TWI484295B - Photosensitive resin composition, black matrix, color filter and liquid crystal display element - Google Patents

Description

Photosensitive resin composition, black matrix, color filter and liquid Crystal display element

The present invention relates to a photosensitive resin composition for forming a black matrix, and more particularly to a photosensitive resin composition comprising an alkali-soluble resin and a pigment component, wherein the pigment component comprises a black pigment and a blue pigment.

In order to improve the contrast and display quality of the current liquid crystal display, a black matrix is generally disposed in a stripe and a dot gap of the color filter. The function of the black matrix is to prevent loss of contrast due to light leakage between pixels and a decrease in color purity. Conventionally, a method of fabricating a black matrix is to form a vapor deposited film on a substrate by using a material containing chromium or chromium oxide. However, this method has disadvantages such as complicated process and high material cost. In order to solve the above disadvantages, a technique of forming a black matrix on a substrate by photolithographic printing of a photosensitive resin composition has been proposed.

At present, the industry's blackout requirements for black matrices are getting higher and higher. One of the solutions is to increase the content of black pigments, thereby improving the shading of the black matrix. Japanese Patent Laid-Open No. 2006-259716 discloses a photosensitive resin composition for a black matrix. The photosensitive resin composition contains high a content of a black pigment, an alkali-soluble resin, a photopolymerization initiator, a reactive monomer having a difunctional group, and an organic solvent, wherein the difunctional reactive monomer is a thiol-containing acrylate monomer . The photosensitive photosensitive resin composition of the Japanese Patent Application uses a high content of black pigment for high light-shielding property, and the thiol-containing acrylate monomer is used to increase the degree of crosslinking of the photosensitive resin composition upon exposure. Then, the sensitivity is increased to form a black matrix having a high-definition pattern.

Japanese Patent Laid-Open Publication No. 2008-268854 discloses a photosensitive resin composition for a black matrix. The photosensitive resin composition comprises an alkali-soluble resin having a carboxylic acid group and a polymerizable unsaturated group, a photopolymerizable monomer containing an ethylenically unsaturated group, a photoinitiator, and a high content of black pigment. . In the photosensitive resin composition of the Japanese Patent Application, a high-content black pigment is used for high light-shielding property, and an alkali-soluble resin having a specific carboxylic acid group and a polymerizable unsaturated group is used to enhance the photosensitive resin composition. The degree of crosslinking at the time of exposure, in turn, increases the sensitivity and allows the black matrix formed therefrom to maintain the desired resolution.

However, since the minimum line width required for the black matrix in the industry today is required to be 10 μm or less, the liquid crystal display element provides a higher resolution image quality, and the photosensitive resin for the black matrix disclosed in the above two patents. The black matrix formed by the composition has been unable to meet the industry's requirements for resolution.

In view of the above, the improvement of the photosensitive resin composition to provide a higher resolution for the black matrix, and in turn to provide a high-quality liquid crystal display element, is a subject that can be further broken by those skilled in the art.

Accordingly, a first object of the present invention is to provide a photosensitive resin composition. The photosensitive resin composition has high sensitivity and can form a black matrix having high light blocking property and high resolution.

Thus, the photosensitive resin composition of the present invention comprises: an alkali-soluble resin component (A) comprising a resin (A-1) having an unsaturated group, and the resin (A-1) having an unsaturated group is composed of one The mixture is obtained by polymerization, the mixture comprising an epoxy compound (i) having at least two epoxy groups, and a compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group; An ethylenically unsaturated group-containing compound (B); a photoinitiator (C); a pigment component (D); and a solvent (E); wherein the pigment component (D) comprises a black pigment (D-1) and The blue pigment (D-2), and the weight ratio of the amount of the black pigment (D-1) used to the amount of the blue pigment (D-2) used is in the range of 0.5 to 10.

A second object of the present invention is to provide a black matrix having high light blocking properties and high resolution.

Thus, the black matrix of the present invention is formed of the photosensitive resin composition described above.

A third object of the present invention is to provide a color filter.

Thus, the color filter of the present invention comprises the above-described black matrix .

A fourth object of the present invention is to provide a liquid crystal display element.

Thus, the liquid crystal display element of the present invention comprises the above-described color filter.

The effect of the present invention is to use the resin (A-1) having an unsaturated group, the black pigment (D-1) and the blue pigment (D-2), and the amount of the black pigment (D-1) used is The blue pigment (D-2) is used in a weight ratio ranging from 0.5 to 10, so that the photosensitive resin composition has high sensitivity, and the black matrix formed therefrom has high light-shielding property and high resolution, thereby further including The liquid crystal display element of the black matrix has good contrast and high image quality.

Herein, the (meth)acrylic acid means acrylic acid and/or methacrylic acid; the (meth)acrylate means acrylate. (acrylate) and/or methacrylate; the (meth)acryloyl group represents an acryloyl group and/or a methacryloyl group.

The photosensitive resin composition of the present invention comprises: an alkali-soluble resin component (A) comprising a resin (A-1) having an unsaturated group, and the resin (A-1) having an unsaturated group is a mixture of By polymerization, the mixture comprises an epoxy compound (i) having at least two epoxy groups, and a compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group; An unsaturated group-containing compound (B); a photoinitiator (C); a pigment component (D); and a solvent (E); wherein the pigment component (D) comprises a black pigment (D-1) and blue Pigment (D-2), and the weight ratio of the amount of the black pigment (D-1) used to the amount of the blue pigment (D-2) used is in the range of 0.5 to 10.

Preferably, the content of the unsaturated group-containing resin (A-1) is in the range of 50 to 100 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin component (A), and the ethylenically unsaturated The compound (B) is used in an amount ranging from 30 to 300 parts by weight, the pigment component (D) is used in an amount ranging from 100 to 1000 parts by weight, and the solvent (E) is used in an amount ranging from 1,000 to 5,000 parts by weight. .

Hereinafter, each component in the photosensitive resin composition of the present invention will be further described one by one:

<<Alkali soluble resin component (A)>>

[Resin (A-1) having an unsaturated group]

As described above, the unsaturated group-containing resin (A-1) is obtained by polymerization of the mixture, the mixture comprising the epoxy compound (i) having at least two epoxy groups, and the In addition to at least one carboxylic acid group and at least one ethylenically unsaturated group compound (ii), the mixture is also optional The monocarboxylic acid compound (iii) and/or an epoxy compound (iv) having one epoxy group is optionally contained. The epoxy compound (i) having at least two epoxy groups, the compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group, the carboxylic anhydride compound (iii), and having a ring will be described below. The epoxy compound (iv) of the oxy group is further described.

<Epoxy compound (i) having at least two epoxy groups>

Preferably, the epoxy compound (i) having at least two epoxy groups is an epoxy compound having at least two epoxy groups represented by the formula (I), and having the formula (II) At least two epoxy-based epoxy compounds, or a combination of these:

Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, halogen, C ₁ to C ₅ alkyl, C ₁ to C ₅ alkoxy, C ₆ to C ₁₂ aryl or C ₇ to C ₁₂ aralkyl group.

Wherein R ⁵ to R ¹⁸ each independently represent hydrogen, halogen, C ₁ to C ₈ alkyl or C ₆ to C ₁₅ aryl, and n represents an integer of 0 to 10.

Preferably, the epoxy compound (i) having at least two epoxy groups is an epoxy compound having at least two epoxy groups represented by the formula (I). This formula The epoxy compound having at least two epoxy groups shown in I) is as described above and will not be described again.

Preferably, the epoxy compound (i) having at least two epoxy groups is an epoxy compound having at least two epoxy groups represented by the formula (II). The epoxy compound having at least two epoxy groups represented by the formula (II) is as described above and will not be described again.

More specifically, the epoxy compound having at least two epoxy groups represented by the formula (I) is, for example but not limited to, a composition comprising a bisphenol fluorene and an epihalohydrin. An epoxy group-containing bisphenol quinone type compound obtained by polymerization of a reactant.

Wherein, the bisphenol quinoid compound can be used singly or in combination, such as, but not limited to, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9- Bis(4-hydroxy-3-methylphenyl)fluorene[9,9-bis(4-hydroxy-3-methylphenyl)fluorene], 9,9-bis(4-hydroxy-3-chlorophenyl)indole [ 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene], 9,9-bis(4-hydroxy-3-bromophenyl)fluorene [9,9-bis(4-hydroxy-3-bromophenyl)fluorene ,9,9-bis(4-hydroxy-3-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methyl) 9,9-bis(4-hydroxy-3-methoxyphenyl)fluorene, 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene [9,9- Bis(4-hydroxy-3,5-dimethylphenyl)fluorene], 9,9-bis(4-hydroxy-3,5-dichlorophenyl)indole [9,9-bis(4-hydroxy-3,5- Dichlorophenyl)fluorene], or 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene, etc.

The halogenated propylene oxide can be used singly or in combination, for example, but not Limited to: 3-chloro-1,2-epoxypropane (epichlorohydrin) or 3-bromo-1,2-epoxypropane (epibromohydrin).

