表し、ｓは０〜４の整数を表し、ｒとｓの数の合計は２〜４の整数である。）

Wherein Y ² and Z ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, Represents a heterocyclic group having 2 to 20 carbon atoms, or a halogen atom, and the alkylene moiety in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, ² may form a ring with adjacent Z ² , p represents an integer of 0 to 4, q represents an integer of 0 to 8, r represents an integer of 0 to 4, and s represents The integer of 0-4 is represented, and the sum total of the number of r and s is an integer of 2-4.)

  The present invention also provides a black matrix using the photocurable black composition and a color filter having the black matrix.

  According to the present invention, a photocurable black composition containing a photopolymerizable unsaturated compound having a specific structure and titanium black is excellent in sensitivity, adhesion, and light shielding properties and has a high resistance value. The cured product is suitable for a color filter for display devices, a liquid crystal display panel, and an organic EL display panel.

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

  The photocurable black composition of the present invention is an esterification of 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 acid anhydride. It contains a photopolymerizable unsaturated compound (A) having a structure obtained by the reaction, a photopolymerization initiator (B), and titanium black (C). Hereinafter, each component will be described in order.

<Photopolymerizable unsaturated compound (A)>
The photopolymerizable unsaturated compound (A) used in the photocurable black composition of the present invention is 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 structure obtained by an esterification reaction with a polybasic acid anhydride. The photopolymerizable unsaturated compound (A) used in the photocurable black composition of the present invention is a kind of polymerizable compound having an ethylenically unsaturated bond.

In the general formula (I), R ^1, R ^2, R ³ and an alkyl group having 1 to 5 carbon atoms represented by R ^4, methyl, ethyl, propyl, iso- propyl, butyl, sec- butyl Tert-butyl, iso-butyl, amyl, iso-amyl, tert-amyl and the like,
The R ^1, R ^2, R ³ and alkoxy group having 1 to 8 carbon atoms represented by R ^4, methyloxy, ethyloxy, iso- propyloxy, propyloxy, butyloxy, pentyloxy, iso- pentyloxy, Hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, etc.
Examples of the alkenyl group having 2 to 5 carbon atoms represented by R ¹ , R ² , R ³ and R ⁴ include vinyl, allyl, butenyl, propenyl,
Examples of the halogen atom represented by R ¹ , R ² , R ³ and R ⁴ and Y ¹ , Y ² and Z ² include fluorine, chlorine, bromine and iodine.

In (i) which is X ¹ in the general formula (I), the alkyl group having 1 to 20 carbon atoms represented by Y ¹ is exemplified by the above R ¹ , R ² , R ³ and R ⁴ . 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, perfluorobutyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, Cyclononyl, Kurodeshiru and the like,
Examples of the aryl group having 6 to 30 carbon atoms represented by Y ¹ include phenyl, naphthyl, anthracen-1-yl, phenanthren-1-yl, o-tolyl, m-tolyl, p-tolyl, and 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-trichlorophenyl, 4-triphenyl Fluorophenyl, perfluorophenyl and the like,
Examples of the arylalkyl group having 7 to 30 carbon atoms represented by Y ¹ include benzyl, phenethyl, 2-phenylpropyl, diphenylmethyl, triphenylmethyl, styryl, cinnamyl, 4-chlorophenylmethyl, and the like.
Examples of the heterocyclic group having 2 to 20 carbon atoms represented by Y ¹ 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.

In (b) which is X ¹ in the general formula (I), an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 7 carbon atoms represented by Y ² and Z ² Examples of the ˜30 arylalkyl group and the heterocyclic group having 2 to 20 carbon atoms include those exemplified in (i) which is X ¹ in the general formula (I).

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 black composition of the present invention, the content of the photopolymerizable unsaturated compound (A) is preferably 5 to 80% by mass in the composition other than the solvent in the photocurable black composition. 10 to 40% by mass is more preferable. The content is preferably 5% by mass or more from the viewpoint of curability, and it is preferably 80% by mass or less from the viewpoint of light shielding properties.

