CN105319847A - Photosensitive resin composition for color filter and application thereof - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for color filters and its application. The photosensitive resin composition includes an alkali-soluble resin (A), a compound having an ethylenically unsaturated group (B), a photoinitiator (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, wherein the first mixture at least contains a hindered Ethylenically unsaturated monomer with amine structure (a1-1), ethylenically unsaturated monomer with oxetanyl group (a1-2), and ethylenically unsaturated monomer with carboxylic acid group (a1-3 ). The photosensitive resin composition for color filters of the present invention has good alkali resistance and voltage retention.

Description

Photosensitive resin composition for color filter and its application

technical field

The invention relates to a photosensitive resin composition for a color filter of a liquid crystal display and the formed color filter, in particular to provide a color filter with good alkali resistance and voltage retention Photosensitive resin composition.

Background technique

At present, color filters have been widely used in application fields 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 manufacturing techniques of color filters are also becoming more diversified. For example, methods such as dyeing, printing, electroplating, and dispersion have been developed successively. Now, the dispersion method is the mainstream production technology of color filters.

The aforementioned dispersion method is to disperse the pigment in the photosensitive resin to form a photosensitive resin composition. Then, the photosensitive resin composition is coated on the glass substrate, and after steps such as exposure and development, a specific pattern can be obtained. Then, after repeating the above-mentioned coating, exposure, and development processes three times, the pixel coloring of red (R), green (G) and blue (B) required in the pixel coloring layer of the color filter can be obtained. pattern. Generally speaking, in order to further improve the contrast of the color filter, a light-shielding layer (or black matrix) can be arranged between the pixel coloring layers formed by the pixels.

The process of the above-mentioned pigment dispersion method is to first disperse the pigment in the photocurable resin to form a colored photosensitive resin composition, and finally form the resin composition into a pixel colored layer. Furthermore, in the process of the pigment dispersion method, usually on a transparent support such as a glass substrate, a light-shielding layer (black matrix) is formed with a metal such as chromium or chromium oxide or a photosensitive resin light-shielding film. Then, the photosensitive resin (color photoresist) dispersed with a red pigment is coated on a transparent support by spin coating, exposed through a mask, and developed after exposure to get red pixels. Next, red, green, blue and other three-color pixels can be respectively produced on the support in the same operation mode, that is, the repeated use of coating, exposure, and development.

In recent years, the use of color liquid crystal displays is no longer limited to personal computers, but is also widely used in color TVs and various monitor screens (especially large-size color liquid crystal screens), so the requirements for the color saturation of liquid crystal displays Higher and higher. Therefore, the pigment ratio contained in the photosensitive resin composition is also getting higher and higher, but when the pigment ratio increases, the contrast of the color liquid crystal display will be reduced, and because the relative usage of the alkali-soluble resin and the photosensitive monomer becomes less, The degree of crosslinking after exposure is reduced, leading to problems such as poor alkali resistance.

In the content disclosed in Japanese Patent Laid-Open No. 2004-138950, it uses a specific alkali-soluble resin to form a pixel coloring layer with a flat surface, and a color filter with 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, which leads to the defect of afterimage when displaying a picture.

In view of this, there is an urgent need to develop a photosensitive resin composition for color filters that has high contrast, good alkali resistance and voltage retention at the same time, so as to overcome the above-mentioned problems of known color filters.

Contents of the invention

Therefore, one aspect of the present invention is to provide a photosensitive resin composition for color filters. The photosensitive resin composition can improve the alkali liquid resistance and voltage retention rate of the color filter.

Another aspect of the present invention is to provide a method for manufacturing a color filter, which uses the aforementioned photosensitive resin composition for a color filter to form a pixel layer.

Another aspect of the present invention is to provide a color filter, which is manufactured by the aforementioned manufacturing method.

Another aspect of the present invention is to provide a liquid crystal display, which includes the aforementioned color filter.

According to the above aspects of the present invention, a photosensitive resin composition for a color filter is proposed, the photosensitive resin composition comprising an alkali-soluble resin (A), a compound (B) having an ethylenically unsaturated group, a photosensitive Initiator (C), organic solvent (D) and pigment (E) are described below.

Photosensitive resin composition

Alkali soluble resin (A)

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

The first alkali soluble resin (A-1)

The first alkali-soluble resin (A-1) is obtained by copolymerizing the first mixture, and the first mixture contains at least ethylenically unsaturated monomer (a1-1) with hindered amine structure, and oxetane An ethylenically unsaturated monomer (a1-2) having a carboxylic acid group and an ethylenically unsaturated monomer (a1-3) having a carboxylic acid group. In addition, the first mixture may also optionally include the ethylenically unsaturated monomer (a1-1) having a hindered amine structure, the ethylenically unsaturated monomer (a1-2) having an oxetanyl group and other copolymerizable ethylenically unsaturated monomers (a1-4) other than the ethylenically unsaturated monomer (a1-3) having a carboxylic acid group.

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

The ethylenically unsaturated monomer (a1-1) having a hindered amine structure comprises an unsaturated monomer having a structure shown in the following formula (I):

In formula (I), X represents _a hydrogen atom, a straight-chain alkyl group with a carbon number of 1 to 18, a branched chain alkyl group with a carbon number of 3 to 18, a cycloalkyl group with a carbon number of 3 to 18, a carbon number It is an aryl group with 6 to 20, an aralkyl group with a carbon number of 7 to 12, an acyl group, an oxygen radical or -OX ₄ ; X ₄ represents a hydrogen atom, a straight-chain alkyl group with a carbon number of 1 to 18, and a carbon number of Branched chain alkyl with 3 to 18, cycloalkyl with 3 to 18 carbons, aryl with 6 to 20 carbons or aralkyl and acyl with 7 to 12 carbons; X ₂ and X ₃ are independent ground represents methyl, ethyl, phenyl, or X ₂ and X ₃ are bonded to each other to form an aliphatic ring with 4 to 12 carbons; "*" represents a covalent bond.

When X ₁ and X ₄ represent a straight chain alkyl group with 1 to 18 carbons, a branched chain alkyl group with 3 to 18 carbons or a cycloalkyl group with 3 to 18 carbons, the X ₁ and X ₄ Specific examples may include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, cyclohexyl, n-octyl, or hexadecyl. When X represents _an aromatic group having 6 to 20 carbon atoms, specific examples thereof include, but are not limited to, phenyl, α-naphthyl or β-naphthyl. When X ₁ and X ₄ represent an aralkyl group with a carbon number of 7 to 12, X ₁ and X ₄ can be an aromatic group bonded to an alkyl group with a carbon number of 1 to 8, and the carbon number of the aromatic group is 6 to 10, and its specific examples may include but not limited to benzyl, phenethyl, α-methylbenzyl or 2-yl-2-phenylpropane and the like. When X ₁ and X ₄ represent acyl groups, X ₁ and X ₄ may be alkanoyl or aroyl having 2 to 8 carbons, and specific examples thereof may be acetyl or benzoyl.

X ₁ may preferably be a hydrogen atom, an alkyl group having a carbon number of 1 to 5, or an oxygen radical, and more preferably may be a hydrogen atom, an oxygen radical, or a methyl group.