The epoxy group-containing bisphenol quinone type compound can be used singly or in combination, for example, but not limited to: (1) a product manufactured by Nippon Steel Chemical Co., Ltd., for example, ESF-300, etc.; (2) a product manufactured by Osaka Gas For example, PG-100, EG-210, etc.; (3). Products manufactured by SMS Technology Co., for example: SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, and the like.

In more detail, the epoxy compound having at least two epoxy groups represented by the formula (II) may be, for example but not limited to, a compound represented by the formula (II-1), a halogenated propylene oxide, and an alkali metal. The second reactant of the hydroxide is reacted. More specifically, the reaction is carried out by dehydrohalogenation using an excess of halogenated propylene oxide and a compound represented by the formula (II-1) in the presence of an alkali metal hydroxide.

Wherein the compound represented by the formula (II-1):

Wherein R ⁵ to R ¹⁸ each independently represent hydrogen, halogen, C ₁ to C ₈ alkyl or C ₆ to C ₁₅ aryl, and n represents an integer of 0 to 10.

More specifically, the compound represented by the formula (II-1) is produced by a condensation reaction of a second reactant comprising a compound represented by the formula (II-2), a phenol compound, and an acid catalyst. Wherein the compound represented by the formula (II-2):

Wherein R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, a C ₁ to C ₈ alkyl group or a C ₆ to C ₁₅ aromatic group; and X ¹ and X ² each independently represent a halogen atom, C ₁ to A C ₆ alkyl group or a C ₁ to C ₆ alkoxy group. Preferably, the halogen atom is chlorine or bromine. The C ₁ to C ₈ alkyl group and the C ₁ to C ₆ alkyl group are a methyl group, an ethyl group or a tert-butyl group. The C ₁ to C ₆ alkoxy group is a methoxy group or an ethoxy group.

The phenolic compound can be used singly or in combination, such as but not limited to: phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t -t-butylphenol, octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol , vinylphenol, propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol or cyclohexylcresol.

The total amount of the compound represented by the formula (II-2) is 1 mol, and the phenol compound is used in an amount ranging from 0.5 mol to 20 mol. Preferably, the phenolic compound is used in an amount ranging from 2 moles to 15 moles.

The acid catalyst can be used singly or in combination, such as, but not limited to, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminum chloride ( Aluminiu m chloride anhydrous) or zinc chloride or the like. Preferably, the acid catalyst is selected from p-toluenesulfonic acid, sulfuric acid or hydrochloric acid. The amount of the acid catalyst used is not particularly limited. Preferably, the total amount of the compound represented by the formula (II-2) is 100 wt%, and the acid catalyst is used in an amount ranging from 0.1 to 30 wt%.

The condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. The organic solvent can be used singly or in combination, such as, but not limited to, toluene, xylene or methyl isobutyl ketone. The total amount of the compound and the phenol compound represented by the formula (II-2) is 100% by weight, and the organic solvent is used in an amount ranging from 50 to 300% by weight. Preferably, the organic solvent is used in an amount ranging from 100 to 250 wt%. Further, the condensation reaction has an operation temperature of 40 to 180 ° C and an operation time of 1 hour to 8 hours. After completion of the condensation reaction, the solution obtained after the reaction is subjected to a neutralization treatment or a water washing treatment, and then the unreacted phenol compound and the solvent are distilled off by heat treatment under reduced pressure, followed by concentration to obtain a formula ( The compound shown in II-1). Among them, the neutralization treatment is to adjust the pH range of the solution after the reaction to 3 to 7, preferably, the pH is in the range of 5 to 7. The water washing treatment is carried out using a neutralizing agent which is an alkaline substance such as, but not limited to, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; calcium hydroxide (calcium) Alkaline earth metal hydroxides such as hydroxide), magnesium hydroxide, etc.; diethylene triamine, triethylenetetramine, aniline, phenylene diamine, etc. Organic amine; and ammonia (ammonia), sodium dihydrogen phosphate (sodium Dihydrogen phosphate).

The halogenated propylene oxide is selected from the group consisting of 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane, or a combination thereof. Before the dehydrohalogenation reaction, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or during the reaction, and the operation temperature ranges from 20 to 120 ° C, and the operation time ranges from 1 hour to 10 hours. .

In a specific example of the photosensitive resin composition of the present invention, the alkali metal hydroxide used in the dehydrohalogenation reaction may be an aqueous solution thereof, and in this case, an alkali metal hydroxide aqueous solution is continuously added to the reactor. Meanwhile, at the same time, water and halogenated propylene oxide may be continuously distilled under reduced pressure or normal pressure, thereby removing water, and the halogenated propylene oxide obtained by distillation may be continuously refluxed into the reactor.

Tetramethyl ammonium chloride, tetramethyl ammonium bromide or trimethyl benzyl ammonium chloride may be added before the above dehydrohalogenation reaction. The quaternary ammonium salt is used as a catalyst, and reacted at 50 to 150 ° C for 1 hour to 5 hours, and then an alkali metal hydroxide or an aqueous solution thereof is added thereto, and the reaction is carried out at a temperature of 20 ° C to 120 ° C for 1 hour to 10 hours. Hours to carry out the dehydrohalogenation reaction.

The total equivalent weight of the hydroxyl group in the compound represented by the formula (II-1) is 1 equivalent, and the halogenated propylene oxide is used in an amount ranging from 1 to 20 equivalents. Preferably, the halogenated propylene oxide is used in an amount ranging from 2 to 10 equivalents. The total equivalent weight of the hydroxyl group in the compound represented by the formula (II-1) is 1 equivalent, and the alkali metal hydroxide is used in an amount ranging from 0.8 to 15 equivalents. Preferably, the alkali metal hydrogen The oxide is used in an amount ranging from 0.9 to 11 equivalents.

In addition, in order to smoothly carry out the dehydrohalogenation reaction, an aprotic such as dimethyl sulfone or dimethyl sulfoxide may be added in addition to an alcohol such as methanol or ethanol. A polar solvent or the like is used to carry out the reaction. In the case of using an alcohol, the alcohol is used in an amount ranging from 2 to 20% by weight based on the total amount of the halogenated propylene oxide of 100% by weight. Preferably, the alcohol is used in an amount ranging from 4 to 15 wt%. In the case of using an aprotic polar solvent, the aprotic polar solvent is used in an amount ranging from 5 to 100% by weight based on the total amount of the halogenated propylene oxide being 100 wt%. Preferably, the aprotic polar solvent is used in an amount ranging from 10 to 90 wt%.

After the dehydrohalogenation reaction is completed, the water washing treatment can be selectively performed. Thereafter, it is heated and decompressed, for example, at a temperature of 110 to 250. At a pressure of 1.3 kPa (10 mmHg) or less, the halogenated propylene oxide, an alcohol, and an aprotic polar solvent are removed.

In order to avoid the presence of unreacted starting materials such as halogenated propylene oxide to affect physical properties, the dehydrohalogenated reaction solution may be added to a solvent such as toluene or methyl isobutyl ketone, and sodium hydroxide is added. An aqueous alkali metal hydroxide solution such as potassium hydroxide is again subjected to a dehydrohalogenation reaction. In the dehydrohalogenation reaction, the total equivalent weight of the hydroxyl group in the compound represented by the formula (II-1) is 1 equivalent, and the alkali metal hydroxide is used in an amount ranging from 0.01 to 0.3 mol, preferably, The alkali metal hydroxide is used in an amount ranging from 0.05 to 0.2 mol. Further, the dehydrohalogenation reaction has an operating temperature in the range of 50 to 120 ° C and an operating time in the range of 0.5 to 2 hours.

After the dehydrohalogenation reaction is completed, the salts are removed by filtration, washing, and the like. The solvent such as toluene or methyl isobutyl ketone can be distilled off by heating and decompression to obtain an epoxy compound having at least two epoxy groups represented by the formula (II). Commercial products of the epoxy compound having at least two epoxy groups represented by the formula (II) are, for example but not limited to, NC-3000, NC-3000H, NC-3000S, and NC-3000P manufactured by Nippon Kasei Co., Ltd., and the like.

<Compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group>

The compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group may be used singly or in combination, for example but not limited to (1). Acrylic acid, methacrylic acid, 2-methylpropenyloxyethyl butyl 2-methacryloyloxyethylbutanedioic acid, 2-methylpropenyloxybutyl succinic acid, 2-methylpropenyloxyethyl adipate, 2-methylpropenyloxybutyl adipate, 2- Methacryloxyethyl hexahydrophthalic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxypropyl maleic acid, 2-methylpropenyloxybutylene Acid, 2-methylpropenyloxypropyl succinic acid, 2-methylpropenyloxypropyl adipate, 2-methylpropenyloxypropyltetrahydrophthalic acid, 2-methylpropene Phenoxypropyl phthalic acid, 2-methyl propylene oxybutyl phthalic acid, or 2-methyl propylene oxy butyl hydrogen phthalate; or (2) a compound obtained by reacting an acrylate with a dicarboxylic acid compound, wherein the dicarboxylic acid compound is, for example but not limited to, adipic acid, succinic acid, maleic acid or phthalic acid; or the like ). Group (meth) acrylate with a carboxylic acid anhydride compound (iii) obtained by reacting a half ester compound, wherein the hydroxyl group-containing (meth) acrylates such as, but not limited to: 2-hydroxyethyl acrylate [(2-hydroxyethyl)acrylate], 2-hydroxyethylmethacrylate [2-hydroxyethyl) methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropylmethyl Acrylate [(2-hydroxypropyl)methacrylate], 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, or pentaerythritol trimethacrylate Wait.

