TW201421159A - Photosensitive resin composition for color filters and uses thereof - Google Patents

Abstract

This invention relates to a photosensitive resin composition for color filters; it has the advantages of low aberration and high brightness before and after the developing process. This invention also provides a color filter fabrication process, color filters and liquid crystal display devices.

Description

Photosensitive resin composition for color filter and application thereof

The present invention relates to a photosensitive resin composition for a color filter of a liquid crystal display. In particular, it relates to a photosensitive resin composition for a color filter having a small color difference before and after development and a high luminance.

At present, color filters have been widely used in the fields of color liquid crystal displays, color facsimile machines, color cameras and the like. As the market demand is expanding, the production technology of color filters is also diversified. At present, dyeing methods, printing methods, electroplating methods, and pigment dispersion methods have been developed, among which the dispersion method is the mainstream process.

The color dispersion method is formed by using a metal such as metal chromium/chromium oxide or a photosensitive resin to form a black matrix for shading, and then a photosensitive resin (or called red pigment) dispersed on a glass substrate. The color photoresist is coated on the glass substrate, and then subjected to photomask exposure, development curing, etc. to form a red sub-pixel, repeating the same steps and successively forming green sub-pixels and blue sub-frames on the glass substrate. Picture. The red sub-pixels, the green sub-pixels, and the blue sub-pixels are separated by the black matrix to form a pixel colored layer on the glass substrate. Furthermore, a protective film may be formed on the pixel colored layer as needed, and then a transparent conductive film is formed on the protective film, and finally, the color filter is completed by cutting.

A photosensitive resin used in a pigment dispersion process is disclosed in Japanese Laid-Open Patent Publication No. 2004-138950, which uses a specific alkali-soluble resin. A color filter excellent in pattern shape, developability, and brightness is formed to form a pixel-colored layer having a flat surface to increase the brightness of the liquid crystal display.

However, the above-mentioned photosensitive resin composition has a disadvantage of excessive color difference before and after development, and further, as the brightness of the liquid crystal display is becoming stricter, the brightness of the photosensitive resin composition is not in line with the demand of the industry.

Therefore, how to overcome the problem of insufficient brightness and excessive color difference before and after development to meet the requirements of the current industry is an object of diligent research in the technical field to which the present invention pertains.

Summary of invention

The present invention provides a photosensitive resin composition for a color filter having a small color difference and high luminance before and after development by using a component which provides a special alkali-soluble resin and an antioxidant.

Accordingly, the present invention relates to a photosensitive resin composition for a color filter comprising: an alkali-soluble resin (A); an ethylenically unsaturated group-containing compound (B); a photoinitiator (C); a solvent (D); a pigment (E); and an antioxidant (F); wherein the antioxidant (F) comprises a phosphorus-based antioxidant (F-1) and a hindered phenol-based antioxidant (F-2), and the phosphorus Antioxidant (F-1) and the hindered phenolic system The weight ratio of antioxidant (F-2) is from 15/85 to 85/15.

The present invention also provides a method of producing a color filter which forms a pixel layer using the above-mentioned photosensitive resin composition.

The present invention further provides a color filter which is produced by the aforementioned method.

The present invention further provides a liquid crystal display device comprising the above-described color filter.

Detailed description of the invention

The present invention provides a photosensitive resin composition for a color filter comprising: an alkali-soluble resin (A); an ethylenically unsaturated group-containing compound (B); a photoinitiator (C); and an organic solvent (D) a pigment (E); and an antioxidant (F); wherein the antioxidant (F) comprises a phosphorus-based antioxidant (F-1) and a hindered phenol-based antioxidant (F-2), and the phosphorus-based antioxidant The weight ratio of (F-1) and the hindered phenolic antioxidant (F-2) is from 15/85 to 85/15.

The alkali-soluble resin (A) according to the present invention preferably comprises a first alkali-soluble resin (A-1) having an unsaturated group, and the first alkali-soluble resin (A-1) having an unsaturated group is An epoxy resin (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 are subjected to polymerization.

In a specific embodiment of the present invention, the epoxy resin (i) having at least two epoxy groups has a structural formula represented by the following formula (1): Wherein: R ¹ , R ² , R ³ and R ⁴ are independently selected from the group consisting of hydrogen, halogen or C ₁ to C ₅ alkyl, wherein R ¹ , R ² , R ³ and R ⁴ are respectively the same or different.

The epoxy resin (i) having at least two epoxy groups represented by the above formula (1) may include, but is not limited to, a reaction of a bisphenol fluorene with an epihalohydrin. An epoxy group-containing bisphenol quinone type compound.

Specifically, the specific bisphenol quinoid compound described above is, for example, 9,9-bis(4-hydroxyphenyl)fluorene, 9,9-bis (4- 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-fluorophenyl)fluorene, 9,9-bis(4-hydroxy-3-methoxyphenyl) )[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)芴9,9-bis(4-hydroxy-3,5-dichlorophenyl) A compound such as fluorene], 9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorene.

Suitable epihalohydrins as described above may include, but are not limited to, 3-chloro-1,2-epoxyhydrin or 3-bromo-1,2-epoxyhydrin.

The epoxy group-containing bisphenol quinoid compound obtained above includes, but is not limited to, (1) a product manufactured by Nippon Steel Chemical Co., Ltd., such as ESF-300, etc.; (2) a product manufactured by Osaka Gas, such as PG-100, EG- 210, etc.; (3) Goods manufactured by SMS Technology Co.: for example, SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, and the like.

In another embodiment of the present invention, the epoxy resin (i) having at least two epoxy groups has the structural formula represented by the following formula (2): Wherein R ⁵ to R ¹⁸ are independently selected from the group consisting of hydrogen, halogen, C ₁ to C ₈ alkyl, and C ₆ to C ₁₅ aromatic groups, wherein R ⁵ to R ¹⁸ are the same or different; n is an integer from 0 to 10.

In one embodiment of the present invention, the epoxy resin (i) having at least two epoxy groups represented by the above formula (2) can have the following formula (2- in the presence of an alkali metal hydroxide) 1) The compound of the structure is reacted with halogenated propylene oxide to obtain:

In the formula (2-1), with R ⁵ to R ¹⁸ of formula (2) are respectively the same as definitions of n and R ¹⁸ to ^5, and the definition of R n, which is not repeated herein.

In another embodiment of the present invention, the epoxy resin (i) having at least two epoxy groups represented by the above formula (2) is used in the presence of an acid catalyst, and has the following formula (2-2). The compound of the structure is subjected to a condensation reaction with a phenol to form a compound having the structure of the formula (2-1). Next, an excess of the halogenated propylene oxide is added for dehydrohalogenation, and the epoxy resin (i) having at least two epoxy groups represented by the formula (2) is obtained:

In the above formula (2-2), R ¹⁹ and R ²⁰ are each the same or different hydrogen atom, a halogen atom, a C ₁ to C ₈ alkyl group or a C ₆ to C ₁₅ aromatic group; X ¹ and X ^{2 ;} They are the same or different halogen atoms, C ₁ to C ₆ alkyl groups or C ₁ to C ₆ alkoxy groups, respectively. Preferably, the aforementioned halogen atom may be, for example, chlorine or bromine, and the aforementioned alkyl group may be, for example, a methyl group, an ethyl group or a third butyl group, and the aforementioned alkoxy group may be, for example, a methoxy group or an ethoxy group.