When X ₂ and X ₃ in the formula (I) are bonded to form an aliphatic ring structure, specific examples thereof include cyclopentane, cyclohexane, and the like. Preferably, X ₂ and X ₃ can be methyl groups.

This unsaturated monomer having the structure shown in formula (I) can have the structure shown in formula (I-1) and formula (I-2):

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

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

The aforementioned unsaturated monomers having a structure shown in formula (I-1) may have structures shown in the following formulas (I-1-1) to (I-1-7):

In formula (I-1-1) to formula (I-1-7), the definition of X ₅ is as described above, and will not be repeated here.

The aforementioned unsaturated monomers having a structure shown in formula (I-2) may have structures shown in the following formulas (I-2-1) to (I-2-4):

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

The ethylenically unsaturated monomer (a1-1) having a hindered amine structure may include, but is not limited to, 4-methacrylamido-2,2,6,6-tetramethyl-piperidine (4-methacrylamido-2 ,2,6,6-tetramethylpiperidine), 2,2,6,6-tetramethyl-piperidinyl methyl acrylate [that is, the aforementioned formula (I-1-1), and X ₅ represents methyl] or 1 , 2,2,6,6-pentamethyl-piperidinyl methyl acrylate [that is, the aforementioned formula (I-1-2), and X ₅ represents methyl].

These ethylenically unsaturated monomers having a hindered amine structure can be used alone or in combination.

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

If the first alkali-soluble resin (A-1) does not use the ethylenically unsaturated monomer (a1-1) having a hindered amine structure as a copolymerizable monomer, the photosensitive resin combination for the obtained color filter have the disadvantage of poor voltage retention.

Ethylenically unsaturated monomer (a1-2) having an oxetanyl group

The ethylenically unsaturated monomer (a1-2) having an oxetanyl group comprises an unsaturated monomer having a structure shown in the following formula (II):

In formula (II), Y ₁ represents a hydrogen atom or an alkyl group with a carbon number of 1 to 4; Y ₂ represents a hydrogen atom or an alkyl group with a carbon number of 1 to 4; the 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 carbons, or a perfluoroalkyl group having 1 to 4 carbons; and the a represents an integer of 1 to 6.

Specific examples of the unsaturated monomer having the structure shown in formula (II) may include but not limited to methacrylate compounds, acrylate compounds or have the following formula (II-1) to formula (II-4 ) The unsaturated monomer of the structure shown.

The aforementioned methacrylate compounds may include, but are not limited to, 3-(methacryloylmethoxy)oxetane [3-(methacryloyloxy)oxetane; OXMA], 3-(methacryloylmethoxy )-3-ethyloxetane [3-(methacryloyloxy)-3-ethyloxetane; EOXMA], 3-(methacryloylmethoxy)-3-methyloxetane [3-( methacryloyloxy)-3-methyloxetane; MOXMA], 3-(methacryloylmethoxy)-2-methyloxetane, 3-(methacryloylmethoxy)-2-trifluoromethyl Oxetane, 3-(methacryloylmethoxy)-2-pentafluoroethyloxetane, 3-(methacryloylmethoxy)-2-phenyloxetane alkanes, 3-(methacryloylmethoxy)-2,2-difluorooxetane, 3-(methacryloylmethoxy)-2,2,4-trifluorooxetane alkane, 3-(methacryloylmethoxy)-2,2,4,4-tetrafluorooxetane, 3-(methacryloylethoxy)oxetane, 3-( Methacryloylethoxy)-3-ethyloxetane, 2-ethyl-3-(methacryloylethoxy)oxetane, 3-(methacryloylethoxy base)-2-trifluoromethyloxetane, 3-(methacryloylethoxy)-2-pentafluoroethyloxetane, 3-(methacryloylethoxy) -2-Phenyloxetane, 2,2-difluoro-3-(methacryloylethoxy)oxetane, 3-(methacryloylethoxy)-2,2 , compounds such as 4-trifluorooxetane or 3-(methacryloylethoxy)-2,2,4,4-tetrafluorooxetane.

The above-mentioned acrylate compounds may include but not limited to 3-(acryloylmethoxy)oxetane, 3-(acryloylmethoxy)-3-ethyloxetane, 3-(propylene Acylmethoxy)-3-methyloxetane, 3-(acryloylmethoxy)-2-methyloxetane, 3-(acryloylmethoxy)-2-trifluoro Methyloxetane, 3-(acryloylmethoxy)-2-pentafluoroethyloxetane, 3-(acryloylmethoxy)-2-phenyloxetane, 3-(acryloylmethoxy)-2,2-difluorooxetane, 3-(acryloylmethoxy)-2,2,4-trifluorooxetane, 3-(propylene Acylmethoxy)-2,2,4,4-tetrafluorooxetane, 3-(acryloylethoxy)oxetane, 3-(acryloylethoxy)-3-ethane oxetane, 2-ethyl-3-(acryloylethoxy)oxetane, 3-(acryloylethoxy)-2-trifluoromethyloxetane, 3 -(acryloylethoxy)-2-pentafluoroethyloxetane, 3-(acryloylethoxy)-2-phenyloxetane, 2,2-difluoro-3- (acryloylethoxy)oxetane, 3-(acryloylethoxy)-2,2,4-trifluorooxetane or 3-(acryloylethoxy)-2,2 , Compounds such as 4,4-tetrafluorooxetane.

The aforementioned unsaturated monomers having the structures shown in formula (II-1) to formula (II-4) are as follows:

Specific examples of the aforementioned other ethylenically unsaturated monomers having an oxetanyl group may include, but are not limited to, 3-methyl-3-(ethylene methoxy) oxetane [3-methyl-3-( vinyloxy)oxetane; MOXV], 3-ethyl-3-(vinylmethoxy)oxetane [3-ethyl-3-(vinyloxy)oxetane; EOXV], 3-propyl-3-(vinylmethyl 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-ethylenebutoxy)oxetane, 3-propyl-3-(3-vinylbutoxy)oxetane, ethylenediene Alcohol [(3-ethyl-3-oxetanyl)methyl] vinyl ether, propylene glycol [(3-ethyl-3-oxetanyl)methyl] vinyl ether or 3,3- Vinyl ether compounds having an oxetanyl group such as bis[(vinyloxy)methyl]oxetane.

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

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

Ethylenically unsaturated monomers having a carboxylic acid group (a1-3)

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

Specific examples of the ethylenically unsaturated monomer (a1-3) having a carboxylic acid group may include, but are not limited to, acrylic acid, methacrylic acid, crotonic acid, chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-acryloylacetyl Unsaturated monocarboxylic acid compounds such as oxysuccinate, 2-methacryloylethoxysuccinate or 2-methacryloylethoxysuccinate; maleic acid, maleic anhydride, rich Unsaturated dicarboxylic acid compounds or their anhydrides such as malic acid, itaconic acid, itaconic anhydride, citraconic acid or citraconic anhydride; or other unsaturated polycarboxylic acid compounds or their anhydrides containing three or more carboxylic acid groups .

