TW201606433A - Photosensitive resin composition for color filter and application thereof - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for a color filter and an application thereof. The photosensitive resin composition includes an alkali-soluble resin (A), a compound having a vinyl unsaturated group (B), a photo initiator (C), an organic solvent (D) and a pigment (E). The alkali-soluble resin (A) includes a first alkali-soluble resin (A-1), and the first alkali-soluble resin (A-1) is obtained by copolymerizing a first mixture. The first mixture at least includes a vinyl unsaturated monomer having a structure of hindered amine (a1-1), a vinyl unsaturated monomer having an oxetanyl (a1-2) and a vinyl unsaturated monomer having a carboxylic acid group (a1-3).

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 and a color filter formed thereby, and more particularly to providing photosensitivity for a color filter having good alkali resistance and voltage retention. Resin composition.

Currently, color filters have been widely used in applications such as color liquid crystal displays, color facsimile machines, or color cameras. With the increasing market demand for office equipment such as color liquid crystal displays, the production techniques of color filters are also diversified. For example, methods such as dyeing, printing, electroplating and dispersion have been developed. Now, the dispersion method is used as the mainstream production technology for color filters.

The above dispersion method disperses a pigment in a photosensitive resin to form a photosensitive resin composition. Then, the photosensitive resin composition is applied onto a glass substrate, and subjected to steps such as exposure and development to obtain a specific pattern. Then, after repeating the above processes of coating, exposure, and development three times, the desired red (R), green (G), and blue (B) paintings in the pixel colored layer of the color filter can be obtained. Prime coloring pattern. In general, in order to further enhance the color The contrast of the color filter is such that a light shielding layer (or a black matrix) can be disposed between the pixel colored layers formed by the pixels.

The process of the above pigment dispersion method is to form a colored photosensitive resin composition by dispersing a pigment in a photocurable resin, and finally forming the resin composition into a pixel colored layer. Further, in the process of the pigment dispersion method, a black matrix is usually formed on a transparent support such as a glass substrate by using a metal such as chromium or chromium oxide or a photosensitive resin light-shielding film. Then, the photosensitive resin (color resist) in which the red pigment is dispersed is applied onto the transparent support by spin coating, exposed by a photomask, and developed after exposure. You can get red pixels. Then, in the same operation mode, that is, the coating, exposure, and development can be repeatedly used to obtain three-color pixels such as red, green, and blue on the support.

In recent years, the use of color liquid crystal displays is no longer limited to personal computers, but also widely used in color TVs and various surveillance screens (especially large-size color LCD screens), so the requirements for color saturation of liquid crystal displays are increasing. high. Therefore, the proportion of the pigment contained in the photosensitive resin composition is also higher and higher, however, when the ratio of the pigment is increased, the contrast of the color liquid crystal display is lowered, and since the relative use amount of the alkali-soluble resin and the photosensitive monomer is small, The degree of cross-linking after exposure is lowered, resulting in problems such as poor alkali resistance.

In the content disclosed in Japanese Laid-Open Patent Publication No. 2004-138950, a specific color-soluble resin can be used to form a coloring layer having a flat surface, a color filter having excellent pattern shape, alkali resistance, and brightness. However, this method tends to cause the voltage holding ratio of the photosensitive resin composition to be too low. As a result, defects in the residual image are likely to occur when the screen is displayed.

In view of the above, there is an urgent need to develop a photosensitive resin composition for a color filter having high contrast, good alkali resistance, and voltage holding ratio to overcome the above-mentioned problems of the conventional color filter.

Therefore, an aspect of the present invention provides a photosensitive resin composition for a color filter. The photosensitive resin composition can improve the alkali resistance and voltage retention of the color filter.

Another aspect of the present invention provides a method of producing a color filter which forms a pixel layer using a photosensitive resin composition for a color filter.

Still another aspect of the present invention is to provide a color filter which is produced by the aforementioned manufacturing method.

Still another aspect of the present invention is to provide a liquid crystal display comprising the aforementioned color filter.

According to the above aspect of the invention, there is provided a photosensitive resin composition for a color filter comprising an alkali-soluble resin (A), a compound having an ethylenically unsaturated group (B), and light-emitting The starting agent (C), the organic solvent (D), and the pigment (E) are described below.

Photosensitive resin composition

Alkali soluble resin (A)

The alkali-soluble resin (A) of the present invention may comprise a first alkali-soluble resin (A-1). Further, the alkali-soluble resin (A) may optionally contain a second base Soluble resin (A-2).

First alkali soluble resin (A-1)

The first alkali-soluble resin (A-1) is obtained by copolymerization of the first mixture, and the first mixture contains at least an ethylenically unsaturated monomer (a1-1) having a hindered amine structure, having an oxetane The ethylenically unsaturated monomer (a1-2) and the ethylenically unsaturated monomer (a1-3) having a carboxylic acid group. Further, the first mixture may optionally further comprise the ethylenically unsaturated monomer (a1-1) having a hindered amine structure, and the ethylenically unsaturated monomer having an oxetane group (a1-2) And a copolymerizable ethylenically unsaturated monomer (a1-4) other than the carboxylic acid group-containing ethylenically unsaturated monomer (a1-3).

Ethylene unsaturated monomer having hindered amine structure (a1-1)

The ethylenically unsaturated monomer (a1-1) having a hindered amine structure contains an unsaturated monomer having a structure represented by the following formula (I):

In the formula (I), X ₁ represents a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, and a carbon number. An aromatic group of 6 to 20, an aromatic alkyl group having 7 to 12 carbon atoms, a mercapto group, an oxygen radical or -OX ₄ ; X ₄ represents a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, and a carbon number a branched alkyl group of 3 to 18, a cycloalkyl group having 3 to 18 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an aromatic alkyl group having 7 to 12 carbon atoms, an anthracenyl group; X ₂ and X ₃ Each of them independently represents a methyl group, an ethyl group, a phenyl group, or X ₂ and X _{3 are} bonded to each other to form an aliphatic ring having a carbon number of 4 to 12; "*" represents a covalent bond.

When X ₁ and X ₄ represent a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms or a cycloalkyl group having 3 to 18 carbon atoms, the X ₁ and X ₄ Specific examples may include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, cyclohexyl, n-octyl or hexadecyl groups and the like. When X ₁ represents an aromatic group having a carbon number of 6 to 20, specific examples thereof may include, but are not limited to, a phenyl group, an α-naphthyl group or a β-naphthyl group. When X ₁ and X ₄ represent an aromatic alkyl group having a carbon number of 7 to 12, X ₁ and X ₄ may be an aromatic group bonded to an alkyl group having 1 to 8 carbon atoms, and the carbon number of the aromatic group is 6 to 10, specific examples thereof may include, but are not limited to, benzyl, phenethyl, α-methylbenzyl or 2-yl-2-phenylpropane, and the like. When X ₁ and X ₄ represent a fluorenyl group, X ₁ and X ₄ may be an alkanoyl group or an aryl group having 2 to 8 carbon atoms, and specific examples thereof may be an ethyl fluorenyl group or a benzamidine group.

X _{1 is} preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an oxygen radical, and more preferably a hydrogen atom, an oxygen radical or a methyl group.

When X ₂ and X ₃ in the formula (I) are bonded to form a structure of an aliphatic ring, a specific example thereof may be cyclopentane or cyclohexane. Preferably, X ₂ and X ₃ may be methyl.

The unsaturated monomer having a structure represented by the formula (I) may have a structure as shown in the formula (I-1) and the formula (I-2):

In the formula (I-1) and the formula (I-2), X ₅ and X ₈ each independently represent a hydrogen atom or a methyl group; X ₆ represents a methylene group or an alkylene group having a carbon number of 2 to 5; ₇ represents a structure represented by the formula (I); X ₉ represents -CONH-*, -SO ₂ -, -SO ₂ NH-*, wherein "*" represents a covalent bond bonded to X ₇ ; s is 0 An integer of up to 8, preferably 0 to 6.

Preferably, X ₆ may be an ethylene group or a propylene group, and more preferably an ethylene group.

The above unsaturated monomer having a structure represented by the formula (I-1) may be a structure represented by the following formulas (I-1-1) to (I-1-7):

In the formulae (I-1-1) to (I-1-7), the definition of X ₅ is as described above, and will not be further described herein.

The above unsaturated monomer having a structure represented by the formula (I-2) may be a structure represented by the following formulas (I-2-1) to (I-2-4):

In the formulae (I-2-1) to (I-2-4), the definition of X ₈ is as described above, and will not be further described herein.

The ethylenically unsaturated monomer (a1-1) having a hindered amine structure may include, but is not limited to, 4-methylpropenylamine-2,2,6,6-tetramethyl-piperidine (4-methacrylamido- 2,2,6,6-tetramethylpiperidine), or manufactured by Hitachi Chemical Co., Ltd., model FA-712HM [2,2,6,6-tetramethyl-piperidinyl acrylate; that is, the above formula (I) -1-1), and X ₅ represents methyl] or FA-711MM [methyl 1,1,2,6,6-pentamethyl-piperidinyl acrylate; that is, the above formula (I-1-2) And X ₅ represents a product such as methyl].

The ethylenically unsaturated monomer having a hindered amine structure may be used singly or in combination of plural kinds.

An ethylenically unsaturated monomer (a1-1) having a hindered amine structure, and an ethylenically unsaturated monomer (a1-2) having an oxetanyl group described later, and an ethylenically unsaturated monomer having a carboxylic acid group Body (a1-3) and other optional additions The total amount of the ethylenically unsaturated monomer (a1-4) copolymerizable is 100 parts by weight, and the ethylenically unsaturated monomer (a1-1) having a hindered amine structure is used in an amount of 5 parts by weight to 50 parts by weight. The portion is preferably from 10 parts by weight to 40 parts by weight, and more preferably from 10 parts by weight to 30 parts by weight.

When the first alkali-soluble resin (A-1) does not use the ethylenically unsaturated monomer (a1-1) having a hindered amine structure as a copolymerization monomer, the obtained color filter is composed of a photosensitive resin. The object has the defect of poor voltage retention.

Ethylene unsaturated monomer having oxetanyl group (a1-2)

The oxetane group-containing ethylenically unsaturated monomer (a1-2) contains an unsaturated monomer having a structure represented by the following formula (II):

In the formula (II), Y ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; Y ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and Y ₃ , Y ₄ , Y ₅ and Y ₆ independently represents a hydrogen atom, a fluorine atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms or a perfluoroalkyl group having 1 to 4 carbon atoms; and the a represents an integer of 1 to 6.

Specific examples of the unsaturated monomer having a structure represented by the formula (II) may include, but are not limited to, a methacrylate compound, an acrylate compound or have the following formula (II-1) to formula (II-4) ) An unsaturated monomer of the structure shown.