Here, the carboxylic anhydride compound (iii) is selected from a dicarboxylic acid anhydride compound, a tetracarboxylic acid anhydride compound, or a combination thereof. The dicarboxylic anhydride compound may be used singly or in combination, such as but not limited to butanedioic anhydride, maleic anhydride, Itaconic anhydride, phthalic anhydride. ), tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl bridge Methyl endo-methylene tetrahydro phthalic anhydride, chlorendic anhydride or glutaric anhydride or 1,3-dioxoisobenzofuran-5-carboxylic anhydride. The tetracarboxylic carboxylic anhydride compound may be used singly or in combination, for example, but not limited to, benzophenone tetracarboxylic dianhydride (BTDA), diphenyltetracarboxylic dianhydride or diphenyl ether tetracarboxylic dianhydride.

<Carboxylic anhydride compound (iii)>

The carboxylic anhydride-based compound (iii) is as described above and will not be described again.

<Epoxy compound (iv) having one epoxy group>

The epoxy compound (iv) having one epoxy group is selected from the group consisting of glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, an unsaturated group-containing glycidyl ether compound, and An epoxy group of unsaturated compounds, or a combination thereof. Commercially available products of the unsaturated group-containing glycidyl ether compound are, for example but not limited to, Denaco 1 EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, and Denacol EX- manufactured by Nagase Chemical Industry Co., Ltd. 146, Denacol EX-171, Denacol EX-192, and the like.

The unsaturated group-containing resin (A-1) may be an epoxy compound having at least two epoxy groups represented by the formula (I) and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (ii) The polymerization reaction is carried out (the operating temperature ranges from 50 ° C to 130 ° C) to form a hydroxyl group-containing reaction product, followed by addition of a carboxylic anhydride compound (iii) to carry out a reaction. Preferably, the total hydroxyl group equivalent of the hydroxyl group-containing reaction product is 1 equivalent, and the acid anhydride group in the carboxylic anhydride compound (iii) has an equivalent weight ranging from 0.4 to 1 equivalent. More preferably, the acid anhydride group in the carboxylic anhydride-based compound (iii) has an equivalent weight ranging from 0.75 to 1 equivalent. When one or more of the carboxylic anhydride-based compound (iii) is used, it may be added sequentially or simultaneously in the reaction. Preferably, when the carboxylic anhydride compound (iii) is a dicarboxylic anhydride compound and a tetracarboxylic anhydride compound, the molar ratio of the dicarboxylic anhydride compound and the tetracarboxylic anhydride compound ranges from 1/99 to 90/ 10. More preferably, the molar ratio of the dicarboxylic anhydride compound and the tetracarboxylic anhydride compound ranges from 5/95 to 80/20.

The unsaturated group-containing resin (A-1) can be represented by the formula (II) An epoxy compound having at least two epoxy groups is reacted with a compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group to form a hydroxyl group-containing reaction product, followed by addition of a carboxylic anhydride compound (iii) and/or an epoxy compound (iv) having an epoxy group is obtained by carrying out a polymerization reaction. Preferably, the epoxy group having at least two epoxy groups represented by the formula (II) has a total epoxy equivalent of 1 equivalent, and the compound having at least one carboxylic acid group and at least one ethylenically unsaturated group The acid value equivalent of (ii) is from 0.8 to 1.5 equivalents. More preferably, it is from 0.9 to 1.1 equivalents. The total amount of hydroxyl groups based on the hydroxyl group-containing reaction product is 100 mol%, and the carboxylic anhydride compound (iii) is used in an amount ranging from 10 to 100 mol%, preferably 20 to 100 mol%, more preferably Good place, 30 to 100 mol%.

In the preparation of the unsaturated group-containing resin (A-1), in order to accelerate the reaction, a basic compound is usually added as a reaction catalyst to the reaction solution. The reaction catalyst can be used singly or in combination, such as but not limited to: triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine, tetramethyl chloride. Tetramethylammonium chloride or benzyltriethylammonium chloride. Preferably, the reaction is based on the total amount of the epoxy compound (i) having at least two epoxy groups and the compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group in an amount of 100 parts by weight. The catalyst is used in an amount ranging from 0.01 to 10 parts by weight, more preferably from 0.3 to 5 parts by weight.

Further, in order to control the degree of polymerization, a polymerization inhibitor is usually added to the reaction solution. The polymerization inhibitor can be used singly or in combination, for example, but not limited to In: methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-cresol (2,6-di-t-butyl-p-cresol ), or phenothiazine (phenothiazine) and the like. The use of the polymerization inhibitor based on the total amount of the epoxy compound (i) having at least two epoxy groups and the compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group in an amount of 100 parts by weight The amount ranges from 0.01 to 10 parts by weight, preferably from 0.1 to 5 parts by weight.

In the preparation of the unsaturated group-containing resin (A-1), a polymerization solvent can be used as necessary. The polymerization solvent can be used singly or in combination, such as, but not limited to, an alcohol compound such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol or ethylene glycol; methyl ethyl ketone or ring a ketone compound such as ketone; an aromatic hydrocarbon compound such as toluene or xylene; a cellosolve compound such as celecin or butyl cellosolve; carbitol or butyl Carbitol-like compounds such as butyl carbito; propylene glycol alkyl ether compounds such as propylene glycol monomethyl ether; and polypropylene glycol alkyl ethers such as dipropylene glycol monoether [di(propylene glycol) methyl ether] Poly(propylene glycol) alkyl ether] compound; acetate compound such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate or propylene glycol methyl ether acetate An alkyl lactate compound such as ethyl lactate or butyl lactate; or a dialkyl glycol ether. Further, the unsaturated group-containing resin (A-1) has an acid value in the range of 50 mgKOH/g to 200 mgKOH/g, preferably 60 mgKOH/g to 150 mgKOH/ g.

Since the unsaturated group-containing resin (A-1) has excellent heat resistance and can contain a crosslinking bond, the crosslinking reaction can be carried out to enhance the sensitivity of the photosensitive resin composition, and the black matrix formed therefrom Since the photosensitive resin composition does not use the resin (A-1) having an unsaturated group, the sensitivity of the photosensitive composition is poor, and the black matrix formed therefrom has a good The disadvantage of poor resolution. Preferably, the content of the unsaturated group-containing resin (A-1) is in the range of 50 to 100 parts by weight, preferably 60, based on 100 parts by weight of the total of the alkali-soluble resin (A) component. To 100 parts by weight, more preferably, 70 to 100 parts by weight.

[Other alkali soluble resin (A-2)]

The alkali-soluble resin component (A) also includes other alkali-soluble resins (A-2). The other alkali-soluble resin (A-2) is, for example but not limited to, a resin containing a carboxylic acid group or a hydroxyl group, and specific examples thereof include an acrylic resin other than the resin (A-1) having an unsaturated group, and urethane. A resin or a novolac type resin.

The content of the other alkali-soluble resin (A-2) is from 0 to 50 parts by weight, preferably from 0 to 40 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin component (A). Preferably, it is from 0 to 30 parts by weight.

<<Ethylene-unsaturated group-containing compound (B)>>

The ethylenically unsaturated group-containing compound (B) is used in an amount ranging from 30 parts by weight to 300 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin component (A). When the ethylenically unsaturated group-containing compound (B) When the amount of use of the photosensitive resin composition is less than 30 parts by weight, the degree of crosslinking of the photosensitive resin composition is insufficient to form a black matrix of a predetermined pattern; when the amount of the ethylenically unsaturated group-containing compound (B) is more than 300 parts by weight The sensitivity of the photosensitive composition is too high, so that the residue is easily generated after the development of the unilluminated portion. Preferably, the ethylenically unsaturated group-containing compound (B) is used in an amount ranging from 40 parts by weight to 280 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin component (A). More preferably, the ethylenically unsaturated group-containing compound (B) is used in an amount ranging from 50 parts by weight to 260 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin component (A).

The ethylenically unsaturated group-containing compound (B) is a compound (B-1) having one ethylenically unsaturated group and having two or more (including two) ethylenically unsaturated groups (B- 2), or a combination of these.