Specific examples of the above suitable phenols are, for example, phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butanol (t- Butyl phenol, octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol, vinylphenol , propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol or cyclohexylcresol. The aforementioned phenols can be generally used singly or in combination of plural kinds.

In a preferred embodiment of the present invention, the compound having a structure of the formula (2-2) is used in an amount of 1 mol, and the phenol is used in an amount of 0.5 mol to 20 mol; preferably 2 mol. Ears to 15 moles.

Specific examples of the aforementioned acid catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, aluminum chloride anhydrous, and chlorine. Zinc chloride or the like; preferably p-toluenesulfonic acid, sulfuric acid or hydrochloric acid. The above acid catalysts may be used singly or in combination of plural kinds.

Further, the amount of the acid catalyst to be used is not particularly limited, but preferably, the amount of the compound based on the above formula (2-2) is 100 parts by weight, and the amount of the acid catalyst used is 0.1. Parts by weight to 30 parts by weight.

The aforementioned condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Next, specific examples of the above organic solvent include toluene, Xylene or methyl isobutyl ketone. The above organic solvents may be used singly or in combination of plural kinds.

In one embodiment of the present invention, the amount of the compound and the phenol used in the structure of the formula (2-2) is 100 parts by weight, and the organic solvent is used in an amount of 50 parts by weight to 300 parts by weight; preferably 100 parts by weight to 250 parts by weight. Further, the aforementioned condensation reaction has an operation temperature of 40 ° C to 180 ° C, and the condensation reaction has an operation time of 1 hour to 8 hours.

After completion of the aforementioned condensation reaction, a neutralization treatment or a water washing treatment may be carried out as needed. The aforementioned neutralization treatment adjusts the pH of the solution after the reaction to pH 3 to pH 7; preferably pH 5 to pH 7. The water washing treatment may be carried out using a neutralizing agent, wherein the neutralizing agent is a basic substance, and specific examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; hydrogen Alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; diethylene triamine, triethylenetetramine, aniline, phenylenediamine (diethyltetramine) Organic amines such as phenylene diamine; and ammonia, sodium dihydrogen phosphate, and the like. The aforementioned washing treatment can be carried out by a conventional method. For example, an aqueous solution containing a neutralizing agent is added to the solution after the reaction, and extraction can be carried out repeatedly. After the neutralization treatment or the water washing treatment, the unreacted phenols and the solvent are distilled off by heating under reduced pressure, and concentrated to obtain a compound having the structure of the formula (2-1).

Specific examples of the above-mentioned suitable halogenated propylene oxide are, for example, 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane or any combination thereof. Carrying out the aforementioned Before the dehydrohalogenation reaction, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or during the reaction. The aforementioned dehydrohalogenation reaction has an operating temperature of from 20 ° C to 120 ° C and an operation time ranging from 1 hour to 10 hours.

In a specific example of the present invention, an aqueous solution of the alkali metal hydroxide added to the dehydrohalogenation reaction may be used. In this specific example, while the above aqueous alkali metal hydroxide solution is continuously added to the dehydrohalogenation reaction system, water and halogenated propylene oxide can be continuously distilled off under reduced pressure or normal pressure, thereby separating and removing Water, at the same time, the halogenated propylene oxide can be continuously refluxed into the reaction system.

Before the dehydrohalogenation reaction is carried out, tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethyl benzyl ammonium chloride or the like may be added. The quaternary ammonium salt is used as a catalyst, and reacted at 50 ° C 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 allowed to proceed for 1 hour at a temperature of 20 ° C to 120 ° C. Up to 10 hours to carry out the dehydrohalogenation reaction.

In one embodiment of the present invention, the total equivalent weight of the hydroxyl group in the compound having the structure of the above formula (2-1) is 1 equivalent, and the halogenated propylene oxide is used in an amount of 1 mole to 20 moles; Preferably, it is from 2 moles to 10 moles; on the other hand, the total equivalent weight of the hydroxyl group in the compound having the structure of the above formula (2-1) is 1 equivalent, and the alkali metal hydroxide added in the above dehydrohalogenation reaction It is used in an amount of from 0.8 moles to 15 moles; preferably from 0.9 moles to 11 moles.

Preferably, in order to facilitate the above-described dehydrohalogenation reaction, in addition to adding In addition to an alcohol such as methanol or ethanol, a reaction may be carried out by adding an aprotic polar solvent such as dimethyl sulfone or dimethyl sulfoxide. In the case of using an alcohol, the alcohol is used in an amount of from 2 parts by weight to 20 parts by weight, based on 100 parts by weight of the total of the above-mentioned halogenated propylene oxide; preferably from 4 parts by weight to 15 parts by weight. In the case of using an aprotic polar solvent, the aprotic polar solvent is used in an amount of 5 parts by weight to 100 parts by weight, based on 100 parts by weight of the halogenated propylene oxide; preferably 10 parts by weight to 90 parts by weight.

After completion of the dehydrohalogenation reaction, a water washing treatment can be selectively performed. Thereafter, the halogenated propylene oxide, the alcohol, and the aprotic polar solvent are removed by heating and decompression, for example, at a temperature of 110 ° C to 250 ° C and a pressure of 1.3 kPa (10 mmHg) or less.

In order to avoid the formation of the epoxy resin containing a hydrolyzable halogen, the solution after the dehydrohalogenation reaction may be added to a solvent such as toluene or methyl isobutyl ketone, and a base such as sodium hydroxide or potassium hydroxide may be added. The metal hydroxide aqueous solution is again subjected to a dehydrohalogenation reaction. In the dehydrohalogenation reaction, the total equivalent weight of the hydroxyl group in the compound having the structure of the above formula (2-1) is 1 equivalent, and the alkali metal hydroxide is used in an amount of 0.01 mol to 0.3 mol; preferably 0.05. Moor to 0.2 m. Further, the above dehydrohalogenation reaction has an operating temperature in the range of 50 ° C to 120 ° C and an operation time ranging from 0.5 hour to 2 hours.

After completion of the dehydrohalogenation reaction, the salts are removed by filtration, washing, and the like. Further, by heating and depressurizing, a solvent such as toluene or methyl isobutyl ketone can be distilled off, and at least two of the formula (2) can be obtained. Epoxy based epoxy resin (i). The epoxy resin (i) having at least two epoxy groups represented by the above formula (2) may include, but is not limited to, those commercially available under the trade names of NC3000, NC3000H, NC3000S, and NC3000P.

In a specific embodiment of the present invention, the compound (ii) having at least one carboxylic acid group and at least one ethylenically unsaturated group is selected from the group consisting of the following (1) to (3): (1) Acrylic acid, methacrylic acid, 2-methaacryloyloxyethylsuccinic acid, 2-methylpropenyloxybutyl succinic acid, 2-methylpropenyloxyethyl adipate, 2-methylpropenyloxybutyl adipate, 2-methylpropenyloxyethylhexahydrophthalic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxypropane Kamalyx, 2-methylpropenyloxybutyl maleic acid, 2-methylpropenyloxypropyl succinic acid, 2-methylpropenyloxypropyl adipate, 2-methylpropene oxime Oxybutylbutyrate, 2-methylpropenyloxypropyltetrahydrophthalic acid, 2-methylpropenyloxypropyl phthalate, 2-methylpropenyloxybutyl phthalate Or 2-methylpropenyloxybutylhydrophthalic acid; (2) a compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a dicarboxylic acid compound, wherein the dicarboxylic acid compound comprises Not limited to two , succinic acid, maleic acid, succinic acid, phthalic acid; (3) a half ester compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a carboxylic anhydride compound, wherein a hydroxyl group (meth) Acrylates include, but are not limited to, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate [(2) -hydroxypropyl)acrylate], 2-hydroxypropyl methacrylate [(2- Hydroxypropyl)methacrylate], 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, or pentaerythritol trimethacrylate. Further, the carboxylic anhydride compound according to the present invention may be used as described below for the epoxy resin (i) having at least two epoxy groups and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group ( Ii) The carboxylic anhydride compound (iii) which is subjected to the polymerization reaction is the same, and therefore will not be further described.