The ethylenically unsaturated monomer (a1-3) having a carboxylic acid group is preferably acrylic acid, methacrylic acid, 2-acryloylethoxysuccinate, 2-methacryloylethoxybutanedi ester or 2-methacryloylethoxysuccinate, and more preferably 2-acryloylethoxysuccinate, 2-methacryloylethoxysuccinate or 2-methacryloylethyl Oxysuccinate.

Based on the ethylenically unsaturated monomer (a1-1) having a hindered amine structure, the ethylenically unsaturated monomer (a1-2) having an oxetane group and the ethylenically unsaturated monomer (a1-2) having a carboxylic acid group ( a1-3), and the total amount of other copolymerizable ethylenically unsaturated monomers (a1-4) selectively added later is 100 parts by weight, and the ethylenically unsaturated monomer (a1) having a carboxylic acid group -3) is used in an amount of 10 to 40 parts by weight, preferably 12 to 35 parts by weight, and more preferably 15 to 30 parts by weight.

Other copolymerizable ethylenically unsaturated monomers (a1-4)

The aforementioned first mixture may optionally contain other copolymerizable ethylenically unsaturated monomers (a1-4), and the other copolymerizable ethylenically unsaturated monomers (a1-4) may include but are not limited to Aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene or methoxystyrene; N-phenylmaleimide, N-o-hydroxyphenylmaleimide Toimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m-form Phenylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide Maleimides such as imine, N-p-methoxyphenylmaleimide or N-cyclohexylmaleimide; 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, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzene acrylate Methyl ester, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, triethylene glycol methoxy acrylate, triethylene glycol methoxy methacrylate, lauryl methacrylate, formazan Myristyl acrylate, cetyl methacrylate, stearyl methacrylate, eicosyl methacrylate, behenyl methacrylate or dicyclopentenyl acrylate Unsaturated carboxylic acid esters such as ethyl oxide; Acrylic acid-N,N-dimethylaminoethyl ester, methacrylic acid-N,N-dimethylaminoethyl ester, Acrylic acid-N,N-Diethylamino Acrylic compounds such as propyl ester, N,N-dimethylaminopropyl methacrylate, N,N-dibutylaminopropyl acrylate, and iso-ButylaminoethylMethacrylate; acrylic epoxy Glycidyl esters of unsaturated carboxylic acids such as propyl ester or glycidyl methacrylate; vinyl carboxylates such as vinyl acetate, vinyl propionate or vinyl butyrate; vinyl methyl ether , vinyl ethyl ether, allyl glycidyl ether or methallyl glycidyl ether and other unsaturated ethers; acrylonitrile, methacrylonitrile, α-chloroacrylonitrile or vinylidene cyanide, etc. Cyanide vinyl compounds; acrylamide, methacrylamide, α-chloroacrylamide, N-hydroxyethylacrylamide or N-hydroxyethylmethacrylamide, etc. aliphatic conjugated dienes such as 1,3-butadiene, isopentene or chlorinated butadiene.

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

These other copolymerizable ethylenically unsaturated monomers (a1-4) can be used alone or in combination.

Based on the ethylenically unsaturated monomer (a1-1) having a hindered amine structure, the ethylenically unsaturated monomer (a1-2) having an oxetane group, and the ethylenically unsaturated monomer (a1-2) having a carboxylic acid group ( The total usage amount of a1-3) and other copolymerizable ethylenically unsaturated monomers (a1-4) is 100 parts by weight, and the usage amount of the other copolymerizable ethylenically unsaturated monomers (a1-4) 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.

Based on 100 parts by weight of the total amount of the alkali-soluble resin (A), the amount of the first alkali-soluble resin (A-1) is 30 parts by weight to 100 parts by weight, preferably 40 parts by weight to 90 parts by weight, And more preferably 50 to 80 parts by weight.

The second alkali soluble resin (A-2)

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

The aforementioned second mixture includes 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. Secondly, the second mixture may optionally contain a carboxylic acid anhydride compound (a2-3), a compound having an epoxy group (a2-4), or any combination of the above materials.

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

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

In formula (III), R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom, a halogen atom, an alkyl or alkoxy group with 1 to 5 carbons, or an alkoxy group with 6 to 12 carbons. Aryl or aralkyl.

The compound having the structure shown in formula (III) can be obtained by reacting bisphenolfluorene and epihalohydrin.

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

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

Specific examples of compounds having bisphenol-stilbene type can include Nipponsteelchemical Co. Ltd. (Nipponsteelchemical Co. Ltd.), manufactured by model ESF-300; Osaka Gas Co. Ltd. (OsakaGasCo. Ltd.), manufactured by model PG-100 or EG -210 goods; SMS-F9PhPG, SMS-F9CrG or SMS-F914PG manufactured by S.M.S Technology Co. Ltd.

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

The compound having the structure shown in formula (IV) can use the compound shown in following formula (III-1) to react with halogenated propylene oxide in the presence of alkali metal hydroxide:

In the formula (IV-1), the definitions of R ₅ to R ₁₈ and b are as described above, and will not be repeated here.

The synthetic method of the compound with the structure shown in formula (IV-1) is first under the presence of acid catalyst, the compound shown in following formula (IV-2) and phenol (phenol) compound are carried out condensation reaction, with A compound represented by formula (IV-1) is formed. Then, add an excessive amount of halogenated propylene oxide, so that the halogenated propylene oxide and the compound shown in formula (IV-1) undergo dehydrohalogenation reaction (dehydrohalogenation), and the structure shown in formula (IV) can be obtained compound of:

In formula (IV-2), the definitions of R ₇ to R ₁₀ are as described above, and will not be repeated here; R ₁₉ and R ₂₀ each independently represent a halogen atom or an alkyl or alkane with a carbon number of 1 to 6 Oxygen.

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

Specific examples of the aforementioned phenolic compounds may include, but are not limited to, phenol (phenol), cresol (cresol), ethylphenol (ethylphenol), n-propylphenol (n-propylphenol), isobutylphenol (isobutylphenol), tert-butylphenol ( t-butylphenol), octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol, vinylphenol ), propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol or cyclohexylcresol, etc. These phenolic compounds may be used alone or in combination.

Based on the amount of the compound represented by formula (III-2) being 1 mole, the amount of the phenolic compound used is 0.5 to 20 moles, and preferably 2 to 15 moles.

Specific examples of the acid catalyst may include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid (p-toluenesulfonic acid), oxalic acid (oxalic acid), boron trifluoride (borontrifluoride), anhydrous aluminum chloride (aluminiumchlorideanhydrous) or zinc chloride (zincchloride), etc. compound of. The acid catalyst is preferably p-toluenesulfonic acid, sulfuric acid, hydrochloric acid or any mixture of the above compounds.

The usage amount of the aforementioned acid catalyst is not particularly limited. However, based on 100% by weight of the compound represented by formula (IV-2), the amount of the acid catalyst used is preferably 0.1% by weight to 30% by weight.

The above-mentioned condensation reaction can be carried out without a solvent or in the presence of an organic solvent. Specific examples of the organic solvent may include, but not limited to, organic solvents such as toluene, xylene, or methylisobutylketone. The above-mentioned organic solvents may be used alone or in combination.