<Photoinitiator (B)>
As the photopolymerization initiator (B) used in the photocurable black composition of the present invention, conventionally known compounds can be used, for example, benzophenone, phenylbiphenyl ketone, 1-hydroxy-1-benzoylcyclohexane. 4-benzoyl-4′-methyldiphenyl sulfide, benzoin butyl ether, 2-hydroxy-2-benzoylpropane, 2-hydroxy-2- (4′-isopropyl) benzoylpropane, 4-butylbenzoyltrichloromethane, 4-phenoxybenzoyl Dichloromethane, methyl benzoylformate, benzoin, 2-morpholyl-2- (4′-methylmercapto) benzoylpropane, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-benzyl-1-dimethylamino- 1- (4′-morpholino Alkylphenone compounds such as benzoyl) propane; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2 Oxime ester compounds such as -methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); thioxanthone compounds such as thioxanthone, 1-chloro-4-propoxythioxanthone, isopropylthioxanthone, diethylthioxanthone; Anthraquinone compounds such as ethyl anthraquinone; biimidazole compounds such as 2,2-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1-2′-biimidazole; 2-methyl-4, 6-bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis Triazine compounds such as (trichloromethyl) -s-triazine and 2-naphthyl-4,6-bis (trichloromethyl) -s-triazine; azo compounds such as 4,4-azobisisobutyronitrile; benzoyl peroxide and the like 1,7-bis (9′-acridinyl) heptane, 9-n-butyl-3,6-bis (2′-morpholinoisobutyroyl) carbazole, triphenylphosphine, camphorquinone, etc. As commercially available products, N-1414, N-1717, N-1919, PZ-808, NCI-831, NCI-930 (manufactured by ADEKA), IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE OXE 01, IRGACURE OX 02 (BASF ( ) Co., Ltd.), and the like.

  Especially as a photoinitiator (B) used for the photocurable black composition of this invention, the compound represented with the following general formula (II) is preferable from the point of a sensitivity and heat resistance.

（式中、Ｒ⁶及びＲ⁷は、それぞれ独立に、水素原子、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、
Ｒ⁸及びＲ⁹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、Ｒ¹⁰、ＯＲ¹¹、ＳＲ¹²、ＮＲ¹³Ｒ¹⁴、ＣＯＲ¹⁵、ＳＯＲ¹⁶、ＳＯ₂Ｒ¹⁷又はＣＯＮＲ¹⁸Ｒ¹⁹を表し、
Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵、Ｒ¹⁶、Ｒ¹⁷、Ｒ¹⁸及びＲ¹⁹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の複素環基を表し、
Ｘ²は、酸素原子、硫黄原子、セレン原子、ＣＲ²⁰Ｒ²¹、ＣＯ、ＮＲ²²又はＰＲ²³を表し、
Ｘ³は、単結合又はＣＯを表し、
Ｒ²⁰、Ｒ²¹、Ｒ²²及びＲ²³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、該アルキル基又はアリールアルキル基中のメチレン基は、−Ｏ−で中断されていてもよく、
Ｒ²⁰、Ｒ²¹、Ｒ²²及びＲ²³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く、
ａは、０〜４の整数を表し、
ｂは、１〜５の整数を表す。）

Wherein R ⁶ and R ⁷ are each independently a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl having 7 to 30 carbon atoms. Represents a group or a heterocyclic group having 2 to 20 carbon atoms,
R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, R ¹⁰ , OR ¹¹ , SR ¹² , NR ¹³ R ¹⁴ , COR ¹⁵ , SOR ¹⁶ , SO _2. Represents R ¹⁷ or CONR ¹⁸ R ¹⁹ ,
R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently an alkyl group having 1 to 20 carbon atoms or 6 to 6 carbon atoms. A 30 aryl group, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms;
X ² represents an oxygen atom, a sulfur atom, a selenium atom, CR ²⁰ R ²¹ , CO, NR ²² or PR ²³ ,
X ³ represents a single bond or CO,
R ²⁰ , R ²¹ , R ²² and R ²³ 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. Methylene group in the alkyl group or arylalkyl group may be interrupted by -O-,
R ²⁰ , R ²¹ , R ²² and R ²³ may each independently form a ring together with one of the adjacent benzene rings,
a represents an integer of 0 to 4,
b represents an integer of 1 to 5. )

  In the photocurable black composition of the present invention, the content of the photopolymerization initiator (B) is 0.1 to 30% by mass, particularly 0.5 in the solid content of the photocurable black composition of the present invention. -10 mass% is preferable. When the content of the photopolymerization initiator is less than 0.1% by mass, curing by exposure may be insufficient, and when it is greater than 30% by mass, the initiator may be precipitated in the resin composition. .