The compound (B-1) having one ethylenically unsaturated group can be used singly or in combination, such as, but not limited to, (meth)acrylamide, (meth)acryloquinone morpholine, Methyl)acrylic acid-7-amino-3,7-dimethyloctyl ester, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth)acrylate, (methyl) Isobornyl acrylate, 2-ethylhexyl (meth) acrylate, ethyl diethylene glycol (meth) acrylate, trioctyl (meth) acrylamide, diacetone (methyl) propylene Indoleamine, dimethylaminoethyl (meth)acrylate, dodecyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentene (meth)acrylate Ester, nitrogen, nitrogen-dimethyl(meth)acrylamide, tetrachlorophenyl (meth)acrylate, 2-tetrachlorophenoxyethyl (meth)acrylate, tetrahydro(meth)acrylate Tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl (meth)acrylate,-2-tetrabromo(meth)acrylate Phenoxyethyl ester, 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl (meth)acrylate, 2-tribromophenoxyethyl (meth)acrylate, 2- Ethyl hydroxy-(meth)acrylate, propyl 2-hydroxy-(meth)acrylate, vinyl caprolactam, nitrogen-vinylpyrrolidone, phenoxyethyl (meth)acrylate, (methyl) Pentachlorophenyl acrylate, pentabromophenyl (meth) acrylate, polyethylene mono(meth) acrylate, poly (mono) (meth) acrylate or methacrylate (meth) acrylate.

The compound (B-2) having two or more (including two) ethylenically unsaturated groups can be used singly or in combination, such as, but not limited to, ethylene glycol di(meth)acrylate, di(meth)acrylic acid. Dicyclopentenyl ester, triethylene glycol di(meth) acrylate, tetraethylene glycol di(meth) acrylate, tris(2-hydroxyethyl)isocyanate di(meth) acrylate, three (2-hydroxyethyl) isocyanate tri(meth)acrylate, caprolactone modified tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, tris(meth)acrylic acid Trimethylolpropyl propyl ester, trimethylolpropyl tris(meth)acrylate modified with ethylene oxide (EO), tris(meth)acrylic acid modified by propylene oxide (PO) Hydroxymethyl propyl ester, tripropylene glycol di(meth) acrylate, neopentyl glycol di(meth) acrylate, 1,4-butanediol di(meth) acrylate, 1,6-hexanediol Di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol Hexa(meth) acrylate, dipentaerythritol (Meth) acrylate, dipentaerythritol tetra(meth) acrylate, dipentaerythritol hexa(meth) acrylate modified with caprolactone, dipentaerythritol penta (meth) acrylate modified by caprolactone , bis(trimethylolpropyl) tetrakis(meth)acrylate [di(trimethylolp) Ropene)tetra(meth)acrylate], ethylene oxide modified bisphenol A di(meth)acrylate, propylene oxide modified bisphenol A di(meth)acrylate, epoxy Alkyne-modified hydrogenated bisphenol A di(meth)acrylate, propylene oxide modified hydrogenated bisphenol A di(meth)acrylate, propylene oxide modified tris(meth)acrylate Ethylene oxide modified bisphenol F di(meth) acrylate or novolak polyglycidyl ether (meth) acrylate.

The ethylenically unsaturated group-containing compound (B) is selected from trimethylolpropyl acrylate, trimethylolpropyl triacrylate modified with ethylene oxide, and modified with propylene oxide. Trimethylolpropyl acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate, four Ditrimethylolpropyl acrylate, propylene oxide modified glycerol triacrylate, or a combination thereof.

<<Light initiator (C)>>

The photoinitiator (C) can be used singly or in combination, such as, but not limited to, an O-indenyl lanthanide compound (C-1), a triazabenzene compound, an acetophenone compound, and a diimidazole system. A compound, a benzophenone-based compound, an α-diketone-based compound, a keto alcohol-based compound, a ketol ether-based compound, a phosphonium oxynitride-based compound, an anthraquinone-based compound, a halogen-containing compound, a peroxide, and the like.

The O-indenyl lanthanide compound (C-1) can be used singly or in combination, such as, but not limited to, 1-[4-(phenylthio)phenyl]-heptane-1,2-dione 2- (O- Phenylhydrazinium), 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-phenylhydrazinium) (for example, OXE 01 manufactured by Ciba Specialty Chemicals) , 1-[4-(phenylhydrazino)phenyl]-heptane-1,2-dione 2-(O-phenylhydrazinyl), 1-[9-ethyl-6-(2-methyl Benzoyl)-9H-indazole-3-substituted]-ethanone 1-(O-ethenylhydrazine) (for example, OXE 02 manufactured by Ciba Specialty Chemicals), 1-[9-ethyl-6- (3-Methylphenylhydrazino)-9H-indazole-3-substituted]-ethanone 1-(O-acetamidoxime), 1-[9-ethyl-6-benzoinyl-9H -carbazole-3-substituted]-ethanone 1-(O-acetamidoxime), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylphenylhydrazine) ))-9H-carbazole-3-substituted]-1-(O-acetylindenyl), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyridyl) Benzyl phenyl hydrazino)-9H-carbazole-3-substituted]-1-(O-ethyl fluorenyl), ethane ketone-1-[9-ethyl-6-(2-methyl-5 -tetrahydrofuranylbenzoyl)-9H-carbazole-3-substituted]-1-(O-ethylindenyl), ethane ketone-1-[9-ethyl-6-(2-methyl- 5-tetrahydropyranylphenylhydrazinyl)-9H-indazole-3-substituted]-1-(O-ethylindenyl), ethane ketone-1-[9-ethyl-6-(2 -methyl-4-tetrahydrofuranylmethoxyphenyl)]-9H-indazole-3-substituent]- 1-(O-ethylindenyl), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzoinyl)-9H-carbazole -3-Substituent]-1-(O-acetamidofluorene), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylmethoxyphenyl)- 9H-carbazole-3-substituted]-1-(O-acetylindenyl), ethane ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranyl) Oxyphenyl fluorenyl)-9H-carbazole-3-substituted]-1-(O-acetylindenyl), ethane ketone-1-[9-ethyl-6-{2-methyl-4 -(2,2-dimethyl-1,3-dioxolanyl)phenylhydrazinyl}-9H-indazole-3-substituted]-1-(O-ethylindenyl), or B Alkanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoquinone}-9H - carbazole-3-substituted]-1-(O-ethylindenyl) and the like.

Preferably, the O-fluorenyl lanthanide compound (C-1) is selected from 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O- Benzoyl hydrazine) [OXE 01, manufactured by Ciba Specialty Chemicals], 1-[9-ethyl-6-(2-methylphenylhydrazino)-9H-indazole-3-substituted]-ethanone 1 -(O-acetylhydrazine) [OXE 02, manufactured by Ciba Specialty Chemicals], ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranmethoxyphenyl)- 9H-carbazole-3-substituted]-1-(O-acetylindenyl) or ketone-1-[9-ethyl-6-{2-methyl-4-(2,2- Dimethyl-1,3-dioxolanyl)methoxyphenylhydrazinyl}-9H-indazole-3-substituted]-1-(O-ethenylhydrazine).

The triazabenzene compound can be used singly or in combination, such as but not limited to: vinyl-halomethyl-s-triazabenzene compound, 2-(naphtho-1-substituted)-4,6- A bis-halogenomethyl-s-triazabenzene compound, or a 4-(p-aminophenyl)-2,6-di-halomethyl-s-triazabenzene compound or the like.

The vinyl-halomethyl-s-triazabenzene compound can be used singly or in combination, such as but not limited to: 2,4-bis(trichloromethyl)-6-p-methoxystyryl- S-triazabenzene, 2,4-bis(trichloromethyl)-3-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazabenzene Or 2-trichloromethyl-3-amino-6-p-methoxystyryl-s-triazabenzene and the like.

The 2-(naphtho-1-substituted)-4,6-bis-halomethyl-s-triazabenzene compound can be used singly or in combination, for example but not limited to: 2-(naphtho-1- Substituent)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(4-methoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl -s-triazabenzene, 2-(4-ethoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(4-butyl Oxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-[4-(2-methoxy B -naphthyl-1-substituted]-4,6-bis-trichloromethyl-s-triazabenzene, 2-[4-(2-ethoxyethyl)-naphtho-1- Substituent]-4,6-bis-trichloromethyl-s-triazabenzene, 2-[4-(2-butoxyethyl)-naphthyl-1-substituted]-4,6- Bis-trichloromethyl-s-triazabenzene, 2-(2-methoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(6-methoxy-5-methyl-naphtho-2-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(6-methoxy- Naphtho-2-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, 2-(5-methoxy-naphtho-1-substituted)-4,6-double -trichloromethyl-s-triazabenzene, 2-(4,7-dimethoxy-naphtho-1-substituted)-4,6-bis-trichloromethyl-s-triaza Benzene, 2-(6-ethoxy-naphtho-2-substituted)-4,6-bis-trichloromethyl-s-triazabenzene, or 2-(4,5-dimethoxy -naphthyl-1-substituted)-4,6-bis-trichloromethyl-s-triazabenzene and the like.