In a preferred embodiment of the present invention, the first alkali-soluble resin (A-1) having an unsaturated group may be an epoxy resin (i) having at least two epoxy groups and having at least one carboxylic acid group. The at least one ethylenically unsaturated group compound (ii) and the carboxylic anhydride compound (iii) and/or the epoxy group-containing compound (iv) are obtained by a polymerization reaction.

The above carboxylic anhydride compound (iii) is preferably selected from the group consisting of (1) succinic anhydride, maleic anhydride, itaconic anhydride, and the group of (1) to (2) (Itaconic anhydride), phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, A Methyl hexahydrophthalic anhydride, methyl endo-methylene tetrahydro phthalic anhydride, chlorendic anhydride, glutaric anhydride or trimellitic anhydride ( a carboxylic acid anhydride compound such as 1,3-dioxoisobenzofuran-5-carboxylic anhydride; and (2) benzophenone tetracarboxylic dianhydride (BTDA), diphenyltetracarboxylic acid A tetracarboxylic anhydride compound such as an anhydride or a diphenyl ether tetracarboxylic dianhydride.

The above epoxy group-containing compound (iv) is preferably selected from the group consisting of glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, an unsaturated group-containing glycidyl ether compound, and a ring-containing compound. An oxy unsaturated compound or a group consisting of any combination of the above. The unsaturated group-containing glycidyl ether compound includes, but is not limited to, trade names Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, and Denacol EX-192. Etc. (The above is a product of Changchun Chemical Industry Co., Ltd.).

In a preferred embodiment of the present invention, the first alkali-soluble resin (A-1) having an unsaturated group may be an epoxy resin (i) having at least two epoxy groups and having at least one carboxylic acid group and The at least one ethylenically unsaturated group compound (ii) is subjected to a polymerization reaction to form a hydroxyl group-containing reaction product, followed by addition of a carboxylic anhydride compound (iii) to carry out a reaction. Preferably, the hydroxyl group-based reaction product has a total hydroxyl equivalent of 1 equivalent, and the carboxylic anhydride compound (iii) has an acid anhydride group equivalent of from 0.4 equivalents to 1 equivalent; preferably from 0.75 equivalents to 1 equivalent. When a plurality of carboxylic anhydride compounds (iii) are used, they 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 is from 1/99 to 90/10; Good for 5/95 to 80/20. Further, the above reaction has an operating temperature in the range of 50 ° C to 130 ° C.

In another preferred embodiment of the present invention, the first alkali-soluble resin (A-1) having an unsaturated group may be an epoxy resin having at least two epoxy groups. (i) reacting 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 group The base compound (iv) is obtained by carrying out a polymerization reaction. Preferably, the total equivalent weight of the epoxy group based on the epoxy resin (i) having at least two epoxy groups is 1 equivalent, and the aforementioned compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (ii) The acid value equivalent is 0.8 equivalents to 1.5 equivalents; preferably 0.9 equivalents to 1.1 equivalents; on the other hand, the total amount of hydroxyl groups based on the aforementioned hydroxyl group-containing reaction product is 100 mole percent (mole %), the carboxyl group The acid anhydride compound (a-3) is used in an amount of from 10 mol% to 100 mol%; preferably from 20 mol% to 100 mol%; more preferably from 30 mol% to 100 mol%.

In the preparation of the above-mentioned 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 aforementioned reaction catalysts may be used singly or in combination, and the aforementioned reaction catalysts include, but are not limited to, triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine. ), tetramethylammonium chloride, benzyltriethylammonium chloride, and the like. Preferably, the epoxy resin (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 are used in an amount of 100 parts by weight, The reaction catalyst is used in an amount of from 0.01 part by weight to 10 parts by weight; preferably from 0.3 part by weight to 5 parts by weight.

In addition, in order to control the degree of polymerization, it is usually added to the reaction solution to inhibit polymerization. Agent. The above polymerization inhibitor may include, but is not limited to, methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-cresol (2,6-di). -t-butyl-p-cresol), or phenothiazine or the like. The above-mentioned polymerization inhibitors can be generally used singly or in combination of plural kinds. Preferably, the epoxy resin (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 are used in an amount of 100 parts by weight. The polymerization agent is used in an amount of from 0.01 part by weight to 10 parts by weight; preferably from 0.1 part by weight to 5 parts by weight.

In a specific example of the present invention, in the preparation of the first alkali-soluble resin (A-1) having an unsaturated group, a polymerization solvent may be used as necessary. Specific examples of the above polymerization solvent include alcohols such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol or ethylene glycol; ketone compounds such as methyl ethyl ketone or cyclohexanone; An aromatic hydrocarbon compound such as toluene or xylene; a cellosolve compound such as celecin or butyl cellosolve; a carbital compound such as carbital or butyl carbitol a propylene glycol alkyl ether compound such as propylene glycol monomethyl ether; a poly(propylene glycol alkyl ether) compound such as di(propylene glycol) methyl ether; ethyl acetate, acetic acid Acetate compounds such as butyl ester, ethylene glycol monoethyl ether acetate or propylene glycol methyl ether acetate; ethyl lactate or butyl lactate ( Butyl lactate), such as an alkyl lactate compound; or a dialkyl glycol ether. The foregoing The polymerization solvent can be generally used singly or in combination of plural kinds. Further, the acid value of the aforementioned first alkali-soluble resin (A-1) having an unsaturated group is from 50 mgKOH/g to 200 mgKOH/g; preferably from 60 mgKOH/g to 150 mgKOH/g.

In one embodiment of the present invention, the amount of the alkali-soluble resin (A) used is 100 parts by weight, and the amount of the first alkali-soluble resin (A-1) having an unsaturated group is 30 parts by weight to 100 parts by weight. Parts; preferably from 50 parts by weight to 100 parts by weight; more preferably from 70 parts by weight to 100 parts by weight. When the first alkali-soluble resin (A-1) having an unsaturated group is used, the brightness of the produced liquid crystal display is increased.

In a specific example of the present invention, the alkali-soluble resin (A) may optionally include other alkali-soluble resin (A-2). The other alkali-soluble resin (A-2) includes, but is not limited to, a resin containing a carboxylic acid group or a hydroxyl group, and specifically, for example, an acrylic resin other than the resin (A-1) having an unsaturated group, or a urethane resin. And novolac type (novolac) resin.

Preferably, the other alkali-soluble resin (A-2) is used in an amount of from 0 part by weight to 70 parts by weight, based on 100 parts by weight based on the total amount of the alkali-soluble resin (A); preferably from 0 part by weight to 50% by weight. More preferably, it is 0 part by weight to 30 parts by weight.

The ethylenically unsaturated group-containing compound (B) according to the present invention is meant to include, but is not limited to, the following first compound, second compound or any combination thereof according to the present invention.

The first compound is a (meth) acrylate-based compound obtained by reacting a caprolactone-modified polyol with (meth)acrylic acid.