The aforementioned methacrylate compound may include, but is not limited to, 3-(methacryloyloxy)oxetane [3-(methacryloyloxy)) Oxetane; OXMA], 3-(methacryloylmethoxy)-3-ethyloxetane [3-(methacryloyloxy)-3-ethyloxetane; EOXMA], 3-(methacrylomethoxymethoxy) -3-methyloxetane [3-(methacryloyloxy)-3-methyloxetane; MOXMA], 3-(methacrylomethoxymethoxy)-2-methyloxetane, 3-( Methyl propylene methoxy)-2-trifluoromethyl oxetane, 3-(methacryl methoxymethoxy)-2-pentafluoroethyl oxetane, 3-(methyl Propylene 醯methoxy)-2-phenyloxetane, 3-(methacryl methoxymethoxy)-2,2-difluorooxetane, 3-(methacryl oxime methoxy) -2,2,4-trifluorooxetane, 3-(methylpropenylmethoxy)-2,2,4,4-tetrafluorooxetane, 3-(methyl Propylene oxime ethoxy) oxetane, 3-(methacryl oxime ethoxy)-3-ethyl oxetane, 2-ethyl-3-(methacryl oxime ethoxy) Oxetane, 3-(methacrylium ethoxy)-2-trifluoromethyl oxetane, 3-(methacryl oxime ethoxy)-2-pentafluoroethyl oxalate Cyclobutane, 3-(methacryl oxime ethoxy)-2-phenyl oxetane, 2,2-difluoro-3-(methacryl oxime ethoxy) Heterocyclobutane, 3-(methacryl oxime)-2,2,4-trifluorooxetane or 3-(methacryl oxirane)-2,2,4,4 a compound such as tetrafluorooxetane.

The above acrylate compound may include, but is not limited to, 3-(propylene methoxy) oxetane, 3-(propylene methoxymethyl)-3-ethyloxetane, 3-(propylene醯Methoxy)-3-methyloxetane, 3-(propylene methoxymethyl)-2-methyloxetane, 3-(propylene methoxymethyl)-2-trifluoro Methyl oxetane, 3-(propylene methoxy)-2-pentafluoroethyl oxetane, 3-(propylene methoxymethyl)-2-phenyl oxetane, 3-(propylene methoxymethoxy)-2,2-difluorooxetane, 3-(propylene methoxymethyl)-2,2,4-trifluorooxetane, 3-(propylene methoxymethoxy)-2,2,4,4-tetrafluorooxetane, 3-(acryloyloxy)oxetane, 3-(acryloximeethoxy) 3-ethyloxetane, 2-ethyl-3-(propylene oxime ethoxy) oxetane, 3-(polypropylene ethoxy)-2-trifluoromethyl oxane Butane, 3-(acrylomethoxyethoxy)-2-pentafluoroethyloxetane, 3-(acryloyloxy)-2-phenyloxetane, 2,2-di Fluoro-3-(acryloyloxy)oxybutane, 3-(polypropylene ethoxy)-2,2,4-trifluorooxetane or 3-(acryloximeethoxy) a compound of -2,2,4,4-tetrafluorooxetane or the like.

The above unsaturated monomer having a structure represented by the formula (II-1) to the formula (II-4) is as follows:

Specific examples of the other oxetane group-containing ethylenically unsaturated monomer may include, but are not limited to, 3-methyl-3-(vinylmethoxy)oxetane [3-methyl-3-( Vinyloxy)oxetane;MOXV], 3-ethyl-3-(vinylmethoxy)oxetane [3-ethyl-3-(vinyloxy)oxetane; EOXV], 3-propyl-3-(vinylidene) Oxy)oxetane, 3-methyl-3-(2-vinylethoxy)oxetane, 3-ethyl-3-(2-vinylethoxy)oxetane , 3-propyl-3-(2-vinylethoxy)oxetane, 3-methyl-3-(3-vinylpropoxy)oxetane, 3-ethyl-3- (3-vinylpropoxy)oxetane, 3-propyl-3-(3-vinylpropoxy)oxetane, 3-methyl-3-(3-vinylbutoxy) Oxetane, 3-ethyl-3-(3-vinylbutoxy)oxetane, 3-propyl-3-(3-vinylbutoxy)oxetane, ethylene Alcohol [(3-ethyl-3-oxetanyl)methyl]vinyl ether, propylene glycol [(3-ethyl-3-oxetanyl)methyl]vinyl ether or 3,3- A vinyl ether compound having an oxetane group such as bis[(ethyleneoxy)methyl]oxetane.

An ethylenically unsaturated monomer (a1-1) having a hindered amine structure and an ethylenically unsaturated monomer (a1-2) having an oxetanyl group, and an ethylenically unsaturated monomer having a carboxylic acid group described later The total amount of the monomer (a1-3) and the other copolymerizable ethylenically unsaturated monomer (a1-4) to be selectively added is 100 parts by weight, and the ethylenically unsaturated monomer having an oxetane group (a1-2) usage It is from 10 parts by weight to 60 parts by weight, preferably from 15 parts by weight to 60 parts by weight, and more preferably from 20 parts by weight to 55 parts by weight.

When the first alkali-soluble resin (A-1) does not use an ethylenically unsaturated monomer (a1-2) having an oxetanyl group as a copolymerizable monomer, the photosensitive filter for the color filter is obtained. The resin composition has a defect of poor alkali resistance.

Ethylene-unsaturated monomer having a carboxylic acid group (a1-3)

The ethylenically unsaturated monomer (a1-3) having a carboxylic acid group may be an ethylenically unsaturated monomer having one or more carboxylic acid groups.

Specific examples of the carboxylic acid group-containing ethylenically unsaturated monomer (a1-3) may include, but are not limited to, acrylic acid, methacrylic acid, crotonic acid, chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-acrylic acid An unsaturated monocarboxylic acid compound such as oxysuccinate, 2-methylpropenyl ethoxy succinate or 2-isobutenyl ethoxy succinate; maleic acid, maleic anhydride, rich An unsaturated dicarboxylic acid compound such as horse acid, itaconic acid, itaconic anhydride, citraconic acid or citraconic anhydride or an anhydride thereof; or another unsaturated polycarboxylic acid compound containing three or more carboxylic acid groups or an anhydride thereof .

The ethylenically unsaturated monomer (a1-3) having a carboxylic acid group may preferably be acrylic acid, methacrylic acid, 2-propenyl ethoxy succinate, 2-methyl propylene ethoxy ethoxylate An acid ester or 2-isobutylene ethoxylate succinate, and more preferably 2-propenyl ethoxy succinate, 2-methyl propylene ethoxy succinate or 2-isobutyl ketone Oxysuccinate.

An ethylenically unsaturated monomer (a1-1) having a hindered amine structure, an ethylenically unsaturated monomer having an oxetane group (a1-2), and an ethylenically unsaturated monomer having a carboxylic acid group ( A1-3), and other optional additions described later The total amount of the ethylenically unsaturated monomer (a1-4) copolymerizable is 100 parts by weight, and the ethylenically unsaturated monomer (a1-3) having a carboxylic acid group is used in an amount of 10 parts by weight to 40 parts by weight. The portion is preferably from 12 parts by weight to 35 parts by weight, and more preferably from 15 parts by weight to 30 parts by weight.

Other copolymerizable ethylenically unsaturated monomers (a1-4)

The foregoing first mixture may optionally comprise other copolymerizable ethylenically unsaturated monomers (a1-4), and the other copolymerizable ethylenically unsaturated monomers (a1-4) may include, but are not limited to, An aromatic vinyl compound such as styrene, α-methylstyrene, vinyl toluene, p-chlorostyrene or methoxystyrene; N-phenylmaleimide, N-o-hydroxyphenyl horse Indole, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-A Phenyl phenyl maleimide, N-p-methylphenyl maleimide, N-o-methoxyphenyl maleimide, N-m-methoxyphenyl mala An imine, an N-p-methoxyphenyl maleimide or a N-cyclohexylmaleimine, such as maleic imine; methyl acrylate, methyl methacrylate, ethyl acrylate, Ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, methacrylic acid Isobutyl ester, acrylic acid Dibutyl ester, second butyl methacrylate, tert-butyl acrylate, third butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxy propyl acrylate Ester, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, acrylic acid - 3-hydroxybutyl ester, 3-hydroxybutyl methacrylate Ester, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, methyl Phenyl acrylate, triethylene glycol methacrylate, triethylene glycol methacrylate, dodecyl methacrylate, tetradecyl methacrylate, cetyl methacrylate , unsaturated carboxylic acid esters such as octadecyl methacrylate, eicosyl methacrylate, behenyl methacrylate or dicyclopentenyl acrylate; acrylic acid-N, N-dimethylaminoethyl ester, N,N-dimethylaminoethyl methacrylate, N-N-diethylaminopropyl acrylate, N-N-dimethylaminopropyl methacrylate Acrylic acid such as ester, acrylic acid-N,N-dibutylaminopropyl ester or iso-Butylaminoethyl Methacrylate; epoxy acrylate or epoxypropyl methacrylate a saturated carboxylic acid glycidyl ester; a vinyl carboxylate such as vinyl acetate, vinyl propionate or vinyl butyrate An unsaturated ether such as vinyl methyl ether, vinyl ethyl ether, allyl epoxypropyl ether or methallyl epoxypropyl ether; acrylonitrile, methacrylonitrile, α-chloroacrylonitrile or a vinyl cyanide compound such as vinyl cyanide; acrylamide, methacrylamide, α-chloropropenylamine, N-hydroxyethyl acrylamide or N-hydroxyethyl methacrylamide An unsaturated decylamine; an aliphatic conjugated diene such as 1,3-butadiene, isoamylene or chlorinated butadiene.

Preferably, the other copolymerizable ethylenically unsaturated monomer (a1-4) may be styrene, N-phenylmaleimide, methyl acrylate, methyl methacrylate, acrylic acid-2- Hydroxyethyl ester, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate or dicyclopentenyl acrylate.

The other copolymerizable ethylenically unsaturated monomer (a1-4) may be used singly or in combination of plural kinds.

An ethylenically unsaturated monomer (a1-1) having a hindered amine structure, an ethylenically unsaturated monomer having an oxetane group (a1-2), and an ethylenically unsaturated monomer having a carboxylic acid group ( The total amount of the a1-3) and other copolymerizable ethylenically unsaturated monomers (a1-4) is 100 parts by weight, and the amount of the other copolymerizable ethylenically unsaturated monomer (a1-4) is used. It is 5 parts by weight to 75 parts by weight, preferably 10 parts by weight to 65 parts by weight, and more preferably 15 parts by weight to 55 parts by weight.

Second alkali soluble resin (A-2)

The alkali-soluble resin of the present invention may optionally comprise a second alkali-soluble resin (A-2), and the second alkali-soluble resin (A-2) is obtained by a second mixture reaction.

The aforementioned second mixture comprises an epoxy compound (a2-1) having at least two epoxy groups, and a compound (a2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group. Next, the second mixture may optionally contain a carboxylic anhydride compound (a2-3), a compound having an epoxy group (a2-4), or any combination of the above materials.

Epoxy compound having at least two epoxy groups (a2-1)

The epoxy compound (a2-1) having at least two epoxy groups includes a compound having a structure represented by the following formula (III) or formula (IV), or any combination of the above materials:

In the formula (III), R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group, or a carbon number of 6 to 12. Aromatic or aralkyl.

The compound having a structure represented by the formula (III) can be obtained by reacting a bisphenol fluorene with an epihalohydrin.