The 4-(p-aminophenyl)-2,6-di-halomethyl-s-triazabenzene compound can be used singly or in combination, for example but not limited to: 4-[p-N,N- Di(ethoxycarbonylmethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-di ( Ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[p-N,N-bis(chloroethyl)aminobenzene -2,6-bis(trichloromethyl)-s-triazabenzene, 4-[o-methyl-p-N,N-di(chloroethyl)aminophenyl]-2, 6-bis(trichloromethyl)-s-triazabenzene, 4-(p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s-triaza Benzene, 4-(p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4-[p-N,N-di (phenyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(p-N-chloroethylcarbonylaminophenyl)-2,6- Bis(trichloromethyl)-s-triazabenzene, 4-[p-N-(p-methoxyphenyl)carbonylaminophenyl]-2,6-di(trichloromethyl)- S-triazabenzene, 4-[m-N,N-bis(ethoxycarbonylmethyl)aminobenzene -2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-bromo-p-N,N-di(ethoxycarbonylmethyl)aminophenyl]- 2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6 - bis(trichloromethyl)-s-triazabenzene, 4-[m-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di ( Trichloromethyl)-s-triazabenzene, 4-[o-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethane) -s-triazabenzene, 4-[o-chloro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl-2,6-di(trichloromethyl)-s -Triazabenzene, 4-[o-fluoro-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazo Benzene, 4-[o-bromo-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[ o-chloro-p-N,N-bis(chloroethyl)aminophenyl]-2,6-di(trichloromethyl)-s-triazabenzene, 4-[o-fluoro-p- N,N-bis(chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-bromo-p-N,N-di ( Chloroethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-chloro-p-N,N-di ( Ethyl)aminophenyl]-2,6-bis(trichloromethyl)-s-triazabenzene, 4-[m-fluoro-p-N,N-bis(chloroethyl)aminobenzene 2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di (trichloromethyl)-s-triazabenzene, 4-(m-chloro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s -Triazabenzene, 4-(m-fluoro-p-N-ethoxycarbonylmethylaminophenyl)-2,6-di(trichloromethyl)-s-triazabenzene, 4- (o-bromo-p-N-ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-chloro-p-N -ethoxycarbonylmethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-fluoro-p-N-ethoxycarbonylmethylamine Phenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-bromo-p-N- Chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(m-chloro-p-N-chloroethylaminophenyl)-2, 6-bis(trichloromethyl)-s-triazabenzene, 4-(m-fluoro-p-N-chloroethylaminophenyl)-2,6-di(trichloromethyl)-s -Triazabenzene, 4-(o-bromo-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o- Chloro-p-N-chloroethylaminophenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, 4-(o-fluoro-p-N-chloroethylamino group Phenyl)-2,6-bis(trichloromethyl)-s-triazabenzene, or 2,4-bis(trichloromethyl)-6-[3-bromo-4-[N,N- Bis(ethoxycarbonylmethyl)amino]phenyl]-1,3,5-triazabenzene and the like.

Preferably, the triazabenzene compound is selected from 4-[m-bromo-p-N,N-bis(ethoxycarbonylmethyl)aminophenyl]-2,6-di(III) Chloromethyl)-s-triazabenzene or 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene.

The acetophenone-based compound can be used singly or in combination, such as, but not limited to, p-dimethylacetone, α,α'-dimethoxyoxyazopropenone, 2,2'-di Methyl-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, Or 2-benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone or the like. Preferably, the ethyl acetophenone compound is selected from 2-methyl-1-[4-(methylthio)phenyl]-2-morpholine-1-propanone, or 2-benzyl -2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone.

The diimidazole compound can be used singly or in combination, such as but not limited to: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2' - bis(o-fluorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5' -tetraphenyldiimidazole, 2,2'-double (o-a- Oxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-ethylphenyl)-4,4',5,5'-tetraphenyl Diimidazole, 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis (2,2',4,4 '-Tetramethoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'- Tetraphenyldiimidazole, or 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, and the like. Preferably, the diimidazole compound is 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole.

The benzophenone compound can be used singly or in combination, such as, but not limited to, thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-oxime, benzophenone, 4,4' - bis(dimethylamine)benzophenone or 4,4'-bis(diethylamine)benzophenone. Preferably, the benzophenone compound is 4,4'-bis(diethylamine)benzophenone.

The α-diketone compound is, for example but not limited to, benzoin or ethenyl. The ketol-based compound is, for example but not limited to, benzophenone. The ketol ether-based compound is, for example but not limited to, benzophenone methyl ether, benzophenone ethyl ether or benzophenone isopropyl ether. The phosphonium phosphide-based compound is, for example but not limited to, 2,4,6-trimethylphenylhydrazine diphenylphosphine oxide or bis-(2,6-dimethoxybenzoquinone)-2,4,4 - Trimethylphenylphosphine oxide or the like. The oxime compound is, for example but not limited to, hydrazine, 1,4-naphthoquinone or the like. The halogen-containing compound is, for example but not limited to, benzoquinone methyl chloride, tribromomethylphenylhydrazine or tris(trichloromethyl)-s-triazabenzene. The peroxide is, for example but not limited to, di-tert-butyl peroxide or the like. The α-diketone compound, the keto alcohol compound, the ketone ether compound, the phosphonium oxide compound, the oxime compound, the halogen-containing compound, the peroxide, or the like can be used singly or in combination.

The amount of the photoinitiator (C) to be used may be adjusted as needed. Preferably, the total amount of the ethylenically unsaturated group-containing compound (B) is 100 parts by weight based on the total amount of the photoinitiator (C). The amount used is in the range of 10 to 60 parts by weight. More preferably, the photoinitiator (C) is used in an amount ranging from 15 to 55 parts by weight based on 100 parts by weight of the total of the ethylenically unsaturated group-containing compound (B). Still more preferably, the photoinitiator (C) is used in an amount ranging from 20 to 50 parts by weight based on 100 parts by weight of the total of the ethylenically unsaturated group-containing compound (B).

<<Pigment component (D)>>

The pigment component (D) is used in an amount ranging from 100 to 1000 parts by weight. When the amount of the pigment component (D) used is less than 100 parts by weight, the black matrix formed of the photosensitive resin composition has poor light-shielding properties. When the amount of the pigment component (D) used is more than 1000 parts by weight, the viscosity of the photosensitive resin composition is too high, so that it is not easily spread evenly when applied to the substrate, which is unfavorable. A film is formed on the substrate or the thickness of the formed film is not uniform.

Preferably, the black pigment (D-1) is used in an amount ranging from 50 to 600 parts by weight, preferably from 75 to 500 parts by weight, based on 100 parts by weight of the total of the alkali-soluble resin component (A). More preferably, it is 100 to 400 parts by weight; the blue pigment (D-2) is used in an amount of from 50 to 400 parts by weight, preferably from 60 to 350 parts by weight, more preferably from 70 to 300 parts by weight. If the black pigment (D-1) is not used at all, the black matrix formed of the photosensitive resin composition has poor light-shielding property; if the blue pigment (D-2) is not used at all, the photosensitive resin composition The sensitivity of the object is not good, and the resolution of the formed black matrix is also poor.

The pigment component (D) in the photosensitive resin composition is formed by using the blue pigment (D-2) to expose light energy having a wavelength range of 325 to 380 nm to a photosensitive resin in contact with the substrate. Therefore, the degree of crosslinking reaction of the photosensitive resin composition at the place is increased, and the sensitivity of the overall photosensitive resin composition is improved, so that a line width of less than 4 μm can be left on the substrate after development, and the black color is increased. The resolution of the matrix.

When the weight ratio of the amount of the black pigment (D-1) to the amount of the blue pigment (D-2) used is less than 0.5, the black matrix formed of the photosensitive resin composition has poor light-shielding properties. When the weight ratio of the amount of the black pigment (D-1) to the amount of the blue pigment (D-2) used is more than 10, the photosensitive resin composition has poor sensitivity and is formed of the photosensitive resin composition. The resolution of the black matrix is not good. The black pigment (D-1) and the blue pigment (D-2) will be described in more detail below:

[black pigment (D-1)]

The black pigment (D-1) is preferably one having heat resistance, light resistance, and solvent resistance.

The black pigment (D-1) can be used singly or in combination, for example but not limited to: (1). A black organic pigment such as perylene black, cyanine black or aniline black ( Aniline black), etc.; (2). From red, blue, green, purple, yellow, cyanine or magenta, two or more pigments are selected for mixing to make near black (3). A light-shielding material such as carbon black, chromium oxide, iron oxide, titanium black or graphite, etc., wherein the carbon black is, for example but not limited to, CI pigment black 7 and so on, the specific example is three MA100, MA230, MA8, #970, #1000, #2350 and #2650 made by Ling Chemical.

[Blue pigment (D-2)]

The blue pigment (D-2) is preferably selected so as not to absorb a light source having a wavelength range of 380 nm or less. The blue pigment can be used singly or in combination, such as, but not limited to, a blue pigment having a copper phthalocyanine structure or an indanthrone blue blue pigment. The blue pigment having a copper phthalocyanine structure is, for example but not limited to, CI Pigment Blue 15:1 (CIPB 15:1), CI Pigment Blue 15:2 (CIPB 15:2), CI Pigment Blue 15:3 (CIPB15 : 3), CI Pigment Blue 15:4 (CIPB 15:4), CI Pigment Blue 15:5 (CIPB 15:5), or CI Pigment Blue 15:6 (CIPB 15:6).