<Titanium Black (C)>
Examples of the titanium black (C) used in the photocurable black composition of the present invention include a nitrogen-containing reducing agent such as ammonia gas or amine gas after a vanadium compound is attached to titanium dioxide or titanium hydroxide as necessary. Can be obtained by baking at a high temperature by a gas phase reaction method such as an electric furnace method or a thermal plasma method, or can be obtained commercially as titanium black, and these can be used alone. Or two or more of them may be used in combination.

The particle diameter of the titanium black (C) is preferably 5 to 150 nm from the viewpoint of dispersibility, and the specific surface area measured by the BET method is preferably 30 to ²⁰⁰ m ² from the viewpoint of light shielding properties.

  The titanium black (C) is mainly composed of TiN, but may contain oxygen atoms due to oxygen contamination during the synthesis or oxidation of the particle surface. The amount of oxygen contained is preferably 20% by mass or less because the OD value of the cured product of the photocurable black composition is increased.

  In the photocurable black composition of the present invention, the content of the titanium black (C) is preferably 1 to 350 parts by mass with respect to a total of 100 parts by mass of the polymerizable compounds having an ethylenically unsaturated bond. Preferably it is 10-250 mass parts. If it exceeds 350 parts by mass, the black pigment tends to aggregate and the storage stability will deteriorate.

A black pigment (D) other than titanium black can be further used in the photocurable black composition of the present invention. Examples of the black pigment (D) other than the titanium black include carbon black obtained by furnace method, channel method, thermal method, or carbon black such as acetylene black, ketjen black or lamp black; The carbon black was previously dispersed with a resin in a solvent and 20 to 200 mg / g of resin was adsorbed, the carbon black was treated with an acidic or alkaline surface, and the average particle size was 8 nm or more and DBP oil absorption of 90 ml / 100 g or less, and the total oxygen amount calculated from CO and CO ₂ in volatile matter at 950 ° C. is 9 mg or more per 100 m ² of the surface area of carbon black; graphite, graphitization Carbon black, activated carbon, carbon fiber, carbon Tube, carbon microcoil, carbon nanohorn, carbon aerogel, fullerene; aniline black, perylene black, pigment black 7, and the like.

  When the photocurable black composition of the present invention contains a black pigment (D) other than titanium black, the content of the titanium black (C) and the black pigment (D) other than titanium black is 100 masses in total of the pigment. It is preferable that the titanium black (C) is 80 to 20 parts by mass and the black pigment (D) other than titanium black is 20 to 80 parts by mass with respect to parts.

  The photocurable black composition of the present invention may further contain an inorganic color material or organic color material other than the above-described titanium black (C) and black pigment (D) other than titanium black. These color materials 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; hydrophobic Resin, chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate ultramarine, bitumen, ultramarine, cerulean blue, pyridian, Main lardo green, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, can be used inorganic or organic pigments amber like.

  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. And dyes such as phthalocyanine dyes and cyanine dyes.

  A dispersant can be further used in the photocurable black composition of the present invention. The dispersing agent may be anything as long as it can disperse and stabilize the above-described titanium black (C), black pigment (D) other than titanium black, and the like, for example, a commercially available dispersing agent such as BYK series manufactured by BYK Chemie. A polymer dispersant comprising a basic functional group polyester, polyether, polyurethane, a basic functional group having a nitrogen atom, the functional group having a nitrogen atom being an amine, and / or a quaternary thereof A salt having an amine value of 1 to 100 mgKOH / g is preferably used.