Specific examples of the aforementioned bisphenol quinone type compound may include, but are not limited to, 9,9-bis(4-hydroxyphenyl)fluorine, 9,9-bis (4- 9,9-bis(4-hydroxy-3-methylphenyl)fluorine, 9,9-bis(4-hydroxy-3-chlorophenyl)fluorene [9,9- Bis(4-hydroxy-3-chlorophenyl)fluorine], 9,9-bis(4-hydroxy-3-bromophenyl)fluorine, 9, 9-bis(4-hydroxy-3-fluorophenyl)fluorine, 9,9-bis(4-hydroxy-3-methoxyphenyl) )[9,9-bis(4-hydroxy-3-methoxyphenyl)fluorine], 9,9-bis(4-hydroxy-3,5-dimethylphenyl)anthracene [9,9-bis(4- Hydroxy-3,5-dimethylphenyl)fluorine], 9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorine [9,9-bis(4-hydroxy-3,5-dichlorophenyl)fluorine] 9,9-bis(4-hydroxy-3,5-dibromophenyl)anthracene [9,9-bis(4-hydroxy-3,5-dibromophenyl)fluorine], or any combination of the above compounds.

Specific examples of the above halogenated propylene oxide may include, but are not limited to, 3-chloro-1,2-epoxyhydrin, 3-bromo-1,2-epoxyhydrin (epibromohydrin) or any combination of the above compounds.

Specific examples of the compound having a bisphenol quinone type may be manufactured by Nippon Steel Chemical Co., Ltd., a product of the type ESF-300; manufactured by Osaka Gas Co. Ltd., model number is A product of PG-100 or EG-210; manufactured by SMS Technology Co. Ltd., model of SMS-F9PhPG, SMS-F9CrG or SMS-F914PG.

In the formula (IV), R ₅ to R ₁₈ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aromatic group having 6 to 15 carbon atoms, and b represents an integer of 0 to 10 .

The compound having a structure represented by the formula (IV) can be reacted with a halogenated propylene oxide in the presence of an alkali metal hydroxide using a compound represented by the following formula (III-1):

In the formula (IV-1), R ₅ to R ₁₈ and b are each as defined above, and are not described herein.

A method for synthesizing a compound having a structure represented by the formula (IV-1) is a condensation reaction of a compound represented by the following formula (IV-2) with a phenol compound in the presence of an acid catalyst. To form a compound as shown in the formula (IV-1). Then, an excess of the halogenated propylene oxide is added to carry out dehydrohalogenation of the halogenated propylene oxide with the compound of the formula (IV-1) to obtain a structure having the formula (IV). compound of:

In the formula (IV-2), R ₇ to R _{10 are} as defined above and will not be further described herein; R ₁₉ and R ₂₀ each independently represent a halogen atom or an alkyl or alkane having 1 to 6 carbon atoms; Oxygen.

The aforementioned halogen atom may be a chlorine atom or a bromine atom; the alkyl group may preferably be a methyl group, an ethyl group or a tert-butyl group; the alkoxy group may preferably be a methoxy group or an ethoxy group.

Specific examples of the aforementioned phenolic compound may include, but are not limited to, phenol, cresol, ethylphenol, n-propanol (n-propylphenol), isobutylphenol, t-butylphenol, octylphenol, nonylphenol, xylenol, methylbutylphenol , di-t-butylphenol, vinylphenol, propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol or cyclohexyl Phenol (cyclohexylcresol) and the like. The phenolic compounds may be used singly or in combination of plural kinds.

The compound represented by the above formula (III-2) is used in an amount of 1 mol, and the phenol compound is used in an amount of from 0.5 mol to 20 mol, and preferably from 2 mol to 15 mol.

Specific examples of the acid catalyst may include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, aluminum chloride anhydrous or chlorinated. a compound such as zinc chloride. The acid catalyst is preferably p-toluenesulfonic acid, sulfuric acid, hydrochloric acid or any combination of the above compounds.

The amount of the aforementioned acid catalyst used is not particularly limited. However, the use amount of the compound represented by the above formula (IV-2) is 100% by weight, and the acid catalyst is preferably used in an amount of from 0.1% by weight to 30% by weight.

The above condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Specific examples of the organic solvent may include, but are not limited to, an organic solvent such as toluene, xylene or methyl isobutyl ketone. The above organic solvents may be used singly or in combination of plural kinds.

The total amount of the compound and the phenol used as shown in the formula (IV-2) is 100% by weight, and the organic solvent is used in an amount of 50% by weight to 300% by weight, and preferably 100% by weight to 250% by weight. Further, the above 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 above condensation reaction, a neutralization treatment or a water washing treatment may be performed. The neutralization treatment adjusts the pH of the solution after the reaction to 3 to 7, and preferably 5 to 7. The water washing treatment can be carried out using a neutralizing agent, and the neutralizing agent is a basic substance, and specific examples thereof include an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; An alkaline earth metal hydroxide such as calcium hydroxide or magnesium hydroxide; diethylene triamine, triethylenetetramine, aniline or benzodiazepine An organic amine such as phenylene diamine; ammonia, sodium dihydrogen phosphate or any combination of the above. The above neutralizing agents may be used singly or in combination of plural kinds. The above water washing treatment can be carried out by a conventional method, for example, by adding an aqueous solution containing a neutralizing agent to the solution after the reaction, and carrying out the extraction repeatedly.

After the neutralization treatment or the water washing treatment, the unreacted phenols and the solvent can be removed by distillation under reduced pressure, and concentrated to obtain a compound represented by the formula (IV-1).

Specific examples of the above halogenated propylene oxide may include, but are not limited to, 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane or any of the above compounds. combination. An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or added to the reaction before the dehydrohalogenation reaction. The above dehydrohalogenation reaction may be carried out at a temperature of from 20 ° C to 120 ° C and may be operated for from 1 hour to 10 hours.

In one embodiment, the alkali metal hydroxide added in the dehydrohalogenation reaction may also be an aqueous solution thereof. In this embodiment, 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 to remove water, and The halogenated propylene oxide can be continuously refluxed into the reaction system.

Before the above dehydrohalogenation reaction is carried out, tetramethyl ammonium chloride, tetramethyl ammonium bromide or trimethyl benzyl ammonium chloride may be added. The quaternary ammonium salt acts as a catalyst and reacts at 50 ° C to 150 ° C. After 1 hour to 5 hours, an alkali metal hydroxide or an aqueous solution thereof is added. Then, the dehydrohalogenation reaction is carried out at a temperature of from 20 ° C to 120 ° C, and the reaction time is from 1 hour to 10 hours.

The halogenated propylene oxide is used in an amount of 1 equivalent to 20 equivalents, and preferably 2 equivalents to 10 equivalents, based on the total equivalent of the hydroxyl group in the compound represented by the above formula (IV-1). The total amount of hydroxyl groups in the compound represented by the above formula (III-1) is 1 equivalent, and the amount of the alkali metal hydroxide to be added in the dehydrohalogenation reaction is 0.8 to 15 equivalents, and preferably From 0.9 equivalents to 11 equivalents.

In order to make the above dehydrohalogenation reaction proceed smoothly, it is also possible to add a An alcohol solvent such as an alcohol or ethanol. Further, the dehydrohalogenation reaction can also be carried out using an aprotic polar solvent such as dimethyl sulfone or dimethyl sulfoxide. In the case of using an alcohol solvent, the total amount of the halogenated propylene oxide used is 100% by weight, and the alcohol is used in an amount of 2% by weight to 20% by weight, and preferably 4% by weight to 15% by weight. In the case of using an aprotic polar solvent, the total amount of the halogenated propylene oxide used is 100% by weight, and the aprotic polar solvent is used in an amount of 5 to 100% by weight, and preferably 10% by weight. Percentage to 90 weight percent.

After the completion of the dehydrohalogenation reaction, the water washing treatment can be selectively carried out. Then, the halogenated propylene oxide, the alcohol and the aprotic polarity are removed by means of vacuum distillation, for example, in an environment having a temperature of 110 ° C to 250 ° C and a pressure of less than 1.3 kPa [10 mm Hg). Solvent.

In order to prevent the obtained epoxy resin from having a hydrolyzable halogen, a solvent such as toluene or methyl isobutyl ketone and an aqueous alkali metal hydroxide solution such as sodium hydroxide or potassium hydroxide may be added to The dehydrohalogenation reaction is carried out again in the solution after the dehydrohalogenation reaction. In the dehydrohalogenation reaction, the total equivalent weight of the hydroxyl group in the compound represented by the above formula (III-1) is 1 equivalent, and the alkali metal hydroxide is used in an amount of 0.01 mol to 0.3 mol, and preferably 0.05 moles to 0.2 moles. The above dehydrohalogenation reaction has an operating temperature of 50 ° C to 120 ° C and an operation time of 0.5 hours to 2 hours.

When the dehydrohalogenation reaction is completed, the salt is filtered, washed, etc. Step removal. Further, a solvent such as toluene or methyl isobutyl ketone is removed by distillation under reduced pressure to obtain a compound represented by the formula (IV). Specific examples of the compound represented by the above formula (IV) may include, but are not limited to, those manufactured by Nippon Kayaku Co., Ltd., model number NC-3000, NC-3000H, NC-3000S or NC-3000P.

a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (a2-2)

Specific examples of the compound (a2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group are selected from the group consisting of (1) to (3): (1) acrylic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methylpropenyloxybutyl succinic acid, 2-methylpropenyl oxyethyl adipate, 2 -Methacrylic acid oxiranium adipic acid, 2-methylpropenyloxyethylhexahydrophthalic acid, 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxypropyl Maleic acid, 2-methylpropenyloxybutyl maleic acid, 2-methylpropenyloxypropyl succinic acid, 2-methylpropenyloxypropyl adipate, 2-methylpropene oxime Propyl tetrahydrophthalic acid, 2-methylpropenyl propyl phthalate, 2-methylpropenyl butyl phthalate or 2-methyl propylene oxybutyl phthalate Formic acid; (2) a compound obtained by reacting a (meth) acrylate having a hydroxyl group with a dicarboxylic acid compound, wherein the dicarboxylic acid compound comprises adipic acid, succinic acid, maleic acid or phthalic acid And (3) by having a hydroxyl group a half ester compound obtained by reacting a (meth) acrylate with a carboxylic anhydride compound (a2-3) described later, wherein a (meth) acrylate having a hydroxyl group comprises 2-hydroxyethyl acrylate ], 2-hydroxyethyl methacrylate [(2-hydroxyethyl)methacrylate], 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate [(4-hydroxybutyl)acrylate], 4-hydroxybutyl methacrylate or pentaerythritol trimethacrylate.

Carboxylic anhydride compound (a2-3)

The carboxylic anhydride compound (a2-3) may be selected from the group consisting of (1) and (2) described later: (1) butanedioic anhydride, maleic anhydride, and clothing. Itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride , methyl hexahydrophthalic anhydride, methyl endo-methylene tetrahydro phthalic anhydride, chlorendic anhydride, glutaric anhydride or trimellitic acid a dicarboxylic anhydride compound such as 1,3-dioxoisobenzofuran-5-carboxylic anhydride; and (2) benzophenone tetracarboxylic dianhydride (BTDA) or diphenyltetracarboxylic dianhydride or diphenyl A tetracarboxylic anhydride compound such as ether tetracarboxylic dianhydride.