The pigment component also includes a violet pigment and/or a red pigment.

The purple pigment is preferably selected so as not to absorb a light source having a wavelength range of 380 nm or less. The purple pigment can be used singly or in combination, such as, but not limited to, CI Pigment Violet 14 (CIPV14), CI Pigment Violet 19 (CIPV19), CI Pigment Violet 23 (CIPV23), CI Pigment Violet 29 (CIPV29), CI pigment violet 32 (CIPV32), CI pigment violet 33 (CIPV33), CI pigment violet 36 (CIPV36), CI pigment violet 37 (CIPV37), CI pigment violet 38 (CIPV38), CI pigment violet 40 ( CIPV40), or CI Pigment Violet 50 (CIPV50), etc.

The red pigment is selected from a red pigment having an azo condensation structure, a red pigment having an onion structure, a quinacridone red pigment, an anthraquinone red pigment, and a pyridin-8,16-diketone red pigment. Or a combination of these. Wherein, the red pigment having an azo condensation structure can be used alone or in combination For example, but not limited to: C.I. Pigment red 83, C.I. Pigment red 89, or C.I. Pigment red 177 (C.I. Pigment red 177). Preferably, the red pigment having an azo condensation structure is selected from C.I. Pigment Red 89, C.I. Pigment Red 177, or a combination thereof. The red pigment having an onion structure can be used singly or in combination, such as, but not limited to, CI Pigment Red 144, CIPigment red 166, CIPigment red 214, CI Pigment Red 220, CIPigment red 221, CI Pigment Red 242, CIPigment red 248, CI Pigment Red 262, or CI Pigment Red 262 Pigment red 262) and so on. Preferably, the red pigment having a green onion structure is selected from C.I. Pigment Red 166, C.I. Pigment Red 242, or a combination thereof.

<<Solvent (E)>>

The solvent (E) is capable of dissolving the alkali-soluble resin component (A), the ethylenically unsaturated group-containing compound (B), the photoinitiator (C), and the pigment component (D), and is not related to the above components. It is preferred that the reaction takes place with appropriate volatility.

The solvent (E) can be used singly or in combination, for example, but not limited to, an alkyl glycol monoalkyl ether compound, an alkyl glycol monoalkyl ether acetate compound, other ether compounds, a ketone compound, or a lactate. An ester compound, another ester compound, an aromatic hydrocarbon compound, or a carboxylic acid amine compound.

The alkyl glycol monoalkyl ether compound can be used singly or in combination, such as, but not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol Alcohol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, or tripropylene glycol monomethyl ether or tripropylene glycol monoethyl ether.

The alkyl glycol monoalkyl ether acetate compound can be used singly or in combination, such as, but not limited to, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate or propylene glycol methyl ether acetate, or propylene glycol diethyl ether acetate. .

The other ether compounds may be used singly or in combination, such as, but not limited to, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether or tetrahydrofuran.

The ketone compound can be used singly or in combination, such as, but not limited to, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone or diacetone alcohol.

The lactate alkyl ester compound can be used singly or in combination, and is, for example, but not limited to, methyl lactate or ethyl lactate.

The other ester compounds can be used singly or in combination, such as, but not limited to, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3 -methyl methyl butyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, acetic acid Propyl ester, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyrate Ester, methyl pyruvate, ethyl pyruvate, pyruvic acid Propyl ester, ethyl acetate methyl acetate, ethyl acetate ethyl acetate or ethyl 2-oxybutyrate.

The aromatic hydrocarbon compound can be used singly or in combination, and is not limited to, for example, toluene or xylene.

The carboxylic acid amine compound can be used singly or in combination, such as, but not limited to, N-methylpyrrolidone, N,N-dimethylformamide or N,N-dimethylacetamide.

Preferably, the solvent (E) is used in an amount ranging from 1,000 parts by weight to 5000 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A). More preferably, the solvent (E) is used in an amount ranging from 1200 parts by weight to 4800 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A). Still more preferably, the solvent (E) is used in an amount ranging from 1,500 parts by weight to 4,500 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A).

<<Additives (F)>>

The photosensitive resin composition of the present invention further contains an additive (F), such as, but not limited to, a surfactant, a filler, a adhesion promoter, a bridging agent, an antioxidant, an anti-agglomerating agent, without affecting the efficacy of the present invention. Or a polymer other than the alkali-soluble resin component (A) and capable of adding various properties such as mechanical properties.

The surfactant is selected from a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, a polyoxyalkylene surfactant, a fluorosurfactant, or the like. Wait for a combination. More specifically, the surfactant is, for example but not limited to, polyethoxylated alkyl ethers, polyethoxylated alkylphenyl ethers, polyethylene glycol diesters Classes, sorbitan fatty acid esters, fatty acid modified polyesters, or tertiary amine modified polyurethanes. Among them, the polyethoxylated alkyl ethers are, for example but not limited to, polyethoxydodecyl ether or polyethoxylated decyl ether or polyethoxy oleyl ether. The polyethoxyalkylphenyl ethers are, for example but not limited to, polyethoxyoctylphenyl ether or polyethoxylated nonylphenyl ether. The polyethylene glycol diesters are, for example but not limited to, polyethylene glycol dilaurate or polyethylene glycol distearate. The above surfactants can be used singly or in combination.

A commercially available product of the surfactant used is, for example, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), SF-8427 (manufactured by Toray Dow Corning Silicon Co., Ltd.), Polyflow (manufactured by Kyoei Oil & Fats Chemical Industry Co., Ltd.), and F-Top (Tochem Product Co., Ltd.), Megafac (manufactured by Dainippon INK Chemical Industry Co., Ltd.), Fluorade (manufactured by Sumitomo 3M), Asahi Guard, Surflon (made by Asahi Glass Co., Ltd.), or SINOPOL E8008 (manufactured by Sino-Japanese Synthetic Chemical Co., Ltd.).

The filler can be used singly or in combination, such as but not limited to glass or aluminum.

The adhesion promoter can be used singly or in combination, such as but not limited to vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(2-methoxyethoxy) decane, N-(2- Aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxy Baseline, 3-glycidylpropyltrimethoxydecane, 3-glycidylpropylmethyldiethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane , 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane or 3-mercaptopropyl Trimethoxy decane and the like.

The antioxidant can be used singly or in combination, such as, but not limited to, 2,2-thiobis(4-methyl-6-tert-butylphenol) or 2,6-di-t-butylphenol.

The anti-agglomerating agent is for example but not limited to sodium polyacrylate.

The bridging agent is, for example, but not limited to, an epoxy compound such as 1031S or 157S-70 manufactured by Nippon Epoxy Co., Ltd., or a resin.

The total amount of the alkali-soluble resin component (A) is 100 parts by weight, and any of the additives other than the filler, the adhesion promoter, the antioxidant, the anti-aggregation agent, or the alkali-soluble resin (A) The amount used is in the range of 0 parts by weight to 10 parts by weight, preferably, the amount used is in the range of 0 parts by weight to 6 parts by weight.

The surfactant is used in an amount ranging from 0 parts by weight to 6 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin component (A). Preferably, the surfactant is used in an amount of 0 weight. Parts to 4 parts by weight.

The bridging agent is used in an amount ranging from 0 parts by weight to 100 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin component (A). Preferably, the bridging agent is used in an amount ranging from 0 parts by weight to 80 parts by weight.

The method for producing the photosensitive resin composition of the present invention is not particularly limited, and for example, the alkali-soluble resin component (A), the ethylenically unsaturated group-containing compound (B), the photoinitiator (C), and the pigment group can be used. The fraction (D) and the solvent (E) are placed in a stirrer and stirred uniformly to form a solution state, and if necessary, an additive (F) may be added and uniformly mixed. Alternatively, for example, the base can be dissolved first. The resin component (A), the ethylenically unsaturated group-containing compound (B), the photoinitiator (C) and the solvent (E) are placed in a stirrer and uniformly mixed to form a solution, and the pigment group is further formed. Part (D) is directly added to the solution to be dispersed, whereby the photosensitive resin composition of the present invention is obtained. Or a part of the pigment component (D) is dispersed in a part of the alkali-soluble resin component (A) and a part of the solvent (E) to form a pigment dispersion, and then the ethylenically unsaturated group is mixed. The photosensitive resin composition of the present invention is obtained by using the compound (B), the photoinitiator (C), and the remaining alkali-soluble resin component (A) and the solvent (E).

The black matrix of the present invention is formed of the above-described photosensitive resin composition.

When the black matrix film thickness of the present invention is 1 μm, the optical density (O.D. value) is 3.5 or more; preferably, when the black matrix film thickness is 1 μm, the optical density ranges from 3.8 to 5.5.