  In the photocurable black composition of the present invention, a polymerizable compound having an ethylenically unsaturated bond other than the photopolymerizable unsaturated compound (A) 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.
In the photocurable black composition of the present invention, when a polymerizable compound having an ethylenically unsaturated bond other than the photopolymerizable unsaturated compound (A) is used, ethylenic other than the photopolymerizable unsaturated compound (A) is used. The content of the polymerizable compound having an unsaturated bond is preferably 1 to 30% by mass and more preferably 5 to 15% by mass in the composition other than the solvent in the photocurable black composition.

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 photosensitive composition of the present invention. When using the compound which has the said acid value, it is preferable to make the usage-amount become 50-99 mass% of the whole polymeric compound which has the said ethylenically unsaturated bond.
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.

  Moreover, the photocurable black composition of the present invention may contain a compound that does not have an ethylenically unsaturated bond and imparts alkali developability, and such a compound has an acid value. The compound is not particularly limited as long as it is a compound that is soluble in an alkaline 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 20 to 1000 parts by mass per 100 parts by mass of the reaction raw material. 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, styrene-maleic anhydride copolymer, polyvinylhydroxybenzoate, and the like.

  A solvent can be further added to the photocurable black composition of the present invention. As the solvent, the above-described components (the photopolymerizable unsaturated compound (A) of the present invention, the photopolymerization initiator (B), titanium black (C), etc.) can be dissolved or dispersed as required. Solvents 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-dimethoxyethane, 1,2 Ether solvents such as diethoxyethane and dipropylene glycol dimethyl ether; ester solvents such as methyl acetate, ethyl acetate, acetic acid-n-propyl, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, and texanol Solvent; ethylene glycol monomer Cellosolve solvents such as ether, 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 monoethyl acetate, Ether ester solvents such as propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and ethoxyethyl propionate; BTX solvents such as benzene, toluene and xylene Aliphatic hydrocarbon solvents such as hexane, heptane, octane and cyclohexane; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; minerals Paraffinic solvents such as Litt, Swazol # 310 (Cosmo Matsuyama Oil Co., Ltd.), Solvesso # 100 (Exxon Chemical Co., Ltd.); Halogenation of carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane, etc. Aliphatic hydrocarbon solvents; halogenated aromatic hydrocarbon solvents such as chlorobenzene; carbitol solvents, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N, N-dimethylformamide, N, N-dimethyl Examples include acetamide, N-methylpyrrolidone, dimethyl sulfoxide, water, and the like, and these solvents can be used as one or a mixture of two or more. Among these, ketones, ether ester solvents and the like, particularly propylene glycol-1-monomethyl ether-2-acetate (PGMEA), cyclohexanone, and the like are preferable because the compatibility of the resist and the photopolymerization initiator in the colored composition is good.

  In the photocurable black 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 is increased. This is not preferable because it cannot easily absorb light of a desired wavelength, and 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. Therefore, it is not preferable.

  The photocurable black 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 black composition of the present invention, the content of the inorganic compound is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts per 100 parts by mass of the photopolymerizable unsaturated compound. It is a mass part, and these inorganic compounds can use 1 type (s) or 2 or more types.

By containing an inorganic compound in the photocurable black 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 black 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. Antifoaming agent, leveling agent, surface conditioner, antioxidant, ultraviolet absorber, dispersion aid, aggregation inhibitor, catalyst, effect promoter, cross-linking agent, thickener, etc. it can.

  In the photocurable black composition of the present invention, the content of optional components other than the photopolymerizable unsaturated compound (A), the photopolymerization initiator (B), and titanium black (C) is appropriately determined according to the purpose of use. Although it is selected and not particularly limited, it is preferably 50 parts by mass or less in total with respect to 100 parts by mass of the photopolymerizable unsaturated compound.

  In the photocurable black composition of the present invention, a chain transfer agent, a sensitizer, a surfactant, a melamine compound, 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 photocurable black composition of the present invention, the optical density (OD) is preferably 2.0 to 5.0 / [mu] m because high light shielding properties are obtained.