Compound having an epoxy group (a2-4)

The epoxy group-containing compound (a2-4) may be selected from the group consisting of glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, a glycidyl ether compound having an unsaturated group, and having an epoxy group. Sodium-unsaturated compound or above Any combination of the compounds.

The above glycidyl ether compound having an unsaturated group may be manufactured by Nagase Chemical Co., Ltd., model No. Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX- 171 or Denacol EX-192 and other products.

The second alkali-soluble resin (A-2) may be an epoxy compound (a2-1) having at least two epoxy groups and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (a2-2) a reaction product having a hydroxyl group formed by a polymerization reaction, wherein the epoxy compound (a2-1) having at least two epoxy groups may comprise a compound represented by the formula (III), as shown in the formula (IV) A compound or any mixture of the above materials. Next, a carboxylic anhydride compound (a2-3) is added to the reaction solution to carry out a polymerization reaction. The number of equivalents of the hydroxyl group of the hydroxy group-containing reaction product is 1 equivalent, and the number of equivalents of the acid anhydride group of the carboxylic anhydride compound (a2-3) is from 0.4 equivalents to 1 equivalent, and preferably from 0.75 equivalents to 1 equivalent. When a plurality of carboxylic anhydride compounds (a2-3) are used, such carboxylic anhydride compounds may be added sequentially or simultaneously in the reaction. When a dicarboxylic anhydride compound and a tetracarboxylic anhydride compound are used as the carboxylic anhydride compound (a2-3), the molar ratio of the dicarboxylic anhydride compound and the tetracarboxylic anhydride compound is from 1/99 to 90/10, and It is preferably from 5/95 to 80/20. The above reaction can be operated at a temperature of from 50 ° C to 130 ° C.

The second alkali-soluble resin (A-2) may be an epoxy compound (a2-1) having at least two epoxy groups and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (a2-2) a reaction product having a hydroxyl group formed by the reaction, wherein the epoxy compound having at least two epoxy groups (a2-1) may be a compound represented by formula (III) or formula (IV). Next, a polymerization reaction is carried out by adding a carboxylic anhydride compound (a2-3), a compound having an epoxy group (a2-4), or a combination of the two to the reaction solution. The total number of equivalents of the epoxy group in the compound represented by the formula (III) or the formula (IV) is 1 equivalent, and the above compound (a2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group The acid number equivalents are from 0.8 equivalents to 1.5 equivalents, and preferably from 0.9 equivalents to 1.1 equivalents. The total amount of the hydroxyl group based on the above reaction product having a hydroxyl group is 100 mol%, and the carboxylic anhydride compound (a2-3) is used in an amount of 10 mol% to 100 mol%, preferably 20 mol% to 100%. The percentage of moles, and more preferably from 30 mole percent to 100 mole percent.

When the second alkali-soluble resin (A-2) described above is prepared, in order to shorten the reaction time, a basic compound is generally added to the reaction solution as a reaction catalyst. The reaction catalyst may include, but is not limited to, triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine, tetramethylammonium chloride. Or benzyltriethylammonium chloride or the like. The reaction catalyst may be used singly or in combination of plural kinds.

The total amount of the epoxy compound (a2-1) having at least two epoxy groups and the compound (a2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100 parts by weight, The reaction catalyst is used in an amount of from 0.01 part by weight to 10 parts by weight, and preferably from 0.3 part by weight to 5 parts by weight.

Secondly, in order to control the degree of polymerization, a polymerization inhibitor can be added to the reaction. (polymerization inhibitor) to the reaction solution. The polymerization inhibitor may comprise methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-t-butyl-p-butyl- (2,6-di-t-butyl- P-cresol) or phenothiazine. The polymerization inhibitor may be used singly or in combination of plural kinds.

The total amount of the epoxy compound (a2-1) having at least two epoxy groups and the compound (a2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100 parts by weight, The polymerization inhibitor is used in an amount of from 0.01 part by weight to 10 parts by weight, and preferably from 0.1 part by weight to 5 parts by weight.

When the second alkali-soluble resin (A-2) is prepared, a polymerization solvent can be selectively used. The polymerization solvent may include an alcohol solvent such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol or ethylene glycol; a ketone solvent such as methyl ethyl ketone or cyclohexanone; toluene; Or an aromatic hydrocarbon solvent such as xylene; a cellophane solvent such as cellosolve or butyl cellosolve; carbitol or butyl carbitol a solvent such as a carbaryl solvent; a propylene glycol alkyl ether solvent such as propylene glycol monomethyl ether; a polypropylene glycol alkyl ether such as dipropylene glycol monoether [di(propylene glycol) methyl ether] Poly(propylene glycol) alkyl ether] solvent; acetic acid such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate or propylene glycol methyl ether acetate Ester solvent; lactic acid such as ethyl lactate or butyl lactate An alkyl lactate solvent; or a dialkyl glycol ether solvent. The polymerization solvent may be used singly or in combination of plural kinds.

The acid value of the second alkali-soluble resin (A-2) is from 50 mgKOH/g to 200 mgKOH/g, and preferably from 60 mgKOH/g to 150 mgKOH/g.

When the alkali-soluble resin (A) contains the second alkali-soluble resin (A-2), the obtained color filter photosensitive resin composition has better alkali resistance.

Compound having ethylenically unsaturated group (B)

The compound (B) having an ethylenically unsaturated group of the present invention may comprise an alkoxy-modified first compound, a caprolactone-modified second compound, the aforementioned alkoxy-modified compound, and caprolactone modified. A third compound other than the compound or any combination of the above compounds.

Alkoxy-modified first compound

The alkoxy-modified first compound may include, but is not limited to, a compound represented by the following formula (V), a compound represented by the following formula (VI), a compound represented by the following formula (VII), or any combination of the above compounds. :

In the formulae (V) to (VII), Z ₁ independently represents or ; Z ₂ each independently represents an acryloyl group, a methacryloyl group or a hydrogen atom; and Z ₃ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aromatic group having 1 to 6 carbon atoms; In the formula (V), the total amount of the acryl fluorenyl group and the methacryl fluorenyl group is 5 or 6; in the formula (VI), the total amount of the acryl fluorenyl group and the methacryl fluorenyl group is 3 or 4; In VII), the total number of propylene fluorenyl groups and methacryl fluorenyl groups is 3; f each independently represents an integer of 0 to 6, and the sum of f is 3 to 24; g each independently represents an integer of 0 to 6, And the sum of g is 2 to 16; h each independently represents an integer of 0 to 10, and the sum of h is 3 to 30; and i represents an integer of 0 to 3.

In formula (V) to formula (VII), when Z ₁ represents or Z _{1 is} preferably bonded to Z ₂ by an oxygen atom.

In the formula (V), Z _{2 is} preferably an allyl group.

The compound represented by formula (V) or formula (VI) can be subjected to the following steps Synthesis: First, a pentaerythritol or dipentaerythritol is reacted to form a ring-opening skeleton by a ring-opening addition reaction of ethylene oxide or propylene oxide. Next, (meth)acrylofluorene chloride is reacted with a terminal hydroxyl group of the ring-opening skeleton to form a (meth)acrylonitrile group.

The compound represented by the formula (V) and the formula (VI) is more preferably a pentaerythritol derivative, a dipentaerythritol derivative or a combination of the above compounds.

Specific examples of the compound represented by the formula (V) may include, but are not limited to, the compounds represented by the following formulas (V-1) to (V-3):

In the formula (V-1), the sum of n may be 6 or 12. In the formula (V-2), the sum of n is 12. In the formula (V-3), the sum of n is 6.

Preferably, the compound of formula (V) may be of formula (V-1).

Specific examples of the compound represented by the formula (VI) may include, but are not limited to, the compound represented by the following formula (VI-1), or Ethoxylated Pentaerythritol tetraacrylate or propoxylated pentaerythritol IV. Propoxylated Pentaerythritol tetraacrylate:

In the formula (VI-1), the sum of p may be 4 or 12.

The compound represented by the formula (VI) may be a commercial product, for example, a product manufactured by Changxing Chemical Industry Co., Ltd., model number EM2411 or EM2421, or a product manufactured by Toyo Chemical Co., Ltd., model Miramer M4004.

Specific examples of the compound represented by the above formula (VII) may include, but are not limited to, Ethoxylated Trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate (Ethoxylated Trimethylolpropane trimethacrylate), Propoxylated Trimethylolpropane Triacrylate or Propoxylation Propoxylated Glyceryl triacrylate.

The compound represented by the formula (VII) may be a commercial product such as a product manufactured by Nippon Kayaku Co., Ltd., and its model number is KAYARAD GPO-303, KAYARAD THE-330, KAYARAD TPA-320 or KAYARAD TPA-330. ; products manufactured by East Asia Synthetic Co., Ltd., model number M-310, M-321, M-350, M-360 or M-460; products manufactured by Satoma Co., Ltd., model number SR415, SR454, SR492, SR499, CD501, SR502, SR9020, SR9021 or SR9035; products manufactured by Changxing Chemical Industry Co., Ltd., model number EM2380, EM2381, EM2382, EM2383, EM2384, EM2385, EM2386, EM2387 or EM3380; Toyo Chemical Co., Ltd. The manufactured product is model Miramer M3130, Miramer M3160, Miramer M3190 or Miramer M360. The above compounds may be used singly or in combination of plural kinds.

Caprolactone modified second compound

The second compound modified by the caprolactone of the present invention may have a compound represented by the following formula (VIII):

In the formula (VIII), Z ₄ and Z ₅ each independently represent a hydrogen atom or a methyl group; m each independently represents an integer of 1 to 2; j represents an integer of 1 to 6; k represents an integer of 0 to 5; The sum of j and k is 2 to 6.

The second compound modified by caprolactone may be a (meth) acrylate compound obtained by reacting a caprolactone-modified polyol with (meth)acrylic acid.

The above-mentioned caprolactone-modified polyol is formed by reacting caprolactone with a polyol having four or more functional groups. The above caprolactone may be γ-caprolactone, δ-caprolactone, ε-caprolactone or any combination of the above compounds. Preferably, the caprolactone may be ε-caprolactone.

The above polyol having four or more functional groups may be pentaerythritol, ditrimethylolpropane, dipentaerythritol or any combination of the above compounds.

The above-mentioned caprolactone is preferably used in an amount of from 1 mol to 12 mol based on the use of the above polyol having four functional groups or more in an amount of 1 mol.

Specific examples of the second compound modified with caprolactone may include, but are not limited to, pentaerythritol caprolactone modified tetra(meth)acrylate compound, ditrimethylolpropane caprolactone modified tetra(methyl) An acrylate compound, a dipentaerythritol caprolactone modified poly(meth) acrylate compound or a combination of the above compounds.