Based on the total amount of the compound represented by formula (IV-2) and phenols being 100% by weight, the amount of the organic solvent used is 50% by weight to 300% by weight, and preferably 100% by weight to 250% by weight. In addition, the operation temperature of the above condensation reaction is 40° C. to 180° C., and the operation time of the condensation reaction is 1 hour to 8 hours.

After the above-mentioned condensation reaction is completed, neutralization treatment or water washing treatment may be performed. The neutralization treatment is to adjust the pH value of the reacted solution to 3-7, and preferably 5-7. The water washing treatment can be carried out using a neutralizing agent, and the neutralizing agent is an alkaline substance, and its specific examples are: alkali metal hydroxides such as sodium hydroxide (sodium hydroxide) or potassium hydroxide (potassium hydroxide); Alkaline earth metal hydroxides such as calcium hydroxide or magnesium hydroxide; diethylenetriamine, triethylenetetramine, aniline or phenylenediamine, etc. organic amine; ammonia (ammonia), sodium dihydrogen phosphate (sodium dihydrogenphosphate) or any combination of the above compounds. The above-mentioned neutralizing agents can be used alone or in combination. The above-mentioned water washing treatment can be carried out by a known method, for example, adding an aqueous solution containing a neutralizing agent to the reacted solution and repeatedly extracting.

After the aforementioned neutralization treatment or water washing treatment, unreacted phenols and solvents can be removed by vacuum distillation and concentrated to obtain the compound represented by formula (IV-1).

Specific examples of the above-mentioned halogenated propylene oxide may include, but are not limited to, 3-chloro-1,2-propylene oxide, 3-bromo-1,2-propylene oxide or any combination of the above compounds. Before carrying out the above-mentioned dehydrohalogenation reaction, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide may be added in advance or during the reaction. The operating temperature of the above dehydrohalogenation reaction may be 20°C to 120°C, and the operating time may be 1 hour to 10 hours.

In one embodiment, the alkali metal hydroxide added in the above dehydrohalogenation reaction can also be its aqueous solution. In this embodiment, while the above-mentioned alkali metal hydroxide aqueous solution is continuously added to the dehydrohalogenation reaction system, water and halogenated propylene oxide can be continuously distilled out under reduced pressure or normal pressure, so as to remove water, and The halogenated propylene oxide can be continuously refluxed into the reaction system.

Before the above-mentioned dehydrohalogenation reaction is carried out, tetramethylammonium chloride (tetramethylammoniumchloride), tetramethylammonium bromide (tetramethylammoniumbromide) or trimethylbenzyl ammonium chloride (trimethylbenzylammoniumchloride) and other quaternary ammonium salts can also be added as catalysts, And react 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 performed at a temperature of 20° C. to 120° C., and the reaction time is 1 hour to 10 hours.

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

In order to make the above-mentioned dehydrohalogenation reaction proceed smoothly, an alcoholic solvent such as methanol or ethanol may be added. In addition, the dehydrohalogenation reaction can also be performed using an aprotic polar solvent such as dimethylsulfone or dimethylsulfoxide. In the case of using an alcohol solvent, based on 100% by weight of the total amount of the halogenated propylene oxide, the amount of alcohol used is 2% to 20% by weight, and preferably 4% to 15% by weight. In the case of using an aprotic polar solvent, based on the total amount of halogenated propylene oxide being 100% by weight, the amount of the aprotic polar solvent used is 5% by weight to 100% by weight, and preferably 10% by weight to 90% by weight.

After the dehydrohalogenation reaction is completed, water washing treatment may be optionally performed. Then, by means of vacuum distillation, for example, in an environment with a temperature of 110°C to 250°C and a pressure of less than 1.3kPa [10 millimeters of mercury (mmHg)], the halogenated propylene oxide, alcohols and aprotic poles are removed. non-toxic solvents.

In order to prevent the prepared epoxy resin from having hydrolytic halogens, solvents such as toluene or methylisobutylketone (methylisobutylketone) and aqueous solutions of alkali metal hydroxides such as sodium hydroxide or potassium hydroxide can be added to dehalogenation In the solution after the hydrogen reaction, the dehydrohalogenation reaction is carried out again. In the dehydrohalogenation reaction, based on the total equivalent of hydroxyl groups in the compound represented by the above formula (III-1) as 1 equivalent, the amount of alkali metal hydroxide used is 0.01 to 0.3 moles, and preferably 0.05 moles to 0.2 moles. The operating temperature of the above dehydrohalogenation reaction is 50° C. to 120° C., and the operating time is 0.5 hours to 2 hours.

After the dehydrohalogenation reaction is completed, the salts are removed by filtering and washing with water. In addition, solvents such as toluene or methyl isobutyl ketone are removed by distillation under reduced pressure to obtain the compound represented by formula (IV). Specific examples of the compound represented by the above formula (IV) may include, but are not limited to, commercial products such as NC-3000, NC-3000H, NC-3000S or NC-3000P manufactured by Nippon Kayaku Corporation.

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

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 the following (1) to (3): (1) acrylic acid, Methacrylic acid, 2-methacryloyloxyethylbutanedioic acid (2-methacryloyloxyethylbutanedioic acid), 2-methacryloyloxybutylbutanedioic acid, 2-methacryloyloxyethylbutanedioic acid, 2- Methacryloyloxybutyl adipic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloyloxypropylmaleic acid Maleic acid, 2-methacryloyloxybutylmaleic acid, 2-methacryloyloxypropylsuccinic acid, 2-methacryloyloxypropyl adipic acid, 2-methacryloyloxypropyl 2-methacryloxypropylphthalate, 2-methacryloyloxybutylphthalate, or 2-methacryloyloxybutylhydrophthalate; (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) A half-ester compound obtained by reacting a (meth)acrylate having a hydroxyl group with a carboxylic anhydride compound (a2-3) described later, wherein the (meth)acrylate having a hydroxyl group includes 2-hydroxyethyl acrylate [( 2-hydroxyethyl)acrylate], 2-hydroxyethyl methacrylate [(2-hydroxyethyl)methacrylate], 2-hydroxypropyl acrylate [(2-hydroxypropyl)acrylate], 2-hydroxypropyl methacrylate [(2-hydroxypropyl)methacrylate], 4-hydroxybutyl acrylate [(4-hydroxybutyl)acrylate], 4-hydroxybutyl methacrylate [(4-hydroxybutyl)methacrylate], pentaerythritol trimethacrylate, etc.

Carboxylic anhydride compound (a2-3)

The carboxylic anhydride compound (a2-3) may be selected from the group consisting of (1) and (2) described below: (1) butanedioicanhydride, maleicanhydride, itaconic Itaconicanhydride, phthalicanhydride, tetrahydrophthalicanhydride, hexahydrophthalicanhydride, methyltetrahydrophthalicanhydride, methylhexahydro Phthalic anhydride, methylendo-methylenetetrahydrophthalicanhydride, chlorendicanhydride, glutaric anhydride, or trimellitic anhydride (1,3-dioxoisobenzofuran-5- and (2) tetracarboxylic anhydride compounds such as benzophenonetetracarboxylic dianhydride (BTDA) or bisphenyltetracarboxylic dianhydride or bisphenyl ether tetracarboxylic dianhydride.