The caprolactone-modified polyol according to the present invention is composed of the caprolactone and The reaction is carried out by reacting a polyol having 4 or more functional groups, wherein the caprolactone may be γ-caprolactone, δ-caprolactone, or ε-caprolactone; preferably ε-caprolactone The polyol having four or more functional groups may be pentaerythritol, ditrimethylolpropane, dipentaerythritol or the like. Preferably, the amount of the polyol having 4 functional groups or more is 1 mole, and the amount of the caprolactone used is 1 to 12 moles.

Specific examples of the first compound include: pentaerythritol caprolactone modified tetra(meth)acrylate compound, ditrimethylolpropane caprolactone modified tetra(meth)acrylate compound, dipentaerythritol A lactone-modified poly(meth)acrylate compound or the like, wherein a specific example of the poly(meth)acrylate compound modified by the dipentaerythritol caprolactone is the second modification of dipentaerythritol caprolactone ( Methyl) acrylate compound, dipentaerythritol caprolactone modified tri(meth) acrylate compound, dipentaerythritol caprolactone modified tetra(meth) acrylate compound, dipentaerythritol caprolactone A hexa (meth) acrylate compound modified with a pentaerythritol (meth) acrylate compound or dipentaerythritol caprolactone.

Further, the structure of the poly(meth) acrylate modified by the above dipentaerythritol caprolactone may be represented by the formula (3): In the formula (3): R ²¹ and R ²² each represent hydrogen or a methyl group; m is an integer of 1 to 2; a is an integer of 1 to 6; and b is an integer of 0 to 5; wherein a + b = 2 to 6; preferably a+b=3 to 6; more preferably a+b=5 to 6; most preferably a+b=6.

More specifically, the first compound is manufactured by Nippon Kayaku Co., Ltd. under the names KAYARAD® DPCA-20, DPCA-30, DPCA-60, DPCA-120, and the like.

The second compound according to the present invention has a functional group represented by the formula (4), Wherein R ²³ represents hydrogen or methyl.

The second compound may, for example, be acrylamide, (meth) propylene morpholine, (meth) acrylate-7-amino-3,7-dimethyloctyl, isobutoxymethyl (methyl) Propylene amide, isobornyl oxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl diglycol (meth) acrylate , third octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethyl amino (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylate Cyclopenteneoxyethyl ester, dicyclopentenyl (meth)acrylate, nitrogen, nitrogen-dimethyl(meth)acrylamide, tetrachlorophenyl (meth)acrylate, (meth)acrylic acid-2 -tetrachlorophenoxyethyl ester, tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl (meth)acrylate,-2-tetrabromo(meth)acrylate Phenoxyethyl ester, 2-trichlorophenoxyethyl (meth)acrylate, tribromophenyl (meth)acrylate, 2-tribromophenoxyethyl (meth)acrylate, (A) Base) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, vinyl caprolactam, nitrogen-vinyl tyrosinone, phenoxyethyl (meth) acrylate, ( Pentachlorophenyl methacrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono(meth) acrylate, propylene glycol poly(meth) acrylate, borneol (meth) acrylate, B Diol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, triethylene glycol diacrylate, tetraethylene glycol di(meth)acrylate, tris(2-hydroxyethyl)isocyanate (Meth) acrylate, tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, caprolactone modified tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, tris(A) Trimethylol propyl acrylate, ethylene oxide (hereinafter referred to as EO) modified tris (meth) acrylate trimethylol propyl ester, propylene oxide (hereinafter referred to as PO) modified three (methyl ) Trimethylolpropyl acrylate, triethylene glycol di(meth)acrylic acid , neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylic acid Ester, pentaerythritol tetra(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(methyl) Acrylate, dipentaerythritol tetra(meth)acrylate, ditrimethylolpropyl tetra(meth)acrylate, EO modified bisphenol A di(meth)acrylate, PO modified bisphenol A (Meth) acrylate, EO modified hydrogenated bisphenol A di(meth) acrylate, PO modified hydrogenated bisphenol A di(meth) acrylate, PO modified glycerol tripropionate, EO Modified bisphenol F di(meth) acrylate, EO modified dipentaerythritol hexa Acrylate Ester (trade name: DPEA-12, manufactured by Nippon Kayaku Co., Ltd.), phenolic polyglycidyl ether (meth) acrylate.

Preferably, the second compound is selected from trimethylol propyl triacrylate, EO modified trimethylol propyl triacrylate, PO modified trimethylol propyl triacrylate, pentaerythritol triacrylate , pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, EO modified dipentaerythritol hexaacrylate (trade name DPEA-12, manufactured by Nippon Kayaku Co., Ltd.), tetraacrylic acid A group consisting of ditrimethylolpropyl propyl ester, PO-modified triglyceride, TO-1382 manufactured by Japan East Asia Synthetic Co., Ltd., and a composition thereof.

In one embodiment of the present invention, the ethylenically unsaturated group-containing compound (B) is used in an amount of from 10 parts by weight to 500 parts by weight based on 100 parts by weight of the alkali-soluble resin (A); It is preferably from 20 parts by weight to 450 parts by weight; more preferably from 30 parts by weight to 400 parts by weight.

Specific examples of the photoinitiator (C) according to the present invention are an acetophenone compound, a biimidazole compound, an acyl oxime compound, or a combination thereof.

Specific examples of the acetophenone-based compound according to the present invention are: p-dimethylamino-acetophenone, α,α'-dimethoxyoxyazobenzophenone (α,α'- Dimethoxyazoxy-acetophenone), 2,2'-dimethyl-2-phenyl-acetophenone, p-methoxy-acetophenone 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone [2-methyl-1-(4-methylthio phenyl)-2-morpholino-1-propanone] , 2-benzyl-2-nitrogen, nitrogen-dimethyl Amino-1-(4-morpholinophenyl)-1-butanone [2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone].

A specific example of the diimidazole-based compound according to the present invention is: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis ( O-chlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-fluorophenyl)-4,4,5,5'-tetraphenyldiimidazole [2 , 2'-bis(o-fluorophenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-methylphenyl)-4,4',5,5' -2,2'-bis(o-methyl phenyl)-4,4',5,5''-tetraphenyl-biimidazole], 2,2'-bis(o-methoxyphenyl) ) 4,4',5,5'-o-methoxyphenyl-4,4',5,5'-tetraphenyl-biimidazole], 2,2'- Bis(o-ethylphenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(o-ethylphenyl)-4,4',5,5'-tetraphenyl- Biimidazole], 2,2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(p-methoxyphenyl)-4,4' ,5,5'-tetraphenyl-biimidazole], 2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyl Imidazole [2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(2-chlorophenyl) -4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(2-chlorophenyl)-4,4',5,5'- Tetraphenyl-biimidazole], 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(2,4-dichlorophenyl) )-4,4',5,5'-tetraphenyl-biimidazole].

Specific examples of the lanthanide compound according to the present invention are: ethane ketone, 1-[9-ethyl-6-(2-methylbenzylidenyl)-9hydro-oxazol-3- substituent]- , 1-(N-acetyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyl oxime), such as Ciba Specialty Chemicals The product name is CGI-242, its structure is shown in formula (5)], 1-(4-phenyl-thio-phenyl)-octane-1,2-dione 2-indole-oxy-benzene [1-(4-phenyl-thio-phenyl)-octane-1,2-dion 2-oxime-O-benzoate, as the product name CGI-124 manufactured by Ciba Specialty Chemicals, the structure is shown in (6) ), ethane ketone, 1-[9-ethyl-6-(2-chloro-4-benzyl-thio-benzhydryl)-9hydro-indazole-3-substituent] -, 1-(9-ethyl-6-(2-cholro-4-benzyl-thio-benzoyl)-9H-carbazole-3-yl]-, 1-((Ethone) O-acetyl oxime), manufactured by Asahi Chemical Co., Ltd., its structure is shown in formula (7)].