Specific examples of the dipentaerythritol caprolactone-modified poly(meth) acrylate compound may be dipentaerythritol caprolactone-modified di(meth) acrylate compound or dipentaerythritol caprolactone modified three (Meth) acrylate compound, dipentaerythritol caprolactone modified tetra(meth) acrylate compound, dipentaerythritol caprolactone modified penta (meth) acrylate compound, dipentaerythritol caprolactone A modified hexa(meth)acrylate compound or any combination of the above compounds.

The second compound modified by the caprolactone may be a product manufactured by Nippon Kayaku Co., Ltd., and its model number is KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 or DPCA-120.

Third compound

The third compound may have a functional group represented by the following formula (IX):

In the formula (IX), Z ₆ represents a hydrogen atom or a methyl group.

Specific examples of the third compound may be acrylamide, (meth) propylene morpholine, (meth) acrylate-7-amino-3,7-dimethyloctyl ester, isobutoxymethyl (a) Base acrylamide, isobornyl oxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl diglycol (meth) acrylate Ester, third octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethyl amino (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylate Dicyclopenteneoxyethyl 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-tetrabromophenoxyethyl (meth)acrylate, (methyl) 2-trichlorophenoxyethyl acrylate, tribromophenyl (meth)acrylate, 2-tribromophenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, vinyl caprolactam, nitrogen-vinyl tyrosone, (meth) propylene Acid phenoxyethyl ester, pentachlorophenyl (meth)acrylate, pentabromophenyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, ( Methyl acrylate borneol ester, 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, triethylene glycol di(meth) acrylate, neopentyl glycol di(meth) acrylate, 1,4-butanediol di(meth) acrylate, 1, 6-hexanediol di(meth)acrylate, trimethylolpropane triacrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexaacrylate, pentaerythritol tetra(methyl) Acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(4) Methyl) acrylate, ditrimethylol propyl tetra(meth)acrylate, EO modified bisphenol A di(meth) acrylate, PO modification Bisphenol A di(meth)acrylate, EO modified hydrogenated bisphenol A di(meth)acrylate, PO modified hydrogenated bisphenol A di(meth)acrylate, EO modified bisphenol F Di(meth)acrylate, phenolic polyglycidyl ether (meth) acrylate or any combination of the above.

Preferably, the third compound may be trimethylolpropyl methacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, tetraacrylic acid tris. A product manufactured by hydroxymethyl propyl ester or Japan East Asia Synthetic Co., Ltd., model number TO-1382, or any combination of the above compounds.

The compound (B) having an ethylenically unsaturated group is used in an amount of 40 parts by weight to 400 parts by weight, preferably 50 parts by weight to 300 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (A). More preferably, it is 60 parts by weight to 200 parts by weight.

Photoinitiator (C)

The photoinitiator (C) of the present invention may have an O-fluorenyl oxime-based photoinitiator, a triazine-based photoinitiator, an acetophenone-based compound, and two A compound of a biimidazole or a benzophenone.

Specific examples of the O-fluorenyl fluorene photoinitiator may include 1-[4-(phenylthio)phenyl]-heptane-1,2-dione-2-(O-phenylhydrazinium). , 1-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-phenylhydrazinyl), 1-[4-(phenylindenyl)phenyl] -heptane-1,2-dione-2-(O-phenylhydrazinium), 1-[9-ethyl-6-(2-methylphenylhydrazino)-9H-carbazole-3-substituted Ethyl]-ethane ketone-1-(O-acetamidoxime), 1-[9-ethyl-6-(3-methylphenylhydrazino)-9H-carbazole-3-substituent]-B Alkanone-1-(O-ethylindenyl), 1-[9-ethyl-6-benzoin-9H-indazole-3-substituted]-ethanone-1-(O-acetamidine) Ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylbenzoyl)-9H-indazole-3-substituted]-1-(O-B Ethyl ketone), ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylphenyl)-9H-indazole-3-substituted]-1- (O-Ethylhydrazine), Ethyl Ketone-1-[9-Ethyl-6-(2-methyl-5-tetrahydrofurylbenzoyl)-9H-indazole-3-Substituent]-1 -(O-acetylhydrazine), ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylphenyl)-9H-indazole-3-substituted 1,-1-(O-ethylindenyl), ethane ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxyphenyl)-9H-carbazole -3-substituent]-1-(O-acetonitrile Ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylmethoxyphenyl)-9H-indazole-3-substituent]- 1-(O-Ethylindole), Ethyl Ketone-1-[9-Ethyl-6-(2-methyl-5-tetrahydrofurylmethoxybenzoinyl)-9H-indazole-3- Substituent]-1-(O-acetamidoxime), ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydropyranylmethoxyphenyl)- 9H-carbazole-3-substituted]-1-(O-acetylindenyl), ethane ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-di Methyl-1,3-dioxolanyl)phenylhydrazinyl}-9H-indazole-3-substituted]-1-(O-acetylindenyl), ethane ketone-1-[9- Ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxyphenylhydrazino}-9H-indazole-3-substituent ]-1-(O-ethylindenyl) or any combination of the above compounds.

Specific examples of the triazine-based photoinitiator may include 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene [2,4] -Bis(trichloromethyl)-6-(p-methoxy)styryl-s-triazine], 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3 -butadienyl-s-tris-tris (trimethylmethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazine], 2-trichloromethyl 4-Aminochloro-4-phenyl-6-(p-methoxy)styryl-s-triazine or any of the above compounds combination.

Specific examples of the acetophenone compound may be p-dimethylamine acetophenone, α,α'-dimethoxyoxyazobenzophenone, 2,2'-dimethyl-2-phenyl Acetophenone, p-methoxyacetophenone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, 2-benzyl-2-N, N-dimethylamine-1-(4-morpholine Phenyl)-1-butanone or any combination of the above.

Specific examples of the biimidazole compound may include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-double (ortho) -fluorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyl Diimidazole, 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-ethylphenyl)- 4,4',5,5'-tetraphenyldiimidazole, 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-chlorobenzene -4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl Imidazole or any combination of the above compounds.

Specific examples of the benzophenone compound may include thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-oxime, diphenylketone, 4,4'-bis (two Methylamine) Diphenyl ketone, 4,4'-bis(diethylamine) diphenyl ketone or any combination of the above.

The foregoing compounds may be used singly or in combination of plural kinds.

Preferably, the photoinitiator (C) is 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-phenylhydrazinium), 1 -[9-ethyl-6-(2-methylphenylhydrazino)-9H-indazole-3-substituted]-ethanone 1-(O-acetamidoxime), ethane ketone-1- [9-Ethyl-6-(2-methyl-4-tetrahydrofuranmethoxyphenyl)]-9H-indazole-3-substituted]-1-(O-ethylindenyl), ethane ketone -1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoquinone}-9H-oxime Zyridin-3-substituted]-1-(O-ethylindenyl), 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazabenzene, 2 -benzyl-2-N,N-dimethylamine-1-(4-morpholinophenyl)-1-butanone, 2,2'-bis(2,4-dichlorophenyl)-4 , 4', 5, 5'-tetraphenyl dimimi Carbazole, 4,4'-bis(diethylamine) diphenyl ketone or any combination of the above.

The photoinitiator (C) is used in an amount of 10 parts by weight to 100 parts by weight, preferably 15 parts by weight to 80 parts by weight, based on the total amount of the alkali-soluble resin (A) used in an amount of 100 parts by weight, and more preferably 20 parts by weight to 60 parts by weight.

Organic solvent (D)

The organic solvent (D) must be capable of dissolving the aforementioned alkali-soluble resin (A), the compound (B) having an ethylenically unsaturated group, the photoinitiator (C), and the pigment (E), dye (F) and additives described later. (G), and the organic solvent (D) does not react with these components and has appropriate volatility.

Specific examples of the organic solvent (D) may include 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, Triethylene glycol ethyl 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 methyl ether, condensate a (poly)alkylene glycol monoalkyl ether solvent such as tripropylene glycol ether; (poly)alkylene such as ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol diethyl ether acetate Base glycol monoalkyl ether acetate solvent; diglyme, diethylene glycol methyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ether solvents; methyl ethyl ketone, cyclohexanone, 2-heptanone a ketone solvent such as 3-heptanone; an alkyl lactate solvent such as methyl 2-hydroxypropionate or ethyl 2-hydroxypropionate; methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2 -ethyl methacrylate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate (EEP) , Group, ethyl hydroxyacetate, 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-Butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetate , other ester solvents such as ethyl acetate, ethyl 2-oxybutyrate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N-dimethylformamide And a carboxylic acid guanamine solvent such as N,N-dimethylacetamide.

The aforementioned organic solvent (D) may be used singly or in combination of plural kinds.

Preferably, the organic solvent (D) may be propylene glycol methyl ether acetate or ethyl 3-ethoxypropionate.

The total amount of the alkali-soluble resin (A) used is 100 parts by weight, and the organic solvent (D) is used in an amount of from 500 parts by weight to 5,000 parts by weight, preferably from 1,000 parts by weight to 4,500 parts by weight, more preferably It is preferably from 1,500 parts by weight to 4,000 parts by weight.

Pigment (E)

The pigment (E) of the present invention may be an inorganic pigment, an organic pigment or any combination of the above pigments.

The above inorganic pigment may be a metal compound such as a metal oxide or a metal salt compound. The metal oxide may be 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 above organic pigment is selected from C.I. 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, 180,185,187,188,190,193,194,202,206,207,208,209,215,216,22 0,224,226,242,243,245,254,255,264,265; 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; CI Pigment Brown 23,25,28; and CI Pigment Black 1,7. The aforementioned organic pigments may be used singly or in combination of plural kinds.

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

The total amount used based on the alkali-soluble resin (A) is 100 parts by weight, The pigment (E) is used in an amount of 30 parts by weight to 300 parts by weight, preferably 40 parts by weight to 250 parts by weight, and more preferably 50 parts by weight to 200 parts by weight.

When necessary, the pigment (E) may optionally contain a dispersant, and specific examples thereof include a surfactant such as a cationic system, an anionic system, a nonionic system, an amphoteric group, a polyoxyalkylene group or a fluorine compound.

The surfactant may include, but is not limited to, polyethylene oxide alkyl ethers such as polyethylene oxide lauryl ether, polyethylene oxide stearyl ether or polyethylene oxide oleyl ether; Polyethylene oxide alkyl phenyl ether surfactant such as ethylene oxide octyl phenyl ether or polyethylene oxide nonyl phenyl ether; polyethylene glycol dilaurate or polyethylene glycol distearyl Polyethylene glycol diester surfactant such as acid ester; sorbitan fatty acid ester surfactant; fatty acid modified polyester surfactant; tertiary amine modified polyurethane interface Active agent; manufactured by Shin-Etsu Chemical Co., Ltd., model KP; manufactured by Toray Dow Corning Silicon, model SF-8427; manufactured by Kyoei Oil & Fat Chemical Industry, model of Polyflow; Tochem Products Co., Ltd. manufactured by F-Top; manufactured by Dainippon Ink Chemical Industry, model Megafac; Sumitomo 3M, model Fluorad; Asahi Glass, model Asahi Guard or Surflon commodity. The surfactant may be used singly or in combination of plural kinds.