Compounds having epoxy groups (a2-4)

Compounds (a2-4) with epoxy groups can be selected from glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, glycidyl ether compounds with unsaturated groups, epoxy unsaturated compound or any combination of the above compounds.

The above-mentioned glycidyl ether compound having an unsaturated group can be manufactured by Nagase Chemical Industry Co., Ltd., and the models are DenacolEX-111, EX-121, Denacol, DenacolEX-141, DenacolEX-145, DenacolEX-146, DenacolEX-171 or DenacolEX-192, etc. Products of.

The second alkali-soluble resin (A-2) can be 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. ) carry out the reaction product with hydroxyl formed by polymerization reaction, wherein the epoxy compound (a2-1) with at least two epoxy groups can comprise the compound shown in formula (III), as shown in formula (IV) Compound or any mixture of the above materials. Next, the carboxylic anhydride compound (a2-3) was added to the reaction solution to conduct a polymerization reaction. Based on the total equivalents of the hydroxyl groups of the above-mentioned hydroxyl-containing reaction product being 1 equivalent, the equivalents of the acid anhydride groups possessed by the carboxylic anhydride compound (a2-3) are 0.4 to 1 equivalent, and preferably 0.75 to 1 equivalent. When a plurality of carboxylic anhydride compounds (a2-3) are used, these carboxylic anhydride compounds may be added sequentially or simultaneously during the reaction. When using dibasic carboxylic anhydride compound and tetrabasic carboxylic anhydride compound as carboxylic anhydride compound (a2-3), the molar ratio of dibasic carboxylic anhydride compound and tetrabasic carboxylic anhydride compound is 1/99 to 90/10, and relatively The best is 5/95 to 80/20. The operating temperature of the above reaction may be from 50°C to 130°C.

The second alkali-soluble resin (A-2) can be 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. ) reacts with a hydroxyl group reaction product, wherein the epoxy compound (a2-1) having at least two epoxy groups can be a compound shown in formula (III) or formula (IV). Next, a polymerization reaction is performed by adding the carboxylic anhydride compound (a2-3), the compound (a2-4) having an epoxy group, or a combination of the above two into the reaction solution. Based on the total equivalents of epoxy groups in the compound shown in formula (III) or formula (IV) as 1 equivalent, the above-mentioned compound (a2-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group The number of acid equivalents is from 0.8 equivalent to 1.5 equivalent, and preferably from 0.9 equivalent to 1.1 equivalent. Based on the total usage amount of the hydroxyl groups of the above-mentioned reaction products having hydroxyl groups being 100 mole percent, the usage amount of the carboxylic anhydride compound (a2-3) is 10 mole percent to 100 mole percent, preferably 20 mole percent to 100 mole percent, and More preferably, it is 30 mole percent to 100 mole percent.

When preparing the above-mentioned second alkali-soluble resin (A-2), 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, triphenylphosphine, triphenylstibine, triethylamine, triethanolamine, tetramethylammoniumchloride, or benzyl chloride Triethylammonium (benzyltriethylammoniumchloride) and so on. This reaction catalyst can be used individually by 1 type or in mixture of multiple types.

Based on the total amount of 100 parts by weight 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, the The usage amount of the reaction catalyst is 0.01 to 10 parts by weight, and preferably 0.3 to 5 parts by weight.

Secondly, in order to control the degree of polymerization, the reaction can add a polymerization inhibitor (polymerization inhibitor) to the reaction solution. Polymerization inhibitors may include methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol (2,6-di-t-butyl-p -cresol) or phenothiazine (phenothiazine), etc. A polymerization inhibitor can be used individually by 1 type or in mixture of multiple types.

Based on the total amount of 100 parts by weight 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, the The polymerization inhibitor is used in an amount of 0.01 to 10 parts by weight, and preferably 0.1 to 5 parts by weight.

When preparing the second alkali-soluble resin (A-2), a polymerization solvent may be optionally used. Polymerization reaction solvents may include alcohol solvents such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, or ethylene glycol; ketone solvents such as methyl ethyl ketone or cyclohexanone; toluene Aromatic hydrocarbon solvents such as or xylene; cellosolve solvents such as cellosolve or butylcellosolve; carbitol or butylcarbitol, etc. propylene glycol monomethyl ether (propylene glycol monomethyl ether) and other propylene glycol alkyl ether solvents; dipropylene glycol monomethyl ether [di (propylene glycol) methylether] and other polypropylene glycol alkyl ether [poly (propylene glycol) alkylether] class Solvents; acetate-based solvents such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, or propylene glycol monomethyl ether acetate; ethyl lactate or butyl lactate and other alkyl lactate (alkyllactate) solvents; or dialkyl glycol ether solvents. These polymerization reaction solvents may be used alone or in combination.

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

Based on 100 parts by weight of the total amount of the alkali-soluble resin (A), the amount of the second alkali-soluble resin (A-2) is 30 parts by weight to 70 parts by weight, preferably 30 parts by weight to 60 parts by weight, and More preferably, it is 30 parts by weight to 50 parts by weight.

When the alkali-soluble resin (A) of the present invention comprises the first alkali-soluble resin (A-1) and the second alkali-soluble resin (A-2), based on the total usage amount of the alkali-soluble resin (A) being 100 parts by weight, The first alkali-soluble resin (A-1) may be used in an amount of 30 to 70 parts by weight, and the second alkali-soluble resin (A-2) may be used in an amount of 30 to 70 parts by weight.

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

Compound (B) having an ethylenically unsaturated group

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

Alkoxy modified first compound

The first compound modified by the alkoxy group may include but not limited to the compound shown in the following formula (V), the compound shown in the following formula (VI), the compound shown in the following formula (VII) or any combination of the above compounds :

In formula (V) to formula (VII), Z ₁ represents independently Z ₂ independently represent an acryloyl group, a methacryloyl group or a hydrogen atom; Z ₃ independently represent a hydrogen atom, an alkyl group with a carbon number of 1 to 6, or an aromatic group with a carbon number of 1 to 6; in the formula (V ), the total number of acryloyl and methacryloyl groups is 5 or 6; in formula (VI), the total number of acryloyl and methacryloyl groups is 3 or 4; in formula (VII), acryloyl and The total number of methacryloyl 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 represent 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 When , Z ₁ is preferably bonded to Z ₂ via an oxygen atom.

In formula (V), Z ₂ are preferably both acryloyl groups.

The compound shown in formula (V) or formula (VI) can be synthesized by the following steps: first, the ring-opening addition reaction of ethylene oxide (Ethyleneoxide) or propylene oxide (Propyleneoxide) makes pentaerythritol Or dipentaerythritol reacts to form a ring-opened skeleton. Next, (meth)acryloyl chloride is reacted with the terminal hydroxyl group of the ring-opened skeleton to form a (meth)acryloyl group.

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

Specific examples of the compound shown in formula (V) may include, but not limited to, compounds shown in the following formula (V-1) to formula (V-3):

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

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

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

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

The compound shown in formula (VI) can be a commercial product, for example: the product manufactured by Changxing Chemical Industry Co., Ltd., its model is EM2411 or EM2421, or the product manufactured by Toyo Chemical Co., Ltd., its model is MiramerM4004 .