Preferably, the photoinitiator (C) is 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-nitrogen. Nitro-dimethylamine-1-(4-morpholinophenyl)-1-butanone, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl Diimidazole, ethane ketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9hydro-oxazol-3-substituted]-, 1-(oxy-acetamidine) , or a combination thereof.

The photoinitiator (C) according to the present invention may further be further added with the following compounds: thioxanthone, 2,4-diethyl-thioxanthanone, thioxanthene Thioxanthone-4-sulfone, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4 , benzophenone-based compound such as 4'-bis(diethylamino)benzophenone; benzil or acetyl Such as α-diketones; benzoin and other acyloins; benzoin methylether, benzoin ethylether, Acetone ethers such as benzoin isopropyl ether; 2,4,6-trimethyl-benzoyl-diphenyl -phosphineoxide), bis-(2,6-dimethoxybenzoquinone)-2,4,4-trimethylphenylphosphine oxide [bis-(2,6-dimethoxy-benzoyl)-2,4, 4-trimethyl-benzyl-phosphineoxide] acylphosphine oxide; anthraquinone, 1,4 - quinone (1,4-naphthoquinone) and other quinones; phenacyl chloride, tribromomethyl-phenylsulfone, tris(trichloromethyl)-s-three Triazine (trichloromethyl)- a s-triazine or the like; and a peroxide such as di-tertbutylperoxide; preferably a benzophenone-based compound; preferably 4, 4'- Bis(diethylamine) benzophenone.

In one embodiment of the present invention, the photoinitiator (C) is used in an amount of from 10 parts by weight to 150 parts by weight per 100 parts by weight of the alkali-soluble resin (A); preferably 15 parts by weight to 125 parts by weight; more preferably 20 parts by weight to 100 parts by weight.

On the other hand, in one embodiment of the present invention, the weight ratio of the first alkali-soluble resin (A-1) having an unsaturated group to the photoinitiator (C) is from 40/60 to 80/20; It is preferably from 45/55 to 75/25; more preferably from 50/50 to 70/30. When the weight ratio of the first alkali-soluble resin (A-1) having an unsaturated group to the photoinitiator (C) is from 40/60 to 80/20, the photosensitive resin composition has a color difference before and after development. Lower advantage.

The organic solvent (D) according to the present invention means that the alkali-soluble resin (A), the ethylenically unsaturated group-containing compound (B) and the photoinitiator (C) can be dissolved without being subjected thereto. React and have the appropriate volatility.

Specific examples of the organic solvent are: ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, and triglyceride. Alcohol diethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol diethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol mono methyl Ether), tripropylene glycol mono ethyl ether, etc. Alcohol monoalkyl ethers; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, etc. (poly)alkylene glycol monoalkyl ether acetate; diethylene glycol Other ethers such as dimethyl ether, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; methyl 2-hydroxypropionate, 2 - alkyl lactate such as ethyl hydroxypropionate; methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3- Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyric acid Methyl ester, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, acetic acid Isopropyl ester, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, butyric acid Butyl ester, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, acetoacetic acid Other esters such as methyl ester, ethyl acetate, ethyl 2-oxybutyrate; aromatic hydrocarbons such as toluene and xylene; and nitrogen-methylpyrrolidone, nitrogen, nitrogen-dimethylformamidine A carboxylic acid amide such as an amine, nitrogen or nitrogen-dimethylacetamide.

Preferably, the organic solvent (D) is propylene glycol methyl ether acetate or ethyl 3-ethoxypropionate, which may be used alternatively or in combination.

In one embodiment of the present invention, the organic solvent (D) is used in an amount of from 500 parts by weight to 5,000 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A); preferably from 800 parts by weight. The portion is 4,500 parts by weight; more preferably, it is from 1000 parts by weight to 4,000 parts by weight.

The pigment (E) according to the invention may be an inorganic pigment, an organic pigment, or Its combination.

The inorganic pigment according to the present invention is a metal compound such as a metal oxide or a metal salt, and specifically, for example, an oxide of a metal such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, lead, or antimony, and a composite oxide of the foregoing metal.

The organic pigment according to the present invention may be used alone or in combination of two or more of the following: CI Pigment Yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175; CI Pigment Orange 1, 5, 13, 14, 16 , 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38, 39; CI Pigment Blue 1, 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 66; CI Pigment Green 7, 36, 37, 58; CI Pigment Brown 23, 25, 28; and CI Pigment Black 1, 7.

The average particle diameter of the primary particles of the pigment (E) is preferably from 10 nm to 200 nm; more preferably from 20 nm to 150 nm; most preferably from 30 nm to 130 nm.

When necessary, the pigment (E) is accompanied by a dispersant. Specific examples of the dispersant are surfactants such as cationic, anionic, nonionic, amphoteric, polyoxyalkylene, and fluorine.

The surfactant according to the present invention may be used singly or in combination of one or more of the following: polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether Polyethylene oxide alkyl ethers; polyethylene oxide alkyl phenyl ethers such as polyethylene oxide octyl phenyl ether and polyethylene oxide nonyl phenyl ether; polyethylene glycol dilaurate Polyethylene glycol diesters such as polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid modified polyesters; tertiary amine modified polyurethanes; Shin-Etsu Chemical Industrial KP products, SF-8427 products manufactured by Toray Dow Corning Silicon, Polyflow products manufactured by Kyoei Oil & Fat Chemical Industry, and love from Tochem Products Co., Ltd. F-Top products, Megafac products made by Dainippon Chemical Industry, Suomen 3M's Fluorade products, Asahi Guard products by Asahi Glass Asahi Glass's Surflon products.

In a specific example of the present invention, the pigment (E) is used in an amount of from 50 parts by weight to 500 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). Parts by weight; preferably from 75 parts by weight to 450 parts by weight; more preferably from 100 parts by weight to 400 parts by weight.

The antioxidant (F) according to the present invention comprises a phosphorus-based antioxidant (F-1) and a hindered phenol-based antioxidant (F-2), and the phosphorus-based antioxidant (F-1) and the hindered phenol-based antioxidant The weight ratio of (F-2) is from 15/85 to 85/15.

A specific example of the phosphorus-based antioxidant (F-1) according to the present invention is: tris[2-[[2,4,8,10-tetra(1,1-dimethylethyl)-dibenzo[ d,f][1,3,2]dioxaphosphocycloheptan-6-yl]oxy]ethyl]amine, tris[2-[[2,6,9,11-tetra-tert-butyldibenzo) [d,f][1,3,2]dioxaphosphopoheptan-2-yl]oxy]ethyl]amine, ethyl bisphosphite (2,4-di-tert-butyl-6-methylbenzene) , bis-(2,6-di-tert-butyl-4-methylphenol) pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl phosphate), tetra (2, 4-di-tert-butyl-5-methylphenyl)-4,4'-biphenylene diphosphinate, 3,5-di-tert-butyl-4-hydroxybenzyl phosphate-two Ethyl ester, bis-(2,6-dicumylphenyl)pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, Triphosphoric acid tri(mixed mono- and di-nonylphenyl phosphate), bis(2,4-di-tert-butylphenyl)pentaerythritol-di-phosphite, bis(2,6-di-tertiary Butyl-4-methoxycarbonylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-octadecyloxycarbonylethylphenyl)pentaerythritol diphosphite.