Dye (F)

The photosensitive resin composition of the present invention may optionally contain a dye (F). The dye (F) is preferably a dye which is commonly used for color filters having high brightness and high contrast. The dye of the present invention may include, but is not limited to, the following specific example.

Specific examples of red dyes, such as: CI acid red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 , 22, 23, 24, 25, 25:1, 26, 26:1, 26:2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42 , 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76 : 1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115 , 116, 120, 123, 125, 127, 128, 131, 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158 160,161,163,164,167,170,171,172,173,175,176,177,181,229,231,237,239,240,241,242,249, 252,253,255,257 , 260, 263, 264, 266, 267, 274, 274, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343 , 344, 347, 348, 350, 351, 35 3. Red dyes such as 354, 356 or 388.

Secondly, the red dye can also be CI direct red, 2:1, 4, 5, 6, 7, 8, 10, 10:1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24 , 26, 26: 1, 28, 29, 31, 33, 33: 1, 34, 35, 36, 37, 39, 42, 43, 43: 1, 44, 46, 49, 52, 53, 54, 55 , 56, 57, 58, 59, 60, 61, 62, 67, 67: 1, 68, 72, 72: 1, 73, 74, 75, 77, 78, 79, 81, 81: 1, 85, 86 , 88, 89, 90, 97, 100, 101, 101: 1, 107, 108, 110, 114, 116, 117, 120, 121, 122, 122: 1, 124, 125, 127, 127: 1, 127: 2, 128, 129, 130, 132, 134, 135, 136, 137, 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171, 172, 173, 174, 175, 176, Red dyes of 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237 or 238.

The yellow dye can be CI acid yellow 2, 3, 4, 5, 6, 7, 8, 9, 9:1, 10, 11, 11:1, 12, 13, 14, 15, 16, 17, 17:1 , 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40:1, 41, 42, 42:1, 43, 44 , 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117 , 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188 a yellow dye such as 189, 190, 191, 192 or 199.

Secondly, the yellow dye can also be CI direct yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44:1. 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, Yellow dye of 118, 119, 120, 121, 126, 127, 129, 132, 133 or 134.

The orange dye can be C.I. Acidic Orange 1, 1:1, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 17, 18, 19, 20, 20: 1, 22, 23, 24, 24: 1, 25, 27, 28, 28: 1, 30, 31, 33, 35, 36, 37, 38, 41, 45, 49, 50, 51, 54, 55, 56, 59, 79, 83, 94, 95, 102, 106, 116, 117, 119, 128, 131, 132, 134, An orange dye of 136 or 138 or the like.

Secondly, the orange dye can also be CI direct orange 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, 17, 19, 20, 21, 24, 25, 26, 29, 29:1. 30, 31, 32, 33, 43, 49, 51, 56, 59, 69, 72, 73, 74, 75, 76, 79, 80, 83, 84, 85, 87, 88, 90, 91, 92, An orange dye of 95, 96, 97, 98, 101, 102, 102: 1, 104, 108, 112 or 114.

The blue dye may be CI Acid Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34, 35, 37, 40, 41, 41: 1, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 62, 62, 6, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 84, 85, 86, 88, 89, 90, 90: 1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127:1 128, 129, 135, 137, 138, 143, 145, 147, 150, 155, 159, 169, 174, 175, 176, 183, 198, 203, 204, 205, 206, 208, 213, 227, 230, Blue of 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278 or 280 Color dyes.

Secondly, the blue dye can also be CI Direct Blue 1, 2, 3, 4, 6, 7, 8, 8:1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21:1. 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98: 1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129, 130, 130: 1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158: 1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, A blue dye of 207, 209, 213, 215, 225, 226, 229, 230, 231, 242, 243, 244, 253, 254, 260 or 263.

The purple dye can be CI Acid Violet 1, 2, 3, 4, 5, 5: 1, 6, 7, 7: 1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21 , 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102 , purple dye of 103 or 109, etc.

Secondly, the purple dye can be CI direct violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27 , 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64 A violet dye of 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93 or 97.

The green dye can be C.I. Acid Green 2, 3, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 25: 1, 27, 34, 36, 37, 38, 40, 41, 42, 44, 54, 55 Green dyes such as 59, 66, 69, 70, 71, 81, 84, 94 or 95.

Secondly, the green dye may also be a green dye of C.I. Direct Green 11, 13, 14, 24, 30, 34, 38, 42, 49, 55, 56, 57, 60, 78, 79 or 80.

The dye (F) is used in an amount of from 4 parts by weight to 40 parts by weight, based on the total amount of the alkali-soluble resin (A), and preferably from 5 parts by weight to 35 parts by weight, and more preferably 6 parts by weight. Up to 30 parts by weight.

The photosensitive resin composition obtained has a preferable contrast ratio when the total amount of the alkali-soluble resin (A) is 100 parts by weight and the dye (F) is used in an amount of 4 parts by weight to 40 parts by weight.

Additive (G)

The photosensitive resin composition of the present invention may further optionally further comprise an additive (G) without affecting the efficacy of the present invention. Specific examples of the additive (G) may include a filler, a polymer other than the alkali-soluble resin (A), an adhesion promoter, an antioxidant, an ultraviolet absorber, or an anti-aggregation agent.

Specific examples of the filler may include glass or aluminum or the like.

Specific examples of the polymer may include polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate or any combination of the above polymers.

Specific examples of the adhesion promoter may include vinyltrimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, and N-(2-aminoethyl)- 3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxysulfonium Alkane, 3-glycidylpropyltrimethoxydecane, 3-glycidylpropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropoxypropyltrimethoxydecane, 3-thiolpropyltrimethoxydecane or the above Any combination of compounds.

Specific examples of the antioxidant may include 2,2-thiobis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol or any combination of the above compounds.

Specific examples of the ultraviolet absorber may be 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide, alkoxyphenone or the above compound Any combination.

Specific examples of the anti-agglomerating agent may include sodium polyacrylate or the like.

The additive (G) is used in an amount of from 0 part by weight to 100 parts by weight, based on the total amount of the alkali-soluble resin (A), preferably from 1 part by weight to 80 parts by weight, and more preferably 5 parts by weight. Parts to 60 parts by weight

Preparation of photosensitive resin composition for color filter

The photosensitive resin composition for a color filter is prepared by using the above-mentioned alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photoinitiator (C), and an organic solvent (D). The pigment (E) is placed in a stirrer to be stirred, and uniformly mixed into a solution state, and if necessary, a dye (F) and an additive (G) are selectively added.

Color filter manufacturing method

The present invention also provides a method of forming a color filter, wherein a pixel layer is formed using the photosensitive resin composition for the color filter, and the pixel layer is hereinafter referred to as a pixel coloring layer.

The present invention also provides a color filter formed by using the above-described method of forming a color filter.

The method for forming a color filter sequentially includes a step of forming a photosensitive layer by using a photosensitive resin composition for a color filter, a step of patterning the photosensitive layer to cure an exposed region, and removing an unexposed region by alkaline development a step of forming a pattern, a step of re-solidifying to form a pixel colored layer, and a step of sputtering an indium tin oxide (ITO) protective film.

The step of forming the photosensitive layer is a method of applying a photosensitive resin composition for a color filter in a solution state on a substrate by a coating method such as spin coating, cast coating or roll coating.

The substrate may be an alkali-free glass, a soda-lime glass, a hard glass (Pyrus glass), a quartz glass, and such a glass to which a transparent conductive film is attached, or used for a photoelectric conversion device (for example, a liquid crystal display device). A substrate (such as a germanium substrate) of a solid-state imaging device.

Further, before the photosensitive resin composition for a color filter is applied onto the substrate, a black matrix for shielding a coloring layer such as red, green, or blue may be formed on the substrate.

After the coating layer is formed, most of the organic solvent of the photosensitive resin composition for a color filter is removed by vacuum drying. Then, the residual organic solvent is completely removed in a pre-bake manner to form a prebaked coating film.

The operating conditions of the above-described reduced-pressure drying and pre-baking may vary depending on the type and blending ratio of each component. The drying under reduced pressure is generally carried out at a pressure of from 0 torr to 200 torr for 1 second to 60 seconds, and prebaking is generally carried out at 70 to 110 ° C for 1 minute to 15 minutes.

The aforementioned exposure step exposes the pre-baked coating film described above with a mask having a specific pattern. The light used in the exposure process is preferably ultraviolet light such as g-line, h-line or i-line, and the device for providing ultraviolet rays may be (ultra) high pressure mercury lamp and metal halide lamp.

In the foregoing development step, the exposed pre-baked coating film is immersed in a developing solution at a temperature of 21 ° C to 25 ° C for about 15 seconds to 5 minutes to remove the exposed pre-baked coating film. A portion required to form a semi-finished product having a pixel-colored layer of a predetermined pattern.

The developer used above may be sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, aqueous ammonia, ethylamine, diethylamine, Dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, acridine or 1,8-diazabicyclo-(5,4,0)-7-undecene An alkaline aqueous solution composed of a compound.

The concentration of the developer may generally be 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.

The aforementioned re-cure step is to clean the substrate (the semi-finished product having the pixel-colored layer on the substrate and having a predetermined pattern on the substrate) with water to remove unnecessary portions of the exposed pre-baked coating film. Then, the semi-finished layer of the pixel-colored layer having the predetermined pattern is dried by using compressed air or compressed nitrogen. Product. Next, the semi-finished product of the above-described pixel-colored layer having a predetermined pattern is subjected to a post-bake treatment using a heating means such as a hot plate or an oven, and the heating temperature may be 150 ° C to 250 ° C. When a hot plate is used, the heating time is from 5 minutes to 60 minutes. If an oven is used, the heating time is from 15 minutes to 150 minutes. After the post-baking treatment, the pattern of the semi-finished product of the pixel-colored layer having the predetermined pattern is fixed to form a pixel-colored layer.

Repeating the above steps, a red, green, blue, and the like pixel colored layer are sequentially formed on the substrate.

The step of sputtering the ITO protective film is performed in a vacuum environment of 220 ° C to 250 ° C to form an ITO protective film on the surface of the aforementioned pixel colored layer by a sputtering process. If necessary, the ITO protective film is etched and patterned, and a liquid crystal alignment film is coated on the surface of the ITO protective film to form a color filter having a pixel layer.

Method for preparing liquid crystal display

The present invention also provides a liquid crystal display comprising the aforementioned color filter.

The liquid crystal display is disposed by arranging the above-described color filter and a substrate provided with a thin film transistor (TFT), and providing a gap (cell gap) between the two. Then, the color filter is attached to the peripheral portion of the above substrate with an adhesive and the injection hole is left. Next, liquid crystal is injected from the injection hole in the gap between the surface of the substrate and the adhesive, and the injection hole is sealed to form a liquid crystal layer. Thereafter, the polarizing plate is disposed in the color filter to contact the other side of the liquid crystal layer and the substrate The other side of the liquid crystal layer is contacted to form a liquid crystal display.

The liquid crystal may be a liquid crystal compound or a liquid crystal composition, and is not particularly limited herein, and any liquid crystal compound and liquid crystal composition may be used.

Further, the liquid crystal alignment film used in the color filter is used to restrict the alignment of the liquid crystal molecules, and is not particularly limited, and any of inorganic substances or organic substances may be used, and the present invention is not limited thereto.