The black matrix can be obtained by the following sequential treatment: (1) The photosensitive resin composition of the present invention is applied onto a substrate by a coating method such as spin coating or cast coating, and dried under reduced pressure (pressure: The solvent (E) in the photosensitive resin composition is removed by less than 200 mmHg, treatment time: 1 second to 20 seconds, and pre-baking treatment (temperature: 70 to 110 ° C, treatment time: 1 minute to 15 minutes) Forming a pre-baked coating film on the substrate; (2) placing the pre-baked coating film under a specified mask with ultraviolet rays [for example: g line, h line or i line, the ultraviolet irradiation device is: (super) High-pressure mercury lamp and metal halide lamp] exposure; (3) immersion in a developer (treatment temperature: 23 ± 2 ° C, processing time: 15 seconds to 5 minutes) to remove the unexposed portion, after Wash with pure water to form the pattern of the specified mask, then use compressed air or pressure Narrowing the nitrogen to dry the pattern; (4.) Post-baking with a heating device (for example: hot plate or oven) (treatment temperature: 150 to 250 ° C, treatment time: 150 to 250 ° C when using a hot plate, when using an oven The black matrix is formed on the substrate for 15 minutes to 150 minutes.

The developer is, for example but not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, aqueous ammonia, ethylamine, diethylamine, dimethyl Ethanolamine, tetramethylamine hydroxide, tetraethylamine hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo-[5,4,0]-7-undecene. The concentration of the developer ranges from 0.001 to 10% by weight. Preferably, the concentration of the developer ranges from 0.005 to 5 wt%, and more preferably, the concentration of the developer ranges from 0.01 to 1 wt%.

The substrate to which the black matrix of the present invention is applied is: an alkali-free glass, a soda-lime glass, a hard glass (Pyrus glass), and a quartz glass used for a liquid crystal display device, and a transparent conductive film attached to the glass. Or a photoelectric conversion device substrate (for example, a germanium substrate) such as a solid-state imaging device.

The color filter of the present invention comprises the above-described black matrix.

The color filter of the present invention can be prepared according to a general preparation method, for example, the above-mentioned black matrix can be formed on a substrate, and each color (mainly including three colors of red, green and blue) is formed in the same formation manner. On the substrate, a pixel colored layer of a color filter is further obtained. Next, an indium tin oxide (ITO) vapor-deposited film is formed on the pixel-colored layer under a vacuum of 220 ° C to 250 ° C, and if necessary, the ITO vapor-deposited film is subjected to etching and wiring, and then the liquid crystal alignment film is coated. A color filter for a liquid crystal display can be obtained by using polyimide.

The liquid crystal display element of the present invention comprises the color filter described above.

In the liquid crystal display device of the present invention, the color filter and the driving substrate provided with the thin film transistor (TFT) are opposed to each other, and a cell gap is interposed between the color filter and the driving substrate. (cell gap) is disposed oppositely, and the color filter is bonded to the peripheral portion of the driving substrate by a blocking agent, leaving only a liquid crystal injection hole, and then distinguished from the surface of the substrate and the sealing agent. The gap is filled with liquid crystal, and the liquid crystal injection hole is sealed to form a liquid crystal cell. Then, on the outer surface of the liquid crystal cell, that is, on the other side faces of the respective substrates constituting the liquid crystal cell, the polarizing plate is bonded to each other to obtain a liquid crystal display element.

The liquid crystal and the liquid crystal alignment film used as described above are not particularly limited, and may be used in the related art, and are not the focus of the present invention, and therefore will not be further described.

The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.

<Example>

[Synthesis Example 1] Preparation of Resin (A-1-1) having an unsaturated group

100 parts by weight of an antimony epoxy compound (Model ESF-300, manufactured by Nippon Steel Chemical Co., Ltd.; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, 0.1 part by weight 2,6-di-t-butyl-p-cresol, and 130 parts by weight of propylene glycol methyl ether acetate were continuously added to a 500 mL four-necked flask, and the feed rate was controlled at 25 parts by weight/min. The temperature of the reaction process is maintained at 100 to 110 ° C, A pale yellow transparent mixture (solid concentration of 50 wt%) was obtained in 15 hours.

Next, 100 parts by weight of the above light yellow transparent mixed solution is dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate to form a mixed solution, and 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight are simultaneously added. The benzophenone tetracarboxylic dianhydride is added to the mixture, and the mixture is heated to 110 ° C to 115 ° C for 2 hours to obtain a resin having an unsaturated group (acid value: 98.0 mgKOH/g; For A-1-1).

[Synthesis Example 2] Preparation of Resin (A-1-2) having an unsaturated group

100 parts by weight of the pale yellow transparent mixture obtained in Preparation Synthesis Example 1 was dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate to form a mixed solution, and 13 parts by weight of benzophenonetetracarboxylic dianhydride was added thereto. In the mixed solution, the mixture is first reacted at 90 to 95 ° C for 2 hours, and then 6 parts by weight of tetrahydrophthalic anhydride is added to the mixture, and reacted at 90 to 95 ° C for 4 hours, that is, A resin having an unsaturated group (acid value: 99.0 mgKOH/g; hereinafter abbreviated as A-1-2) was obtained.

[Synthesis Example 3] Preparation of Resin (A-1-3) having an unsaturated group

400 parts by weight of an epoxy compound [Model NC-3000, manufactured by Nippon Kayaku Co., Ltd.; epoxy equivalent 288], 102 parts by weight of acrylic acid, 0.3 parts by weight of methoxyphenol, and 5 parts by weight Triphenylphosphine, and 264 parts by weight of propylene glycol methyl ether acetate were added to the reaction flask, and the temperature of the reaction was maintained at 95 ° C for 9 hours to obtain an intermediate product (acid value: 2.2 mg KOH / g). Next, 151 parts by weight of tetrahydrophthalic anhydride was added and reacted at 95 ° C. After 4 hours, a resin having an unsaturated group (acid value: 102 mgKOH/g, weight average molecular weight: 3,200; hereinafter abbreviated as A-1-3) was obtained.

[Synthesis Example 4] Preparation of Other Alkali Soluble Resin (A-2-1)

1 part by weight of 2,2'-azobisisobutyronitrile, 240 parts by weight of propylene glycol methyl ether acetate, 20 parts by weight of methacrylic acid, 15 parts by weight of styrene, and 35 parts by weight of benzene methacrylate Methyl ester, 10 parts by weight of glycerol monomethacrylate and 20 parts by weight of N-phenylmaleimide were placed in a round bottom flask equipped with a stirrer and a condenser, and the inside of the flask was filled with nitrogen. Thereafter, the mixture was slowly stirred and heated to 80 ° C, and the components were uniformly mixed and subjected to polymerization for 4 hours. Thereafter, the temperature was further raised to 100 ° C, and 0.5 part by weight of 2,2'-azobisisobutyronitrile was added thereto for polymerization for 1 hour to obtain a further alkali-soluble resin (hereinafter referred to as A-2-1). .

[Synthesis Example 5] Preparation of Other Alkali Soluble Resin (A-2-2)

2 parts by weight of 2,2'-azobisisobutyronitrile, 300 parts by weight of dipropylene glycol monomethyl ether, 15 parts by weight of methacrylic acid, 15 parts by weight of ethyl 2-hydroxyacrylate, and 70 parts by weight The benzyl methacrylate was added to a round bottom flask equipped with a stirrer and a condenser, and the inside of the flask was filled with nitrogen gas, and then slowly stirred and heated to 80 ° C to uniformly mix the components and carry out polymerization. hour. Thereafter, the temperature was further raised to 100 ° C, and 0.5 part by weight of 2,2'-azobisisobutyronitrile was added thereto for polymerization for 1 hour to obtain a further alkali-soluble resin (hereinafter abbreviated as A-2-2). .

[Example 1] Preparation of photosensitive resin composition and black matrix

<Photosensitive resin composition>

100 parts by weight of the unsaturated group-containing resin (A-1-1) of Synthesis Example 1, 60 parts by weight of dipentaerythritol hexaacrylate (hereinafter abbreviated as B-1), and 30 parts by weight of 1-[9-B -6-(2-methylbenzhydryl)-9H-indazole-3-substituted]-ethane ketone 1-(O-ethinyl hydrazine) (hereinafter referred to as C-1-1), 50 Parts by weight of CI Pigment Black 7 (hereinafter referred to as D-1-1), 100 parts by weight of CI Pigment Blue 15:1 (hereinafter referred to as D-2-1), and 5 parts by weight of CI Pigment Violet 23 (hereinafter referred to as D- 3-1), and 1000 parts by weight of propylene glycol methyl ether acetate (hereinafter referred to as E-1) were uniformly stirred in a shaker to form a solution, which is the photosensitive resin composition of Example 1. The properties of the photosensitive resin composition of Example 1 were tested as shown in Table 1.

<black matrix>

The photosensitive resin composition of Example 1 was placed in a coater (manufactured by Shinko Trading Co., Ltd.; model: MS-A150), and coated on a glass substrate of 100 mm × 100 mm by spin coating, and then 100 mmHg. The drying was carried out under reduced pressure for 5 seconds, and pre-baked in an oven at 100 ° C for 2 minutes to form a prebaked film having a film thickness of about 1.2 μm.