Specific examples of the hindered phenol-based antioxidant (F-2) according to the present invention are: 2,4-bis[(laurylthio)methyl]-o-cresol, 1,3,5-tri (3, 5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyano Urea, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, triethylene glycol- Bis [3-(3-tert-butyl-5-) Methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol -tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) Propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,6-di-tert-butyl 4-ethylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butyl) Phenol), 4,4'-butylene-bis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) Butane, 1,3,5-tris(4-hydroxybenzyl)benzene and tetrakis[methylene-3-(3,5'-di-tert-butyl-4'-hydroxy-phenylpropionic acid)] Methane.

According to the phosphorus-based antioxidant (F-1) of the present invention and the hindered phenol-based antioxidant (F-2), the phosphorus-based antioxidant (F-1) and the hindered phenol-based antioxidant (F-) may be used. 2) Mixing at a specific ratio first, and specific examples of the mixture are Chinox B225, Chinox B245, and Chinox TP-10H (double bond chemical).

When the antioxidant (F) according to the present invention is not provided, the photosensitive resin composition is liable to cause a problem of excessive color difference before and after development, and the brightness of the liquid crystal display produced is not good.

The weight ratio of the phosphorus-based antioxidant (F-1) and the hindered phenol-based antioxidant (F-2) according to the present invention is from 15/85 to 85/15; preferably, the weight ratio is from 20/80. Up to 80/20; more preferably, the weight ratio is from 25/75 to 75/25. When the weight ratio is less than 15/85, the pattern formed by the photosensitive resin composition tends to cause a problem that the profile is too low; on the other hand, when the weight ratio is higher than 85/15, the photosensitive resin The pattern formed by the composition is prone to undercut problems.

In one embodiment of the present invention, the antioxidant (F) is used in an amount of from 1 part by weight to 30 parts by weight, based on 100 parts by weight of the alkali-soluble resin (A); preferably from 2 parts by weight The amount is 28 parts by weight; more preferably 3 parts by weight to 25 parts by weight.

In another aspect of the invention, the weight ratio of the photoinitiator (C) to the antioxidant (F) is from 60/40 to 99/1; preferably from 65/35 to 95. /5; better from 60/40 to 90/10. When the weight ratio of the photoinitiator (C) to the antioxidant (F) is from 60/40 to 99/1, the brightness of the produced liquid crystal display increases.

In a specific example of the present invention, the photosensitive resin composition is the alkali-soluble resin (A), the ethylenically unsaturated group-containing compound (B), and the photoinitiator (C). The organic solvent (D), the pigment (E), and the antioxidant (F) are essential components, and an additive such as a surfactant, a filler, or a polymer compound may be further added as needed (other than the alkali-soluble resin) ), adhesion promoter, other antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like.

Wherein, the surfactant according to the present invention can improve the coating property of the present invention, and is specifically, for example, a surfactant which is used in conjunction with the above-mentioned pigment; in a specific example of the present invention, the amount of the alkali-soluble resin is used. The surfactant is used in an amount of from 0 part by weight to 6 parts by weight per 100 parts by weight; preferably from 0 part by weight to 4 parts by weight; more preferably from 0 part by weight to 3 parts by weight.

Specific examples of the filler are glass and aluminum; specific examples of the polymer compound are polyvinyl alcohol, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; Specific examples of the adhesion promoter are vinyltrimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, and nitrogen-(2-aminoethyl)-3-amino Propylmethyldimethoxydecane, nitrogen-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-epoxypropanolpropyltrimethyl Oxydecane, 3-glycidylpropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxy Decane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-thiolpropyltrimethoxydecane; specific examples of such other antioxidants are 2,2- Thiobis(4-methyl-6-tert-butylphenol), 2,6-di-t-butylphenol; a specific example of the ultraviolet absorber is 2-(3-tert-butyl-5- Methyl-2-hydroxyphenyl)-5-chlorophenyl azide or alkoxyphenone; a specific example of the anti-agglomerating agent is sodium polyacrylate.

In a specific example of the present invention, the filler, the polymer compound other than the alkali-soluble resin, the adhesion promoter, and other antioxidants are used in an amount of 100 parts by weight of the alkali-soluble resin (A). The additives such as the ultraviolet absorber, the anti-agglomerating agent and the like are used in an amount of from 0 part by weight to 10 parts by weight; preferably from 0 part by weight to 6 parts by weight; more preferably from 0 part by weight to 3 parts by weight.

In a specific embodiment of the present invention, the photosensitive resin composition of the present invention is prepared by using the alkali-soluble resin (A), the ethylenically unsaturated group-containing compound (B), and the photoinitiator (C). After mixing and dissolving in the organic solvent (D), the pigment (E) and the antioxidant (F) are further added, and if necessary, an additive such as a surfactant or a adhesion promoter is added thereto. By uniformly mixing, the photosensitive resin composition in a solution state can be prepared.

The present invention also provides a method of producing a color filter which forms a pixel layer using the above-mentioned photosensitive resin composition.

The present invention further provides a color filter which is produced by the aforementioned method.

In a specific example of the present invention, in the production of the color filter, the photosensitive resin composition of the present invention in a solution state is applied by a coating method such as rotary coating, cast coating or roll coating. Coated on a substrate. The substrate may be an alkali-free glass, a soda-lime glass, a hard glass (Pyles glass), a quartz glass, or the like to which a transparent conductive film is attached, or used for a photoelectric conversion device (for a liquid crystal display device) a substrate such as a solid-state imaging device (for example, a ruthenium substrate); and, before applying the photosensitive resin composition on the substrate, it is a black color for shading which can be used to isolate colored layers such as red, green, and blue. A black matrix is formed on the substrate.

After coating, most of the organic solvent contained in the photosensitive resin composition is removed by vacuum drying, and the residual organic solvent is completely removed by pre-bake to form a pre-baked coating film. In the process, the operating conditions under reduced pressure drying and pre-baking vary depending on the type and blending ratio of each component. Usually, the drying under reduced pressure is carried out at a pressure of 0 mmHg to 200 mmHg for 1 second to 60 seconds. The baking is carried out at a temperature of 70 ° C to 110 ° C for 1 minute to 15 minutes.

After pre-baking, the pre-baked film is exposed in a mask having a specific pattern. The light used in the exposure process is preferably ultraviolet rays such as g-line, b-line, and i-line, and the device for emitting ultraviolet rays may be (super) high-pressure mercury lamp. And metal halide lamps.

After exposure, the prebaked coating film is immersed in a developing solution having a temperature of 23±2° C. for about 15 seconds to 5 minutes to remove unnecessary portions of the prebaked coating film for the substrate. A predetermined pattern is formed on the upper surface. The developer used may be sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, aqueous ammonia, ethylamine, diethylamine, and Methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, acridine, or 1,8-diazabicyclo-(5,4,0)-7-undecene The alkaline aqueous solution of the compound is generally present in a concentration of from 0.001% by weight to 10% by weight; preferably from 0.005% by weight to 5% by weight; more preferably from 0.01% by weight to 1% by weight.