The following embodiments are used to illustrate the application of the present invention, and are not intended to limit the present invention. Those skilled in the art can make various changes without departing from the spirit and scope of the present invention. Retouching.

100‧‧‧ device

110‧‧‧Photosensitive resin layer

120‧‧‧Polar plate

120a‧‧ Direction

130‧‧‧Polar plate

130a‧‧ Direction

140‧‧‧Light source

150‧‧‧luminometer

200‧‧‧ device

210‧‧‧Photosensitive resin layer

220‧‧‧Polar plate

220a‧‧ Direction

230‧‧‧Polar plate

230a‧‧ Direction

240‧‧‧Light source

250‧‧‧luminometer

Fig. 1 is a perspective view showing a detecting device for contrast in an evaluation method according to the present invention.

Fig. 2 is a perspective view showing another detecting device for contrast in the evaluation mode according to the present invention.

Preparation of first alkali soluble resin (A-1)

The first alkali-soluble resin of Synthesis Examples A-1-1 to A-1-14 was prepared according to Table 1 below.

Synthesis Example A-1-1

A nitrogen inlet is placed on a four-necked cone of 1000 ml volume. Mixer, heater, condenser and thermometer. After introducing nitrogen gas, 5 parts by weight of methyl 1,2,2,6,6-pentamethyl-piperidyl acrylate (hereinafter abbreviated as FA-711MM), and 10 parts by weight of 3-(methacrylonitrile) Oxy) oxetane, 25 parts by weight of 2-methylpropenyl ethoxy succinate (hereinafter abbreviated as HOMS), 20 parts by weight of dicyclopentenyl acrylate (hereinafter abbreviated as FA-511A) 25 parts by weight of styrene (hereinafter abbreviated as SM), 5 parts by weight of benzyl methacrylate (hereinafter abbreviated as BzMA), and 10 parts by weight of methyl methacrylate (hereinafter abbreviated as MMA) are dissolved in 200 parts by weight of ethyl 3-ethoxypropionate (hereinafter abbreviated as EEP), wherein the monomer is fed in a continuous manner.

After stirring evenly, the temperature of the oil bath was raised to 100 °C. Then, 4 parts by weight of a polymerization initiator 2,2'-azobis-2-methylbutyronitrile (hereinafter abbreviated as AMBN) was dissolved in the EEP, and added in an interval of one hour in five equal portions. Into the four-necked flask.

The reaction temperature of the polymerization process was maintained at 100 °C. After 6 hours, the polymerization product was taken out from a four-necked flask, and the solvent was devolatilized to obtain a first alkali-soluble resin (hereinafter abbreviated as A-1-1) of Synthesis Example A-1-1.

Synthesis Examples A-1-2 to A-1-14

Synthesis Examples A-1-2 to A-1-14 were prepared in the same manner as in the production method of the first alkali-soluble resin of Synthesis Example A-1-1 except that Synthesis Examples A-1-2 to A -1-14 is a modification of the kind, usage amount, and polymerization conditions of the raw material in the first alkali-soluble resin, and the formulation and polymerization conditions are as shown in Table 1, and will not be further described herein. In addition, in the first table, "continuous addition" It means that the monomer for copolymerization is continuously added to the reactor, and the reaction is continuously carried out and continuously discharged; and "one-time addition" means that the monomer for copolymerization is completely added to the reactor at one time, and once again, the reaction is completed completely. Discharge.

Preparation of a second alkali soluble resin (A-2)

Synthesis Example A-2-1

First, 100 parts by weight of a ruthenium epoxy compound (manufactured by Nippon Steel Chemical Co., Ltd., model ESF-300, and having an epoxy equivalent of 231), 30 parts by weight of acrylic acid, and 0.3 parts by weight of benzyl chloride Triethylammonium, 0.1 part by weight of 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were added in a continuous manner to a 500 ml four-necked flask. The feed rate was controlled at 25 parts by weight/minute, and the temperature of the reaction process was maintained at 100 ° C to 110 ° C. After 15 hours of reaction, a pale yellow transparent mixture having a solid concentration of 50% by weight was obtained.

Next, 100 parts by weight of the above mixture was added to 25 parts by weight of ethylene glycol ethyl ether acetate, while 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of benzophenone tetracarboxylic dianhydride were added. And heated to 110 ° C to 115 ° C. After reacting for 2 hours, a second alkali-soluble resin (hereinafter abbreviated as A-2-1) of Synthesis Example A-2-1 having an acid value of 98 mgKOH/g and a weight average molecular weight of 2,205 was obtained.

Synthesis Example A-2-2

100 parts by weight of a ruthenium epoxy compound (manufactured by Nippon Steel Chemical Co., Ltd., model ESF-300, and having an epoxy equivalent of 231), 30 parts by weight of acrylic acid, and 0.3 parts by weight of benzyltriethyl chloride Base ammonium, 0.1 weight A portion of 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. The feed rate was controlled at 25 parts by weight/minute, and the temperature of the reaction process was maintained at 100 ° C to 110 ° C. After reacting for 15 hours, a pale yellow transparent mixture having a solid concentration of 50% by weight was obtained.

Next, 100 parts by weight of the above mixed solution was added to 25 parts by weight of ethylene glycol ethyl ether acetate while 13 parts by weight of benzophenonetetracarboxylic dianhydride was added, and heated to 90 ° C to 95 ° C. After reacting for 2 hours, 6 parts by weight of tetrahydrophthalic anhydride is added, and the reaction is carried out at 90 ° C to 95 ° C for 4 hours to obtain a second alkali-soluble resin of Synthesis Example A-2-2 (hereinafter referred to as It is A-2-2), and its acid value is 99.0 mgKOH/g, and the weight average molecular weight is 2630.

Synthesis Example A-2-3

400 parts by weight of an epoxy compound (manufactured by Nippon Kayaku Co., Ltd., model number NC-3000, and having an epoxy equivalent of 288), 102 parts by weight of acrylic acid, 0.3 parts by weight of methoxyphenol, 5 parts by weight of triphenylphosphine and 264 parts by weight of propylene glycol monomethyl ether acetate were added to the reaction flask, and the temperature was maintained at 95 °C. After 9 hours of reaction, an intermediate product having an acid value of 2.2 mgKOH/g was obtained. Next, 151 parts by weight of tetrahydrophthalic anhydride was added and reacted at 95 ° C for 4 hours to obtain a second alkali-soluble resin of Synthesis Example A-2-3 (hereinafter referred to as A). -2-3), the acid value was 102 mgKOH/g, and the weight average molecular weight was 3,200.

Preparation of photosensitive resin composition

The photosensitive resin compositions of Examples 1 to 12 and Comparative Examples 1 to 8 were prepared according to Tables 2 and 3 below.

Example 1

100 parts by weight of the first alkali-soluble resin (A-1-1), 40 parts by weight of dipentaerythritol hexaacrylate (hereinafter abbreviated as B-1), and 3 parts by weight of 2-methyl-1-(4- Methylthiophenyl)-2-morpholino-1-propanone (hereinafter abbreviated as C-1), 3 parts by weight of 2,2'-bis(2,4-dichlorophenyl)-4,4 ',5,5'-tetraphenyldiimidazole (hereinafter abbreviated as C-2), 4 parts by weight of 4,4'-bis(diethylamine)benzophenone (hereinafter referred to as C-3), 30 Parts by weight of pigment (which is a mixture of CIPigment R254/CIPigment Y139=80/20, and hereinafter referred to as E-1) and 0.1 part by weight of 2,2-thiobis(4-methyl-6- Tributylphenol) (hereinafter abbreviated as G-2) is added to 500 parts by weight of ethyl 3-ethoxypropionate (hereinafter abbreviated as D-1), and stirred with a shaking type stirrer. After uniformity, the photosensitive resin composition of Example 1 was obtained. The obtained photosensitive resin composition was evaluated by the following evaluation methods of alkali resistance, voltage holding ratio, and contrast, and the obtained result is shown in Table 2.

Examples 2 to 12 and Comparative Examples 1 to 8

In Examples 2 to 12 and Comparative Examples 1 to 8, the same production method as that of the photosensitive resin composition of Example 1 was used, except that Examples 2 to 12 and Comparative Examples 1 to 8 were used to change the photosensitivity. The type and amount of the raw materials in the resin composition, and the formulations and evaluation results thereof are shown in Tables 2 and 3, respectively, and will not be further described herein.

Evaluation method

Alkali resistance

The photosensitive resin compositions of the above Examples 1 to 12 and Comparative Examples 1 to 8 were applied by spin coating on a glass substrate each having a length and a width of 100 mm. Then, drying under reduced pressure was carried out under a pressure of about 100 mmHg (mmHg). After 30 seconds, the glass substrate was prebaked at 80 ° C for 2 minutes to form a prebaked film having a film thickness of 2.5 μm.

Next, the above prebaked coating film was irradiated with ultraviolet light of 100 mJ/cm ² (mJ/cm ² ) using an exposure machine (manufactured by Canon, model: PLA-501F). After the exposure, the film was baked at 235 ° C for 30 minutes to form a photosensitive resin layer having a film thickness of 2.0 μm on the glass substrate.

The chromaticity (L ^* , a ^* , b ^* ) of the photosensitive resin layer was measured with a colorimeter (manufactured by Otsuka Electronics Co., Ltd., model MCPD). Then, the photosensitive resin layer was immersed in an alkali solution (potassium hydroxide at a concentration of 0.5% by weight) at 23 °C. After 60 minutes, the chromaticity was measured again, and the alkali-resistant chromatic aberration (ΔEab ^* ) of the photosensitive resin layer was calculated by the following formula (X), and evaluated according to the following criteria: ΔEab ^* = [(ΔL) ² +(△a) ² +(△b) ² ] ^1/2 formula (X)

☆: △ Eab ^* <1.

◎: 1 ≦ ΔEab ^* <2.

○: 2≦ΔEab ^* <4.

△: 4≦ΔEab ^* <6.

×: 6≦△Eab ^* .

2. Voltage retention rate

An SiO ₂ film for preventing sodium ions from eluting is formed, and an indium tin oxide (ITO) electrode of a predetermined pattern is further deposited on the soda lime glass substrate. The photosensitive resin compositions obtained in the above Examples 1 to 12 and Comparative Examples 1 to 8 were applied onto the glass substrate by spin coating. Then, prebaking was performed at a temperature of 100 ° C for 1 minute to form a prebaked coating film having a film thickness of 2.0 μm. Next, the mask was not covered, and the aforementioned prebaked coating film was irradiated with light of 700 J/m ² . The exposed coating film was immersed in a developing solution of potassium hydroxide having a temperature of 23 ° C and a concentration of 0.04% by weight. After 1 minute, it was washed with ultrapure water and air dried. Then, the film after development was baked at a temperature of 230 ° C for 30 minutes to form a hard coat film.

Next, the pixel substrate formed of the cured coating film and the ITO electrode having a predetermined pattern were deposited by a sealing agent, and a glass bead having a particle diameter of 1.8 mm was placed between the two. A liquid crystal material (manufactured by Merck, a liquid crystal material of the type MLC6608) was injected into a gap between the sealing agent, the pixel substrate, and the ITO electrode to form a liquid crystal cell.