Specific examples of compounds represented by the aforementioned formula (VII) may include, but are not limited to, ethoxylated trimethylolpropanetriacrylate, ethoxylated trimethylolpropanetrimethacrylate ), Propoxylated Trimethylolpropane Triacrylate or Propoxylated Glyceryltriacrylate.

The compound shown in formula (VII) can be a commercial product, for example: a product manufactured by Nippon Kayaku Co., Ltd., its model is KAYARADGPO-303, KAYARADTHE-330, KAYARADTPA-320 or KAYARADTPA-330; Products manufactured by Sartoma Corporation, whose models are M-310, M-321, M-350, M-360 or M-460; products manufactured by Sartoma Co., Ltd., whose models are SR415, SR454, SR492, SR499, CD501, SR502, SR9020, SR9021, or SR9035; products manufactured by Eternal Chemical Industry Co., Ltd., whose model number is EM2380, EM2381, EM2382, EM2383, EM2384, EM2385, EM2386, EM2387, or EM3380; products manufactured by Toyo Chemical Co., Ltd., Its model is MiramerM3130, MiramerM3160, MiramerM3190 or MiramerM360. The above-mentioned compounds may be used alone or in combination.

Caprolactone-modified second compound

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

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

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

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

The above-mentioned polyhydric alcohol having more than four functional groups may be pentaerythritol, ditrimethylolpropane, dipentaerythritol or any combination of the above compounds.

Based on the usage amount of the aforementioned polyhydric alcohol having four or more functional groups being 1 mole, the usage amount of the caprolactone is preferably 1 mole to 12 moles.

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

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

The caprolactone-modified second compound can be a commercial product manufactured by Nippon Kayaku Co., Ltd., and its model is KAYARADDPCA-20, KAYARADDPCA-30, KAYARADDPCA-60 or DPCA-120.

third compound

The third compound can have a functional group shown in the following formula (IX):

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

Specific examples of the third compound can be acrylamide, (meth)acryloylmorpholine, (meth)acrylic acid-7-amino-3,7-dimethyloctyl ester, isobutoxymethyl (methyl) ) acrylamide, isobornyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, ethyl diglycol (meth)acrylate, tert-octyl(meth)acrylamide, diacetone(meth)acrylamide, dimethylamino(meth)acrylate, dodecyl(meth)acrylate, dicyclopentenyloxy(meth)acrylate Ethyl ester, dicyclopentenyl (meth)acrylate, nitrogen, nitrogen-dimethyl (meth)acrylamide, tetrachlorophenyl (meth)acrylate, 2-tetrachlorophenoxy (meth)acrylate Ethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichloro(meth)acrylate Phenoxyethyl ester, tribromophenyl (meth)acrylate, 2-tribromophenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylate- 2-Hydroxypropyl ester, Vinyl caprolactam, Nitro-vinyl pyosanone, Phenoxyethyl (meth)acrylate, Pentachlorophenyl (meth)acrylate, Pentabromophenyl (meth)acrylate, Polyethylene glycol mono(meth)acrylate, Polypropylene glycol mono(meth)acrylate, Bornyl (meth)acrylate, Ethylene glycol di(meth)acrylate, Dicyclopentanyl di(meth)acrylate Enyl ester, Triethylene glycol diacrylate, Tetraethylene glycol di(meth)acrylate, Tris(2-hydroxyethyl)isocyanate di(meth)acrylate, Tris(2-hydroxyethyl)isocyanate tri(meth)acrylate base) acrylate, caprolactone-modified tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, trimethylolpropyl tri(meth)acrylate, triethylene glycol di(meth)acrylate ester, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylol triacrylate Propyl ester (trimethylolpropanetriacrylate), pentaerythritol tri(meth)acrylate, dipentaerythritol hexaacrylate (dipentaerythritolhexaacrylate), pentaerythritol tetra(meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate base) acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, ditrimethylolpropyl tetra(meth)acrylate, EO Modified bisphenol A di(meth)acrylate, PO modified bisphenol A di(meth)acrylate, EO modified hydrogenated bisphenol A di(meth)acrylate, PO modified hydrogenation Bisphenol A di(meth)acrylate, EO modified bisphenol F di(meth)acrylate, novolac polyglycidyl ether (meth)acrylate or any combination of the above compounds.

Preferably, the third compound can be trimethylolpropyl triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, tetraacrylate Hydroxymethyl propyl ester or the product manufactured by Japan Toagosei Co., Ltd., its model is TO-1382, or any combination of the above compounds.

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

Photoinitiator (C)

The photoinitiator (C) of the present invention may have O-acyl oxime (oxime) series photoinitiator, triazine (triazine) type photoinitiator, acetophenone (acetophenone) type compound, diimidazole Biimidazole or benzophenone compounds.

Specific examples of O-acyl oxime photoinitiators may include 1-[4-(phenylthio)phenyl]-heptane-1,2-dione-2-(O-benzoyl oxime), 1 -[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-benzoyl oxime), 1-[4-(benzoyl)phenyl]-heptane- 1,2-Diketone-2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-substituent]-ethanone -1-(O-acetyl oxime), 1-[9-ethyl-6-(3-methylbenzoyl)-9H-carbazole-3-substituent]-ethanone-1-(O- acetyl oxime), 1-[9-ethyl-6-benzoyl-9H-carbazole-3-substituent]-ethanone-1-(O-acetyl oxime), ethanone-1-[ 9-ethyl-6-(2-methyl-4-tetrahydrofurylbenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethyl ketone-1-[9 -Ethyl-6-(2-methyl-4-tetrahydropyranylbenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethyl ketone-1- [9-ethyl-6-(2-methyl-5-tetrahydrofurylbenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethyl ketone-1-[ 9-Ethyl-6-(2-methyl-5-tetrahydropyranylbenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), Ethanone-1 -[9-Ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethyl ketone -1-[9-Ethyl-6-(2-methyl-4-tetrahydropyranylmethoxybenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime ), Ethanone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofurylmethoxybenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl Oxime), Ethanone-1-[9-Ethyl-6-(2-Methyl-5-tetrahydropyranylmethoxybenzoyl)-9H-carbazole-3-substituent]-1 -(O-acetyl oxime), Ethanone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl )Benzoyl}-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethanone-1-[9-ethyl-6-{2-methyl-4-(2 ,2-Dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazole-3-substituent]-1-(O-acetyl oxime) or any of the above compounds combination.

Specific examples of triazine photoinitiators may include 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine[2,4 -Bis(trichloromethyl)-6-(p-methoxy)styryl-s-triazine], 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3- Butadienyl)-s-triazine[2,4-Bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazine], 2-trichloromethyl- 4-amino-6-p-methoxystyryl-s-triazine [2-trichloromethyl-4-amino-6-(p-methoxy)styryl-s-triazine] or any combination of the above compounds.

Specific examples of acetophenone compounds can be p-dimethylamine acetophenone, α,α'-dimethoxy azoacetophenone oxide, 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-morpholinophenyl)-1-butanone or any combination of the above compounds.