Thereafter, the pattern on the substrate is washed with water, and the pattern is air-dried with compressed air or compressed nitrogen. Finally, the pattern is heat-treated (post-bake) by a heating device such as a hot plate or an oven, and the heating temperature is set at 150. Between ° C and 250 ° C, the heating time is 5 minutes to 60 minutes when the hot plate is used, and 15 minutes to 150 minutes when the oven is used, whereby the pattern is fixed and formed into a single-color colored layer.

By repeating the above steps, a colored layer of red, green, blue or the like can be formed on the substrate in sequence.

Next, an ITO protective film is sputter-sputtered on the surface of the pixel colored layer under a vacuum environment having a temperature between 220 ° C and 250 ° C, and if necessary, etching and wiring the ITO protective film, and then The color filter can be formed by coating an alignment film on the surface of the ITO protective film.

The present invention further provides a liquid crystal display device characterized by comprising the foregoing Color filter.

In a specific embodiment of the present invention, a glass substrate in which a thin film transistor (TFT) is mounted and an alignment film is coated is disposed, and a gap is interposed between the color filter and the glass substrate. In the opposite direction, the liquid crystal molecules are injected into the gap, and then a polarizing plate is attached to the outer surface of the color filter and the outer surface of the glass substrate to obtain the liquid crystal display device.

The invention is illustrated by the following examples, which are not intended to be limited to the scope of the invention.

Synthesis Example 1: Method for producing first alkali-soluble resin (A-1-1) having an unsaturated group

100 parts by weight of an oxime 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 monomethyl ether acetate were continuously added to a 500-mL four-necked flask, and the feed rate was controlled at 25 parts by weight/ In a minute, the temperature of the reaction was maintained at 100 ° C to 110 ° C for 15 hours to obtain a pale yellow transparent mixture having a solid concentration of 50 wt%.

Next, 100 parts by weight of the above-obtained pale yellow transparent mixture is dissolved in 25 parts by weight of ethylene glycol ethyl acetate, and 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of diphenyl are simultaneously added. Methyl ketone tetracarboxylic dianhydride, and heated to 110 ° C to 115 ° C, the reaction for 2 hours, you can get an acid price of 98.0 A resin having an unsaturated group of mgKOH/g (hereinafter abbreviated as A-1-1).

Synthesis Example 2: Method for producing first alkali-soluble resin (A-1-2) having an unsaturated group

100 parts by weight of an oxime 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 monomethyl ether acetate were continuously added to a 500-mL four-necked flask, and the feed rate was controlled at 25 parts by weight/ In a minute, the temperature of the reaction was maintained at 100 ° C to 110 ° C for 15 hours to obtain a pale yellow transparent mixture having a solid concentration of 50 wt%.

Next, 100 parts by weight of the above-obtained pale yellow transparent mixture is dissolved in 25 parts by weight of ethylene glycol ethyl ether acetate, and 13 parts by weight of benzophenone tetracarboxylic dianhydride is added at 90 ° C to 95 ° C. The reaction was carried out for 2 hours, and then, 6 parts by weight of tetrahydrophthalic anhydride was added, and reacted at 90 ° C to 95 ° C for 4 hours to obtain an unsaturated group-containing resin having an acid value of 99.0 mgKOH/g. (hereinafter referred to as A-1-2).

Synthesis Example 3: Method for producing first alkali-soluble 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 p-methoxyphenol, 5 Parts by weight of triphenylphosphine, and 264 parts by weight of propylene glycol monomethyl ether acetate were placed in a reaction flask, and the temperature of the reaction was maintained at 95 ° C for 9 hours. An intermediate product having an acid value of 2.2 mg KOH/g was obtained. Next, 151 parts by weight of tetrahydrophthalic anhydride was added and reacted at 95 ° C for 4 hours to obtain an unsaturated group having an acid value of 102 mgKOH/g and a weight average molecular weight of 3,200. Resin (hereinafter referred to as A-1-3).

Synthesis Example 4: Method for Producing Other Alkali Soluble Resin (A-2-1)

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

Synthesis Example 5: Method for Producing Other Alkali Soluble Resin (A-2-2)

2 parts by weight of 2,2'-azobisisobutyronitrile, 300 parts by weight of dipropylene glycol methyl 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 placed in 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 and polymerize the reactants. Reaction for 3 hours. Thereafter, the temperature is further raised to 100 ° C, and 0.5 parts by weight of 2,2'-azobisisobutyronitrile is added for polymerization for 1 hour to obtain an other alkali-soluble resin (hereinafter referred to as A-2-2). ).

Example 1

100 parts by weight of the first alkali-soluble resin (A-1-1) having an unsaturated group of Synthesis Example 1, 100 parts by weight of dipentaerythritol hexaacrylate (hereinafter referred to as B-1), and 15 parts by weight of 2- Methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone (hereinafter referred to as C-1), 25 parts by weight of 2,2'-bis(2,4-dichloro Phenyl)-4,4',5,5'-tetraphenyldiimidazole (hereinafter referred to as C-2), 30 parts by weight of 4,4'-bis(diethylamine)benzophenone (hereinafter referred to as C -3), 50 parts by weight of CI Pigment Red 254/CI Pigment Yellow 139=80/20 (hereinafter referred to as E-1), 0.15 parts by weight of [2-[[2,4,8,10-four (1) ,1-dimethylethyl)-dibenzo[d,f][1,3,2]dioxaphosphocycloheptan-6-yl]oxy]ethyl]amine (hereinafter referred to as F-1-1) ), 0.85 parts by weight of 2,4-bis[(lauric thio)methyl]-o-cresol (hereinafter referred to as F-2-1), and 500 parts by weight of propylene glycol methyl ether acetate (hereinafter referred to as D-) 1) A photosensitive resin composition of the present invention can be obtained by forming a uniform solution state by a shaking agitator. The obtained photosensitive resin composition was subjected to characteristic measurement in each evaluation method described later, and the obtained results are shown in Table 1.

Examples 2 to 11 and Comparative Examples 1 to 4

Examples 2 to 11 and Comparative Examples 1 to 4 used the same operation method as the method for producing the photosensitive resin composition described in Example 1, except that Examples 2 to 11 and Comparative Examples 1 to 4 changed the photosensitivity. The details and subsequent evaluation results of the raw materials in the resin composition are shown in Table 1 (Examples 1 to 11) and Table 2 (Comparative Examples 1 to 4), respectively.

Evaluation method

Brightness

The photosensitive resin composition is applied by spin coating The glass substrate of 100 mm×100 mm was first dried under reduced pressure at a pressure of 100 mmHg for 30 seconds, and then pre-baked at a temperature of 80 ° C for 3 minutes to form a pre-baked film having a film thickness of 2.5 μm. The prebaked coating film was irradiated with ultraviolet light (Canon PLA-501F) at a light amount of 300 mJ/cm 2 , and then immersed in a developing solution at 23 ° C for 2 minutes, washed with pure water, and then washed with pure water. After baking at 200 ° C for 80 minutes, a photosensitive resin layer having a film thickness of 2.0 μm can be formed on the glass substrate.