Then, the obtained liquid crystal cell was placed in a thermostat at 60 ° C, and the liquid crystal crystal obtained by measuring the liquid crystal voltage holding ratio measuring instrument (manufactured by Toyo Co., Ltd., model VHR-1A type) was measured. Cell voltage retention. The measured voltage is a square wave of 5.5 volts and its measurement frequency is 60 Hz.

The aforementioned voltage holding ratio represents a value, and this value represents (the potential difference after the liquid crystal cell passes after 16.7 milliseconds / the voltage applied by the liquid crystal cell at 0 milliseconds). When the voltage holding ratio of the liquid crystal cell does not exceed 90%, the obtained liquid crystal cell cannot stably maintain the voltage within 16.7 milliseconds, Liquid crystal molecules in a liquid crystal cell are prone to defects in image sticking. The voltage holding ratios measured in the foregoing Examples 1 to 12 and Comparative Examples 1 to 8 were evaluated based on the following criteria:

◎: 95% < voltage holding ratio ≦ 100%.

○: 90% < voltage holding ratio ≦ 95%.

△: 80% < voltage holding ratio ≦ 90%.

×: The voltage holding ratio is ≦80%.

3. Contrast

The photosensitive resin compositions obtained in Examples 1 to 12 and Comparative Examples 1 to 8 were applied by spin coating to a glass substrate having a size of 100 mm × 100 mm. Then, it was dried under reduced pressure at a pressure of 100 mmHg for 30 seconds. Next, a pre-bake process was carried out at a temperature of 80 ° C for 2 minutes to form a pre-baked film having a film thickness of 2.5 μm. After the prebaking process, the prebaked coating film was irradiated with ultraviolet light (exposure machine Canon PLA-501F) having an energy of 100 mJ/cm ² , and the exposed prebaked coating film was immersed in a developing solution at 23 ° C. After 1 minute, the coating film was washed with pure water and subjected to a post-baking process at 235 °C. After 30 minutes passed, a photosensitive resin layer having a film thickness of 2.0 μm was formed on the glass substrate.

The photosensitive resin layer having a film thickness of about 2.0 μm was measured for the luminance value of the photosensitive resin layer by the detecting device shown in Figs. 1 and 2, and the ratio of the luminance was calculated. In the detecting device 100 of FIG. 1, the photosensitive resin layer 110 obtained is disposed between the two polarizing plates 120 and 130, and the light emitted from the light source 140 sequentially passes through the polarizing plate 120 and is photosensitive. The resin layer 110 and the polarizing plate 130. Then, the luminance value (cd/cm ² ) of the light that has passed through the polarizing plate 130 was measured by a luminance meter 150 (Model BM-5A, manufactured by Topcon Corporation).

The polarization direction 120a of the polarizing plate 120 is parallel to the polarization direction 130a of the polarizing plate 130, and the luminance value measured by the apparatus 100 of FIG. 1 is A. The detecting device 200 shown in FIG. 2 is substantially the same as the detecting device 100 shown in FIG. 1 . The difference is that the polarizing direction 220 a of the polarizing plate 220 in the detecting device 200 is perpendicular to the polarizing direction 230 a of the polarizing plate 230 . And the luminance value measured by the device 200 is B.

Next, the contrast of the photosensitive resin composition was calculated by the following formula (XI), and evaluated according to the following criteria:

◎: 1500 ≦ contrast.

○: 1200 ≦ contrast <1500.

△: 900 ≦ contrast <1200.

×: Contrast <900.

From the results of the second and third tables, it is understood that when the first alkali-soluble resin (A-1) of the alkali-soluble resin (A) is an ethylenically unsaturated monomer (a1-1) having a hindered amine structure as a copolymerization monomer At the time, the photosensitive resin composition obtained had a good voltage holding ratio.

Next, when the first alkali-soluble resin (A-1) of the alkali-soluble resin (A) is an ethylenically unsaturated monomer (a1-2) having an oxetanyl group, When the monomer is copolymerized, the obtained photosensitive resin composition has better alkali resistance. Wherein, when the ethylenically unsaturated monomer (a1-2) having an oxetanyl group contains an unsaturated monomer having a structure represented by the formula (II), the obtained photosensitive resin composition has Better lye resistance.

Further, when the alkali-soluble resin (A) contains the second alkali-soluble resin (A-2), the obtained photosensitive resin composition has better alkali resistance.

Further, when the photosensitive resin composition of the present invention contains the dye (F), the resulting photosensitive resin composition has a better contrast.

It should be noted that the present invention describes a photosensitive resin composition for a color filter of the present invention and an application thereof by using specific compounds, compositions, reaction conditions, processes, analytical methods, or specific instruments as an example, but the present invention belongs to It is to be understood by those skilled in the art that the present invention is not limited thereto, and other compounds may be used for the photosensitive resin composition for color filters of the present invention and applications thereof without departing from the spirit and scope of the present invention. , composition, reaction conditions, process, analytical methods or instruments.

The present invention has been disclosed in the above embodiments, and is not intended to limit the present invention. Any one of ordinary skill in the art to which the present invention pertains can make various changes without departing from the spirit and scope of the invention. The scope of protection of the present invention is therefore defined by the scope of the appended claims.

Claims (14)

A photosensitive resin composition for a color filter comprising: an alkali-soluble resin (A); a compound (B) having an ethylenically unsaturated group; a photoinitiator (C); and an organic solvent (D) And a pigment (E), wherein the alkali-soluble resin (A) contains a first alkali-soluble resin (A-1), and the first alkali-soluble resin (A-1) is polymerized from a first mixture And the first mixture comprises at least one ethylenically unsaturated monomer (a1-1) having a hindered amine structure, one ethylenically unsaturated monomer having an oxetane group (a1-2), and one having a carboxy group Acid-based ethylenically unsaturated monomer (a1-3). The photosensitive resin composition for a color filter according to claim 1, wherein the ethylenically unsaturated monomer (a1-1) having a hindered amine structure comprises a formula (I): Structure of unsaturated monomers: In the formula (I), the X ₁ represents a hydrogen atom, a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, An aromatic group having 6 to 20 carbon atoms, an aromatic alkyl group having 7 to 12 carbon atoms, a mercapto group, an oxygen radical or -OX ₄ ; and X ₄ representing a hydrogen atom and a linear alkyl group having 1 to 18 carbon atoms a branched alkyl group having 3 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aromatic group having 6 to 20 carbon atoms or an aromatic alkyl group having 1 to 12 carbon atoms; ₂ and X ₃ each independently represent a methyl group, an ethyl group, a phenyl group, or the X ₂ and X _{3 are} bonded to each other to form an aliphatic ring having 4 to 12 carbon atoms; the * represents a covalent bond. The photosensitive resin composition for a color filter according to claim 1, wherein the oxetane group-containing ethylenically unsaturated monomer (a1-2) comprises the following formula (II) The unsaturated monomer of the structure shown: In the formula (II), the Y ₁ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; the Y ₂ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; the Y ₃ , Y ₄ , Y ₅ and Y ₆ each independently represent a hydrogen atom, a fluorine atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms or a perfluoroalkyl group having 1 to 4 carbon atoms; and the a represents an integer of 1 to 6. The photosensitive resin composition for a color filter according to claim 1, wherein the first mixture comprises the ethylenically unsaturated monomer (a1-1) having a hindered amine structure, and the oxygen heterocycle a butylated alkyl ethylenically unsaturated monomer (a1-2) and one other copolymerizable ethylenically unsaturated monomer (a1) other than the ethylenically unsaturated monomer (a1-3) having a carboxylic acid group 4). The photosensitive resin composition for a color filter according to claim 4, which is based on the ethylenically unsaturated monomer (a1-1) having a hindered amine structure, and having the oxetane group An ethylenically unsaturated monomer (a1-2), the ethylenically unsaturated monomer (a1-3) having a carboxylic acid group, and the ethylenically unsaturated monomer (a1-1) having a hindered amine structure, The ethylenically unsaturated monomer (a1-2) having an oxetane group and the other copolymerizable ethylenically unsaturated monomer other than the ethylenically unsaturated monomer (a1-3) having a carboxylic acid group The total amount of the body (a1-4) used is 100 parts by weight, and the ethylenically unsaturated monomer (a1-1) having a hindered amine structure is used in an amount of 5 parts by weight to 50 parts by weight, which has an oxetane group The alkyl group-containing ethylenically unsaturated monomer (a1-2) is used in an amount of 10 parts by weight to 60 parts by weight, and the carboxylic acid group-containing ethylenically unsaturated monomer (a1-3) is used in an amount of 10 parts by weight. To 40 parts by weight, the other copolymerizable ethylenically unsaturated monomer (a1-4) is used in an amount of 5 parts by weight to 75 parts by weight. The photosensitive resin composition for a color filter according to claim 1, wherein the alkali-soluble resin (A) comprises a second alkali-soluble resin (A-2), and the second alkali-soluble resin ( A-2) is obtained by reacting a second mixture, wherein the second mixture comprises an epoxy compound (a2-1) having at least two epoxy groups, and one having at least one carboxylic acid group and at least one ethylene A compound of the unsaturated group (a2-2). The photosensitive resin composition for a color filter according to claim 6, wherein the epoxy compound (a2-1) having at least two epoxy groups comprises one having the following formula (III) a compound of the structure, a compound having the formula (IV) or a combination of the two: In the formula (III), the R ₁ , the R ₂ , the R ₃ and the R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group, or a carbon number An aromatic group or an aralkyl group of 6 to 12; in the formula (IV), the R ₅ to R ₁₈ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or a carbon number of 6 An aromatic group to 15 and b represents an integer from 0 to 10. The photosensitive resin composition for a color filter according to claim 6, wherein the second alkali-soluble resin (A-2) is used in an amount of 100 parts by weight based on the total amount of the alkali-soluble resin (A). The amount used is from 30 parts by weight to 70 parts by weight. The photosensitive resin composition for a color filter according to claim 1, further comprising a dye (F). The photosensitive resin composition for a color filter according to claim 9, wherein the total amount of the alkali-soluble resin (A) used is 100 parts by weight, and the dye (F) is used in an amount of 4 parts by weight. Parts to 40 parts by weight. The photosensitive resin composition for a color filter according to claim 1, wherein the first alkali-soluble resin (A-1) is used in an amount of 100 parts by weight based on the total amount of the alkali-soluble resin (A). The amount of the compound (B) having an ethylenically unsaturated group is from 40 parts by weight to 400 parts by weight, and the photoinitiator (C) is used in an amount of from 10 parts by weight to 100 parts by weight. The organic solvent (D) is used in an amount of from 500 parts by weight to 5000 parts by weight to 100 parts by weight, and the pigment (E) is used in an amount of from 30 parts by weight to 300 parts by weight. A method of producing a color filter, which comprises forming a pixel layer by using a photosensitive resin composition for a color filter according to any one of claims 1 to 11. A color filter produced by the method of producing a color filter according to claim 12 of the patent application. A liquid crystal display comprising the color filter of claim 13 of the patent application.