Specific examples of biimidazole (biimidazole) compounds may include 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(o-chlorophenyl) -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 base)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole imidazole or any combination of the above compounds.

Specific examples of benzophenone compounds may include thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfone, diphenyl ketone, 4,4'-bis(di Methylamino) diphenyl ketone, 4,4'-bis(diethylamine) diphenyl ketone or any combination of the above compounds.

The aforementioned compounds may be used alone or in combination.

Preferably, the photoinitiator (C) can be 1-[4-(phenylthio)phenyl]-octane-1,2-dione 2-(O-benzoyl oxime), 1- [9-Ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-substituent]-Ethanone 1-(O-acetyl oxime), Ethanone-1-[9- Ethyl-6-(2-methyl-4-tetrahydrofuranmethoxybenzoyl)-9H-carbazole-3-substituent]-1-(O-acetyl oxime), ethyl ketone-1-[9 -Ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazole-3-substituent ]-1-(O-acetyl oxime), 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine, 2-benzyl-2-N ,N-Dimethylamine-1-(4-morpholinophenyl)-1-butanone, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5 '-Tetraphenyldiimidazole, 4,4'-bis(diethylamine)diphenyl ketone or any combination of the above compounds.

Based on the total usage of alkali-soluble resin (A) as 100 parts by weight, the usage of photoinitiator (C) is 10 parts by weight to 100 parts by weight, preferably 15 parts by weight to 80 parts by weight, and more preferably 20 parts by weight to 60 parts by weight.

Organic solvent (D)

The organic solvent (D) must be able to dissolve the aforementioned alkali-soluble resin (A), the compound (B) having an ethylenically unsaturated group, the photoinitiator (C), and the pigment (E), dye (F) and The additive (G), and the organic solvent (D) do not interact with these components and have 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 ethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, dipropylene glycol methyl ether, dipropylene glycol methyl ether (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 ethyl ether acetate Diethylene glycol monoalkyl ether acetate solvent; diglyme, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ether solvents; methyl ethyl ketone, cyclohexanone, 2-heptanone , 3-heptanone and other ketone solvents; 2-hydroxypropionate methyl ester, 2-hydroxypropionate ethyl ester and other lactate solvents; 2-hydroxy-2-methylpropionate, 2-hydroxy-2 -Ethyl methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate (EEP) , ethyl ethoxy acetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methyl Oxybutyl propionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, butyric acid Ethyl ester, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxo Other ester solvents such as ethyl butyrate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. carboxylic acid amide solvents.

The aforementioned organic solvents (D) may be used alone or in combination.

Preferably, the organic solvent (D) can be propylene glycol methyl ether acetate or ethyl 3-ethoxy propionate.

Based on 100 parts by weight of the total amount of the alkali-soluble resin (A), the amount of the organic solvent (D) used is between 500 parts by weight and 5000 parts by weight, preferably between 1000 parts by weight and 4500 parts by weight, more preferably Preferably, it is 1500 parts by weight to 4000 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-mentioned pigments.

The aforementioned inorganic pigments may be metal compounds such as metal oxides or metal complex compounds. The metal oxides may be oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, plumbous, or antimony, and composite oxides of the aforementioned metals.

The organic pigments mentioned above are selected from C.I. , 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; C.I. Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16 , 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49 :2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81 : 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168 , 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224 , 226, 242, 243, 245, 254, 255, 264, 265; C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, 39; C.I. Pigment Blue 1, 2, 15, 15: 3, 15 : 4, 15: 6, 16, 22, 60, 66; C.I. Pigment Green 7, 36, 37; C.I. Pigment Brown 23, 25, 28; and C.I. Pigment Black 1,7. The aforementioned organic pigments may be used alone or in combination.

The average particle size of the primary particles of the pigment (E) is 10nm to 200nm, preferably 20nm to 150nm, more preferably 30nm to 130nm.

Based on 100 parts by weight of the total amount of the alkali-soluble resin (A), the amount of the pigment (E) used is 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 parts to 200 parts by weight.

If necessary, the pigment (E) may optionally contain a dispersant, and specific examples thereof include cationic, anionic, nonionic, amphoteric, polysiloxane-based, or fluorine-based surfactants.

The surfactant may include but 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 surfactants such as ethylene oxide octyl phenyl ether or polyethylene oxide nonyl phenyl ether; polyethylene glycol dilaurate or polyethylene glycol distearate Polyethylene glycol diester surfactants such as acid esters; sorbitan fatty acid ester surfactants; fatty acid modified polyester surfactants; tertiary amine modified polyurethane surfactants Agent; manufactured by Shin-Etsu Chemical Industry Co., Ltd., the product model is KP; manufactured by TorayDowCorningSilicon, product model is SF-8427; manufactured by Kyoeisha Oleochemical Industry, product model is Polyflow; Manufactured by Dainippon Ink Chemical Industry, model number Megafac; Sumitomo 3M, model number Fluorad; Asahi Glass, model number AsahiGuard or Surflon. The surfactant can be used alone or in combination.

Dye (F)

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

Specific examples of red dyes, such as: C.I. 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, 353, 354, 356 or 388 red dyes.

Secondly, the red dye can also be C.I. 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 ,175,176,177,179,180,181,182,185,186,189,204,211,213,214,217,222,224,225,226,227,228,232,236,237 or 238 etc red dye.

The yellow dye can be C.I. 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 , 189, 190, 191, 192 or 199 etc. yellow dyes.

Secondly, the yellow dye can also be C.I. 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 dyes of 118, 119, 120, 121, 126, 127, 129, 132, 133 or 134, etc.

The orange dye can be C.I. Acid 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, 136 or 138 etc. orange dye.

Secondly, the orange dye can also be C.I. 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, 95, 96, 97, 98, 101, 102, 102:1, 104, 108, 112 or 114 etc. orange dyes.

The blue dye can be C.I 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: 1, 63, 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, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278 or 280 etc. blue dye .

Secondly, the blue dye can also be C.I. 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, Blue dyes such as 207, 209, 213, 215, 225, 226, 229, 230, 231, 242, 243, 244, 253, 254, 260 or 263.

The violet dye can be C.I. 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 , 103 or 109 etc. purple dyes.

Second, the violet dye can be C.I. 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 , 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93 or 97 etc. purple dyes.

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, 59, 66, 69, 70, 71, 81, 84, 94 or 95 etc. green dyes.

Secondly, the green dye can also be green dyes such as C.I.

Based on the total usage of alkali-soluble resin (A) as 100 parts by weight, the usage of dye (F) is 4 parts by weight to 40 parts by weight, preferably 5 parts by weight to 35 parts by weight, and more preferably 6 parts by weight to 30 parts by weight.

Based on the total amount of the alkali-soluble resin (A) being 100 parts by weight and the amount of the dye (F) being 4 to 40 parts by weight, the prepared photosensitive resin composition has better contrast.

Additive (G)

On the premise of not affecting the efficacy of the present invention, the photosensitive resin composition of the present invention may further optionally contain an additive (G). Specific examples of the additive (G) may include fillers, polymers other than the aforementioned alkali-soluble resin (A), adhesion promoters, antioxidants, ultraviolet absorbers, or anti-aggregation agents.