In the photocurable black composition of the present invention, the volume resistivity is 1 × 10 ¹¹ Ω · cm or more, and preferably 1 × 10 ¹³ Ω · cm or more from the viewpoint of non-conductivity. The surface resistivity is 1 × 10 ¹³ Ω / sq. From the viewpoint of non-conductivity, preferably 1 × 10 ¹⁴ Ω / sq. That's it.

  The photocurable black 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 a light source of the active light used when hardening the photocurable black composition of this invention, what emits light with a wavelength of 300-450 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 black composition of the present invention (or a cured product thereof) is a color display of a photocurable paint or varnish, a photocurable adhesive, a printed circuit board, a color TV, 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, For manufacturing etching resists, both 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 Compositions for encapsulating resists, electrical and electronic components For manufacturing three-dimensional objects by using resist, magnetic recording materials, micromechanical components, waveguides, optical switches, plating masks, etching masks, color test systems, glass fiber cable coatings, stencils for screen printing, and stereolithography Materials, holographic recording materials, image recording materials, fine electronic circuits, decoloring materials, decoloring materials for image recording materials, decoloring materials for image recording materials using microcapsules, photoresist materials for printed wiring boards, UV and It can be used for various applications such as photoresist material for visible laser direct image system, photoresist material used for dielectric layer formation in sequential lamination of printed circuit boards or protective film, and there are no particular restrictions on its use .

  The photocurable black composition of the present invention is used for the purpose of forming a black matrix, 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.

The black matrix includes (1) a step of forming a coating film of the photocurable black composition of the present invention on a substrate, and (2) irradiating the coating film with active light through a mask having a predetermined pattern shape. It is preferably formed by a step, (3) a step of developing the film after exposure with a developer (particularly an alkali developer), and (4) a step of heating the film after development. 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 30.0 g, acrylic acid 7.52 g, 2,6-di-t-butyl-p-cresol 0.080 g, Tetrabutylammonium chloride 0.183g and PGMEA 11.0g were prepared, and it stirred at 90 degreeC for 1 hour, 105 degreeC for 1 hour, and 120 degreeC for 17 hours. After cooling to room temperature, 8.11 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride and 11.1 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, 12.0 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane, 0.080 g of 2,6-di-t-butyl-p-cresol and 0.600 g of PGMEA were added. After stirring at 90 ° C. for 90 minutes and at 120 ° C. for 5 hours, 24.0 g of PGMEA was added to prepare PGMEA solution as a photopolymerizable unsaturated compound no. 1 was obtained.

[Production Example 2] Photopolymerizable unsaturated compound No. 1 Production of 2 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane 30.0 g, acrylic acid 7.52 g, 2,6-di-t-butyl-p-cresol 0.104 g, Tetrabutylammonium chloride (0.183 g) and PGMEA (11.0 g) were charged and stirred at 90 ° C. for 1 hour, 105 ° C. for 1 hour and 120 ° C. for 17 hours. After cooling to room temperature, 9.24 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 0.154 g of 1,2,3,6-tetrahydrophthalic anhydride, 0.427 g of tetrabutylammonium chloride And PGMEA 12.1 g, and after stirring at 120 ° C. for 5 hours, at 90 ° C. for 1 hour, at 60 ° C. for 2 hours and at 40 ° C. for 3 hours, PGMEA 17.5 g is added, and PGMEA solution is the target photopolymerization Unsaturated compound no. 2 was obtained.

[Production Example 3] Photopolymerizable unsaturated compound No. 1 Preparation of 3 Bis [4- (2,3-epoxypropoxy) phenyl] -4-biphenylyl (cyclohexyl) methane 89.9 g, acrylic acid 23.5 g, 2,6-di-tert-butyl-p-cresol 457 g, benzyltriethylammonium chloride 0.534 g and PGMEA 75.6 g were charged and stirred at 120 ° C. for 16 hours. The mixture was cooled to room temperature, charged with 12.0 g of 2,4-pentanedione and 1.0 g of triethylamine, and stirred at 92 ° C. for 17 hours. After cooling to room temperature, 25.6 g of succinic anhydride, 1.39 g of tetra-n-butylammonium bromide and 40.42 g of PGMEA were added and stirred at 100 ° C. for 5 hours. After cooling to room temperature, 46.7 g of PGMEA was added, and the photopolymerizable unsaturated compound No. 1 as the target product as a PGMEA solution was added. 3 was obtained.