Next, the prebaked coating film was placed under a designated mask, and the prebaked coating film was irradiated with ultraviolet light (exposure machine model: AG500-4N; manufactured by M&R Nano Technology) at 100 mJ/cm ² , and then the pre-baked coating film was applied. The baking coating film was immersed in a developer (0.04% potassium hydroxide) at 23 ° C for 2 minutes to remove the portion of the pre-baked coating film which was not irradiated with ultraviolet light, and then washed with pure water, and then in an oven at 230 After the post-baking treatment for 60 minutes, a black matrix having a film thickness of 1.0 μm was formed on the substrate. The property test results of the obtained black matrix are shown in Table 1.

[Examples 2 to 7 and Comparative Examples 1 to 5] Preparation of Photosensitive Resin Composition and Black Matrix

In Examples 2 to 7 and Comparative Examples 1 to 5, a photosensitive resin composition and a black matrix were prepared in the same manner as in Example 1, except that the types and amounts of the respective materials were changed, as shown in Table 1. The test results of the properties of the obtained photosensitive resin composition and black matrix are shown in Table 1.

[Property test]

To facilitate the description of the measurement process, the following description will be made with reference to Embodiment 1, and the remaining embodiments and comparative examples are measured in accordance with this mode.

Optical Density value (OD value): Referring to FIG. 1, after the black matrix of Example 1 was irradiated with an incident light, the black matrix (film thickness: 1 μm) of the first embodiment was measured and penetrated. The intensity of the emitted light is calculated, and the OD value of the black matrix of Example 1 is calculated by the following formula: OD=-log(I/I ₀ )

Where I ₀ is the intensity of the incident light, and I is the intensity of the outgoing light after the incident light passes through the black matrix.

Resolution: The prebaked coating film of Example 1 was placed under a mask having different line widths, and the prebaked coating film was irradiated with an exposure amount capable of forming a line width of 20 μm, after which the prebaked coating film was applied. Immersed in a developer (0.04% potassium hydroxide) at 23 ° C for 2 minutes to remove the portion of the pre-baked film that was not irradiated with ultraviolet light, and then washed with pure water and then at 230 ° C in an oven. Bake for 60 minutes. Next, use a microscope (made by Nikon, model Eclipse 50i) and scanning electron microscope (manufactured by Hitachi, model S-3000N), the evaluation method: ○: minimum line width ≦ 4 μm; △: 4 μm ≦ minimum line width <10 μm; ×: minimum line width > 10 Mm.

The prebaked coating film of Example 1 was placed under a designated halftone mask (transmittance: 50%), and irradiated with ultraviolet light of different exposure amounts (exposure model AG500-4N; manufactured by M&R Nano Technology). To perform a weak exposure process, a test coating film is formed. Then, a film thickness δ was measured on the test coating film, and then the test coating film was immersed in a developing solution (0.045% KOH) at 23 ° C for 50 seconds, and then measured at the same measurement point. A film thickness δ d is obtained. The residual film ratio was calculated by the following formula: residual film ratio (%) = [(δ d) / (δ)] × 100% was evaluated according to the following criteria: ○: exposure amount ≦ 80 mJ/cm ² , representing sensitization When the resin composition has an exposure amount of 80 mJ/cm ² or less, the residual film rate of the formed test film can be made 90% or more, which means that the sensitivity of the photosensitive resin composition is good; ×: the exposure amount is >80 mJ/ ² cm & lt representative photosensitive resin composition for an at 80mJ / cm ² or ^more, the exposure amount in order to make the film remaining rate of the test film formed over 90%, representing the sensitivity of the photosensitive resin composition is poor.

The results of the experimental data of Table 1 show that the photosensitive resin compositions of Examples 1 to 7 contain the resin (A-1) having an unsaturated group, the black pigment (D-1), and the blue pigment (D-2). And the weight ratio of the amount of the black pigment (D-1) to the amount of the blue pigment (D-2) used is in the range of 0.5 to 10, and the photosensitive resin composition has a preferable sensitivity and is formed therefrom. The black matrix has high light blocking properties (OD value of 4.0 to 4.8) and high resolution (minimum line width of 4 μm or less).

The photosensitive resin composition of Comparative Example 1 was inferior in sensitivity because it did not contain the resin (A-1) having an unsaturated group, and the resolution of the black matrix formed therefrom was poor (minimum line width was more than 10 μm) .

Since the photosensitive resin composition of Comparative Example 2 does not contain the black pigment (D-1), the OD value of the black matrix formed therefrom is only 2.0, so that the light-shielding property is not good and the black matrix formed therefrom is analyzed. Poor degree.

In the photosensitive resin composition of Comparative Example 3, since the blue pigment (D-2) was not contained, the sensitivity of the photosensitive resin composition was poor, and the resolution of the black matrix formed therefrom was not good.

In the photosensitive resin composition of Comparative Example 4, the weight ratio of the amount of the black pigment (D-1) used to the amount of the blue pigment (D-2) used was 0.4, and the OD value of the black matrix formed therefrom was only 3.3 and The resolution is not good.

In the photosensitive resin composition of Comparative Example 5, the weight ratio of the amount of the black pigment (D-1) used to the amount of the blue pigment (D-2) used was 11.0, and the sensitivity of the photosensitive resin composition was poor, and The resolution of the formed black matrix is not good.

In summary, the photosensitive resin composition of the present invention is used by using The unsaturated group-containing resin (A-1), black pigment (D-1), and blue pigment (D-2), and the amount of the black pigment (D-1) used and the blue pigment (D-2) are used. The weight ratio of the amount ranges from 0.5 to 10, so that the photosensitive resin composition has high sensitivity, and the black matrix formed therefrom has high light blocking property (OD value of 4.0 to 4.8) and high resolution.

The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and patent specification content of the present invention, All remain within the scope of the invention patent.

Claims (9)

A photosensitive resin composition comprising: an alkali-soluble resin component (A) comprising a resin (A-1) having an unsaturated group, and the resin (A-1) having an unsaturated group is polymerized from a mixture The reaction comprises the preparation of an epoxy compound (i) having at least two epoxy groups, and a compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group; a saturated group compound (B); a photoinitiator (C); a pigment component (D); and a solvent (E); wherein the pigment component (D) comprises a black pigment (D-1) and a blue pigment (D-2), and the weight ratio of the amount of the black pigment (D-1) used to the amount of the blue pigment (D-2) used is in the range of 0.5 to 4; and the blue pigment (D-2) is selected from a blue pigment having a copper phthalocyanine structure, a blue fluorenone blue pigment or a combination thereof; and a total amount of the alkali-soluble resin component (A) is 100 parts by weight, the black pigment (D-1) The amount used is in the range of 100 to 600 parts by weight, and the blue pigment (D-2) is used in an amount ranging from 60 to 400 parts by weight. The photosensitive resin composition according to claim 1, wherein the epoxy compound (i) having at least two epoxy groups is a ring having at least two epoxy groups represented by the formula (I). An oxygen compound, an epoxy compound having at least two epoxy groups represented by the formula (II), or a combination thereof: Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, halogen, C ₁ to C ₅ alkyl, C ₁ to C ₅ alkoxy, C ₆ to C ₁₂ aryl or C ₇ to C ₁₂ aralkyl Wherein R ⁵ to R ¹⁸ each independently represent hydrogen, halogen, C ₁ to C ₈ alkyl or C ₆ to C ₁₅ aryl, and n represents an integer of 0 to 10. The photosensitive resin composition according to claim 1, wherein the epoxy compound (i) having at least two epoxy groups is an epoxy compound having at least two epoxy groups represented by the formula (I): Wherein R ¹ , R ² , R ³ and R ⁴ each independently represent hydrogen, halogen, C ₁ to C ₅ alkyl, C ₁ to C ₅ alkoxy, C ₆ to C ₁₂ aryl or C ₇ to C ₁₂ aralkyl. The photosensitive resin composition according to claim 1, wherein the epoxy compound (i) having at least two epoxy groups is an epoxy compound having at least two epoxy groups represented by the formula (II): Wherein R ⁵ to R ¹⁸ each independently represent hydrogen, halogen, C ₁ to C ₈ alkyl or C ₆ to C ₁₅ aryl, and n represents an integer of 0 to 10. The photosensitive resin composition according to claim 1, wherein the content of the unsaturated group-containing resin (A-1) is 50, based on 100 parts by weight of the total amount of the alkali-soluble resin component (A). The ethylenically unsaturated group-containing compound (B) is used in an amount of from 30 to 300 parts by weight to 100 parts by weight, and the pigment component (D) is used in an amount ranging from 100 to 1000 parts by weight, the solvent (E) The amount used is in the range of 1,000 to 5,000 parts by weight. The photosensitive resin composition according to claim 1, wherein the photoinitiator (C) is used in an amount of 10 in terms of the total amount of the ethylenically unsaturated group-containing compound (B): 100 parts by weight. Up to 60 parts by weight. A black matrix formed of the photosensitive resin composition according to any one of claims 1 to 6. A color filter comprising the black matrix of claim 7. A liquid crystal display element comprising the color filter of claim 8.