The obtained photosensitive resin layer was measured for the CIE (International Commission on Illumination) color system chromaticity coordinates of the obtained photosensitive resin layer using a colorimeter (manufactured by Otsuka Electronics Co., Ltd., model MCPD) under a C light source condition. The value (x, y) and the brightness Y value. The larger the Y value, the higher the brightness, and the Y value of the red, green and blue photosensitive resin layer is evaluated on the following basis:

Benchmark evaluation of red photosensitive resin layer:

◎: 30≦Y value

○: 28≦Y value <30

△: 26 ≦ Y value < 28

×: Y value <26

Benchmark evaluation of green photosensitive resin layer:

◎: 55≦Y value

○: 53 ≦ Y value <55

△: 51≦Y value <53

×: Y value <51

Benchmark evaluation of blue photosensitive resin layer:

◎: 15≦Y value

○: 13 ≦ Y value < 15

△: 11 ≦ Y value <13

×: Y value <11

2. Color difference before and after development:

The photosensitive resin composition was applied by spin coating to a glass substrate of 100 mm × 100 mm, and dried under reduced pressure at a pressure of 100 mmHg for 30 seconds, and then pre-baked at a temperature of 80 ° C for a period of time. In 2 minutes, a pre-baked film having a film thickness of 2.5 μm was formed. Then, the chromaticity (L*, a*, b*) was measured with a colorimeter (manufactured by Otsuka Electronics Co., Ltd., model MCPD).

Next, the prebaked coating film was irradiated with ultraviolet light (exposure machine Canon PLA-501F) at a light amount of 100 mJ/cm 2 , and then the prebaked coating film was further immersed in a developing solution at 23 ° C for 1 minute, and washed with pure water. The chromaticity change was measured again and evaluated according to its chromaticity change ΔEab* on the following basis:

△Eab*={(△L) ² +(△a) ² +(△b) ² } ^1/2

◎: chromaticity change △ Eab * < 2

○: 2 ≦ chromaticity change △ Eab * < 4

△: 4 ≦ chromaticity change △ Eab * < 6

×: chromaticity change △ Eab * ≧ 6

3. Contour angle:

The profile angle refers to the angle between the surface of the substrate and the tangent in the cross section of the formed pattern. As shown in the first figure, the edge angle of the photosensitive resin layer (171) is a side wall angle with respect to the substrate (14).

○: 20° ≦ θ ₁ ≦ 60°

△: 10° ≦ θ ₁ < 20°

×: θ ₁ <10°

Undercut

The photosensitive resin layer obtained by the brightness was observed by a scanning electron microscope (SEM), and the undercut was evaluated according to the shape of the edge profile.

○: As shown in Fig. 1, the edge angle (the side wall angle with respect to the substrate (14)) of the photosensitive resin layer (171) was 20 ° < θ ₁ ≦ 60 °.

△: As shown in Fig. 2, the edge angle (the side wall angle with respect to the substrate (14)) of the photosensitive resin layer (172) was 60 ° < θ ₂ ≦ 90 °.

×: As shown in Fig. 3, the edge angle (the side wall angle with respect to the substrate (14)) of the photosensitive resin layer (173) was θ ₃ > 90°.

C-3 4,4'-bis(diethylamine)benzophenone C-4 1-(4-phenyl-thio-phenyl)-octane-1,2-dione 2-indole-oxygen -benzoate D-1 propylene glycol methyl ether acetate D-2 3-ethoxypropionate ethyl ester E-1 CI Pigment Red 254/CI Pigment Yellow 139=80/20 E-2 CI Pigment Green 36/CI Pigment Yellow 150=60/40 E-3 CI Pigment Blue 15:6 F-1-1 Tri[2-[[2,4,8,10-tetra(1,1-dimethylethyl)-diphenyl And [d,f][1,3,2]dioxaphosphocycloheptan-6-yl]oxy]ethyl]amine F-1-2 three [2-[[2,6,9,11-four tert-Butyldibenzo[d,f][1,3,2]dioxaphosphoheptan-2-yl]oxy]ethyl]amine F-1-3 Ethyl bisphosphite (2,4- Di-tert-butyl-6-methylphenyl)F-2-1 2,4-bis[(laurylthio)methyl]-o-cresol F-2-2 1,3,5-tri (3 ,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate F-2-3 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethyl Benzyl)isocyanurate

The above-described embodiments are merely illustrative of the principles and effects of the invention, and are not intended to limit the invention. Modifications and variations of the embodiments described above will be apparent to those skilled in the art without departing from the spirit of the invention. The scope of the invention should be as set forth in the appended claims.

14‧‧‧Substrate

171‧‧‧Photosensitive resin layer

172‧‧‧Photosensitive resin layer

173‧‧‧Photosensitive resin layer

Fig. 1 is a schematic view showing the state of the edge side of the photosensitive resin pattern (a).

Fig. 2 is a schematic view showing the state of the edge side of the photosensitive resin pattern (2).

Fig. 3 is a schematic view showing the state of the edge side (3) of the photosensitive resin pattern.

14‧‧‧Substrate

171‧‧‧Photosensitive resin layer

Claims (11)

A photosensitive resin composition for a color filter comprising: an alkali-soluble resin (A); an ethylenically unsaturated group-containing compound (B); a photoinitiator (C); an organic solvent (D); and a pigment (E); and an antioxidant (F); wherein the antioxidant (F) comprises a phosphorus-based antioxidant (F-1) and a hindered phenol-based antioxidant (F-2), and the phosphorus-based antioxidant (F- 1) The weight ratio of the hindered phenolic antioxidant (F-2) is from 15/85 to 85/15. The photosensitive resin composition for a color filter according to claim 1, wherein the weight ratio of the phosphorus-based antioxidant (F-1) and the hindered phenol-based antioxidant (F-2) is from 20/80 to 80/ 20. The photosensitive resin composition for a color filter according to claim 1, wherein the weight ratio of the phosphorus-based antioxidant (F-1) and the hindered phenol-based antioxidant (F-2) is from 25/75 to 75/ 25. The photosensitive resin composition for a color filter according to claim 1, wherein the alkali-soluble resin (A) comprises a first alkali-soluble resin (A-1) having an unsaturated group, and the unsaturated group is The alkali-soluble resin (A-1) is obtained by polymerization of an epoxy resin (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. . The photosensitive resin composition for a color filter according to claim 4, wherein the epoxy resin (i) having at least two epoxy groups has a structural formula represented by the following formula (1) or (2): Wherein: R ¹ , R ² , R ³ and R ⁴ are independently selected from the group consisting of hydrogen, halogen or C ₁ to C ₅ alkyl; Wherein: R ⁵ to R ¹⁸ are independently selected from the group consisting of hydrogen, halogen, C ₁ to C ₈ alkyl and C ₆ to C ₁₅ aromatic groups; and n is an integer of 0 to 10. The photosensitive resin composition for a color filter according to claim 4, wherein the weight ratio of the first alkali-soluble resin (A-1) having an unsaturated group to the photoinitiator (C) is from 40/60 to 80/20. The photosensitive resin composition for a color filter according to claim 1, wherein the weight ratio of the photoinitiator (C) to the antioxidant (F) is from 60/40 to 99/1. A photosensitive resin composition for a color filter according to claim 1, wherein The first alkali-soluble resin (A-1) having an unsaturated group is used in an amount of from 30 to 100 parts by weight based on 100 parts by weight of the alkali-soluble resin (A); the ethylenically unsaturated group-containing compound ( B) is used in an amount of from 10 to 500 parts by weight; the photoinitiator (C) is used in an amount of from 10 to 150 parts by weight; and the organic solvent (D) is used in an amount of from 500 to 5,000 parts by weight; The pigment (E) is used in an amount of from 50 to 500 parts by weight; and the antioxidant (F) is used in an amount of from 1 to 30 parts by weight. A method of producing a color filter, which comprises forming a pixel layer using the photosensitive resin composition according to any one of claims 1 to 8. A color filter produced by the method of claim 9. A liquid crystal display device comprising a color filter according to claim 10.