[Comparative Production Example 1] Comparative photopolymerizable unsaturated compound No. 1 Production of 1 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 a comparative photopolymerizable unsaturated compound No. 1 as a target product as a PGMEA solution was added. 1 was obtained.

[Examples 1-7 and Comparative Examples 1-2] Photocurable black composition No. 1-No. 7 and comparative photocurable black composition no. 1-No. Preparation of 2
Each component was mixed according to the composition of [Table 1], and photocurable black composition No. 1-No. 7 and comparative photocurable black composition no. 1-No. 2 was obtained. In addition, the number concerning A-1 to E-3 represents a mass part.

A-1 Photopolymerizable unsaturated compound No. 1 1
A-2 Photopolymerizable unsaturated compound No. 2
A-3 Photopolymerizable unsaturated compound No. 3
A′-1 Comparative photopolymerizable unsaturated compound No. 1 1
B-1 OXE-01 (manufactured by BASF)
B-2 NCI-831 (made by ADEKA)
B-3 N-1919 (made by ADEKA)
C-1 13M-C (titanium black, manufactured by Mitsubishi Materials Corporation)
C-2 Titanium nitride 50nm (Wako Pure Chemical Industries, Ltd.)
D-1 MA100 (carbon black, manufactured by Mitsubishi Chemical Corporation)
D-2 Periogen Black L0084 (Perylene Black, manufactured by BASF)
E-1 Kayalad R-684 (Tricyclodecane dimethanol diacrylate; manufactured by Nippon Kayaku Co., Ltd.)
E-2 Aronix M-405 (polyfunctional acrylate; manufactured by Toa Gosei Co., Ltd.)
E-3 PGMEA

[Evaluation Examples 1-7 and Comparative Evaluation Examples 1-2]
After spin coating γ-glycidoxypropylmethylethoxysilane on the substrate and spin drying well, the photocurable black composition No. 1 obtained in Examples 1 to 7 was used. 1-No. 7 and comparative photocurable black composition No. 1 obtained in Comparative Examples 1 and 2. 1-No. 2 was spin-coated (1300 rpm, 50 seconds) and dried. After pre-baking at 70 ° C. for 20 minutes, a 5% polyvinyl alcohol solution 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 was performed, soaked in a 2.5% sodium carbonate solution at 25 ° C. for 30 seconds, developed, and washed thoroughly with water. . After washing with water and drying, the pattern was fixed by baking at 230 ° C. for 1 hour. About the obtained pattern, the following sensitivity and adhesive evaluation, OD value, and resistivity were measured. The results are shown in the above [Table 1].
(sensitivity)
During exposure, what exposure was sufficient 70 mJ / cm ² a, inadequate in 70 mJ / cm ^2, those exposed at 100 mJ / cm ² b, insufficient in 100mJ / cm ^2, 150mJ / cm ^The one exposed in ² was designated as c.
(Adhesion test)
In accordance with the test method of JIS D 0202, a cross cut was made on the coating film in the shape of a base, and then a peeling test was performed with a cellophane tape, and the peeling state of the base was visually evaluated. A sample in which no peeling was observed was marked with ○, and a sample in which peeling was observed was marked with ×.
(OD value)
The OD value of the obtained film was measured using an X-Rite 361T transmission densitometer, and the OD value per film thickness was calculated by dividing the OD value by the film thickness after post-baking.
(Volume resistivity)
The photocurable black composition No. 1 obtained in Examples 1 to 7 on a 100 mm × 100 mm, 0.7 mm thick glass substrate on which aluminum was vapor-deposited for electrodes. 1-No. 7 and comparative photocurable black composition No. 1 obtained in Comparative Examples 1 to 3. 1-No. 3 was applied using a spin coater to a 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 aluminum electrodes. A sample was made. The volume resistivity of the coating film was measured by a minute current measuring device (“R8340A type” manufactured by ADVANTEST).
(Surface resistivity)
On the glass substrate of 100 mm x 100 mm and thickness 0.7 mm, the photocurable black composition No. obtained in Examples 1-7. 1-No. 7 and comparative photocurable black composition No. 1 obtained in Comparative Examples 1 to 3. 1-No. 3 was applied using a spin coater to a film thickness of 1.20 μm to obtain a coated substrate. Next, after drying under reduced pressure, exposure was performed using an ultrahigh pressure mercury lamp at an exposure amount of 40 mJ / cm ² . After alkali development, the coated substrate was heated at 230 ° C. for 60 minutes and allowed to cool. The surface resistivity of the coating film was measured by a microcurrent measuring device (“R8340A type” manufactured by ADVANTEST and “Ladyness chamber 12704A”).

  From the above results, the photocurable black composition of the present invention containing a photopolymerizable unsaturated compound having a specific structure is excellent in sensitivity and adhesion, has high light shielding properties and high resistance. Therefore, the photocurable black composition of the present invention is useful for a black matrix.

Claims (5)

Photopolymerizability having a structure obtained by an esterification reaction between an epoxy addition compound having an unsaturated monobasic acid added to an epoxy compound represented by the following general formula (I) and a polybasic acid anhydride A photocurable black composition containing an unsaturated compound (A), a photopolymerization initiator (B), and titanium black (C).

(In the formula, X ¹ represents a substituent represented by the following formula (A) or (B), and R ¹ , R ² , R ^3, and R ⁴ are each independently a hydrogen atom, a carbon atom number of 1 to 5 represents an alkyl group, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or a halogen atom, and m represents an integer of 0 to 10).

(In the formula, Y ¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a complex having 2 to 20 carbon atoms. A cyclic group or a halogen atom is represented, and the alkylene part in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, and Y ¹ is adjacent to Y ^1. And may form a ring, and n represents an integer of 0 to 4.)

Wherein Y ² and Z ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, Represents a heterocyclic group having 2 to 20 carbon atoms, or a halogen atom, and the alkylene moiety in the alkyl group and arylalkyl group may be interrupted by an unsaturated bond, -O- or -S-, ² may form a ring with adjacent Z ² , p represents an integer of 0 to 4, q represents an integer of 0 to 8, r represents an integer of 0 to 4, and s represents The integer of 0-4 is represented, and the sum total of the number of r and s is an integer of 2-4.) The photocurable black composition according to claim 1, wherein the photopolymerization initiator (B) is represented by the following general formula (II).

Wherein R ⁶ and R ⁷ are each independently a hydrogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl having 7 to 30 carbon atoms. Represents a group or a heterocyclic group having 2 to 20 carbon atoms,
R ⁸ and R ⁹ are each independently a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, a carboxyl group, R ¹⁰ , OR ¹¹ , SR ¹² , NR ¹³ R ¹⁴ , COR ¹⁵ , SOR ¹⁶ , SO _2. Represents R ¹⁷ or CONR ¹⁸ R ¹⁹ ,
R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently an alkyl group having 1 to 20 carbon atoms or 6 to 6 carbon atoms. A 30 aryl group, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms;
X ² represents an oxygen atom, a sulfur atom, a selenium atom, CR ²⁰ R ²¹ , CO, NR ²² or PR ²³ ,
X ³ represents a single bond or CO,
R ²⁰ , R ²¹ , R ²² and R ²³ 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. Methylene group in the alkyl group or arylalkyl group may be interrupted by -O-,
R ²⁰ , R ²¹ , R ²² and R ²³ may each independently form a ring together with one of the adjacent benzene rings,
a represents an integer of 0 to 4,
b represents an integer of 1 to 5. )   Furthermore, the photocurable black composition of Claim 1 or 2 containing black pigments (D) other than titanium black.   The black matrix using the photocurable black composition as described in any one of Claims 1-3.   A color filter having a black matrix according to claim 4.