Specific examples of the filler include glass, aluminum, and 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 vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3- Aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidolpropyl Trimethoxysilane, 3-glycidylpropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, or any combination of the above compounds.

Specific examples of antioxidants 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 can be 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide, alkoxyphenone (alkoxyphenone) or any of the above-mentioned compounds combination.

Specific examples of the anti-coagulation agent may include sodium polyacrylate and the like.

Based on 100 parts by weight of the total amount of the alkali-soluble resin (A), the amount of the additive (G) used is 0 to 100 parts by weight, preferably 1 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 preparation of the photosensitive resin composition that this color filter is used is the aforementioned alkali-soluble resin (A), the compound (B) that has ethylenically unsaturated group, photoinitiator (C), organic solvent (D) and pigment (E) are placed in a stirrer and stirred to make them uniformly mixed into a solution state, and dyes (F) and additives (G) can be selectively added if necessary.

Manufacturing method of color filter

The present invention also provides a method for forming a color filter, which uses the photosensitive resin composition for the color filter to form a pixel layer, and the pixel layer is also referred to as a pixel colored layer hereinafter.

The present invention also provides a color filter, which is formed by using the above method for forming a color filter.

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

The step of forming the photosensitive layer is to apply the photosensitive resin composition for the color filter in the solution state on the substrate by rotary coating, casting coating or roll coating and other coating methods.

Above-mentioned substrate can be the non-alkali glass that is used for liquid crystal display device, soda-lime glass, hard glass (Pileus glass), quartz glass, and these glasses that are attached with transparent conductive film, or be used in photoelectric conversion device (such as Solid-state photography device) substrate (such as: silicon substrate).

In addition, before coating the photosensitive resin composition for color filters on the substrate, a light-shielding black matrix (black matrix) capable of isolating red, green, blue and other pixel colored layers must be formed on the substrate.

After the coating is formed, most of the organic solvents of the photosensitive resin composition for color filters are removed by drying under reduced pressure. Then, the residual organic solvent is completely removed by means of pre-bake to form a pre-bake coating film.

The operating conditions of the above-mentioned reduced-pressure drying and pre-baking can vary according to the types and compounding ratios of the components. Drying under reduced pressure is generally performed at a pressure of 0 torr to 200 torr for 1 second to 60 seconds, and prebaking is generally performed at 70° C. to 110° C. for 1 minute to 15 minutes.

The foregoing exposure step is to expose the above-mentioned pre-baked coating film 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 equipment used to provide ultraviolet light can be (ultra) high pressure mercury lamp and metal halide lamp.

The aforementioned developing step is to immerse the above-mentioned exposed pre-baked coating film in a developing solution at a temperature of 21°C to 25°C, and develop for about 15 seconds to 5 minutes, so as to remove the impurities in the above-mentioned exposed pre-baked coating film. necessary parts, whereby a semi-finished product having a pixel coloring layer having a predetermined pattern is formed.

The developer used above can be made of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methyl silicate, ammoniacal liquor, ethylamine, diethylamine, Dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine or 1,8-diazabicyclo-(5,4,0)-7-undecene and other bases Alkaline aqueous solution composed of active compounds.

The concentration of the developing solution is generally 0.001% by weight to 10% by weight, preferably 0.005% by weight to 5% by weight, more preferably 0.01% by weight to 1% by weight.

The aforesaid re-curing step is to wash the substrate (the substrate has a semi-finished product of pixel coloring layer and has a predetermined pattern) with water, so as to remove unnecessary parts in the above-mentioned exposed pre-baked coating film. Then, the above semi-finished product of the pixel coloring layer having a predetermined pattern is dried with compressed air or compressed nitrogen. Next, post-bake the semi-finished product of the pixel coloring layer with a predetermined pattern by using a heating device such as a heating plate or an oven, and the heating temperature may be 150°C to 250°C. If a heating plate is used, the heating time is from 5 minutes to 60 minutes. If an oven is used, the heating time is 15 minutes to 150 minutes. After the post-baking process, the pattern of the above-mentioned semi-finished pixel colored layer having a predetermined pattern is fixed to form the pixel colored layer.

The above steps are repeated to sequentially form red, green, blue and other pixel colored layers on the substrate.

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

Preparation method of liquid crystal display

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

The liquid crystal display is configured by arranging the above-mentioned color filter and a substrate provided with a thin film transistor (thinfilm transistor; TFT) facing each other, and a gap (cell gap) is provided between the two. Then, the color filter and the peripheral portion of the above-mentioned substrate are bonded together with an adhesive agent, and an injection hole is left. Next, liquid crystal is injected through the injection hole into the gap separated by the surface of the substrate and the adhesive, and the injection hole is sealed to form a liquid crystal layer. Afterwards, a polarizing plate is arranged on the other side of the color filter contacting the liquid crystal layer and the other side of the substrate contacting the liquid crystal layer, so that a liquid crystal display can be produced.

The liquid crystal mentioned above can be a liquid crystal compound or a liquid crystal composition, which is not particularly limited here, but any liquid crystal compound and liquid crystal composition can be used.

Moreover, the liquid crystal alignment film used in the color filter is used to restrict the alignment of liquid crystal molecules, and it is not particularly limited, any inorganic or organic matter is acceptable, and the present invention is not limited thereto.

Several embodiments are used below to illustrate the application of the present invention, but it is not intended to limit the present invention. Those with ordinary knowledge in the technical field of the present invention can make various changes without departing from the spirit and scope of the present invention. Move and retouch.

Description of drawings

Fig. 1 is a perspective view showing a contrast detection device according to an evaluation method of the present invention;

Fig. 2 is a perspective view showing another detection device of contrast in the evaluation method according to the present invention; wherein,

100: device 110: photosensitive resin layer

120: Polarizing plate 120a: Direction

130: Polarizing plate 130a: Direction

140: light source 150: luminance meter

200: device 210: photosensitive resin layer

220: Polarizer 220a: Direction

230: Polarizer 230a: Direction

240: light source 250: luminance meter.

detailed description

Preparation of the first alkali-soluble resin (A-1)

The first alkali-soluble resins of Synthesis Examples A-1-1 to A-1-14 were prepared according to Table 1 as follows.

Synthesis Example A-1-1

A nitrogen inlet, a stirrer, a heater, a condenser tube and a thermometer are arranged on a four-neck conical flask with a capacity of 1000 milliliters. After introducing nitrogen, 5 parts by weight of 1,2,2,6,6-pentamethyl-piperidinyl methyl acrylate (a1-1-1), 10 parts by weight of 3-(methacryloylmethoxy base) oxetane, 25 parts by weight of 2-methacryloylethoxysuccinate (hereinafter referred to as HOMS), 20 parts by weight of dicyclopentenyl acrylate (hereinafter referred to as FA-511A) , 25 parts by weight of styrene (hereinafter referred to as SM), 5 parts by weight of benzyl methacrylate (hereinafter referred to as BzMA) and 10 parts by weight of methyl methacrylate (hereinafter referred to as MMA) dissolved in 200 In the 3-ethoxy ethyl propionate (hereinafter referred to as EEP) of weight part, wherein the feeding mode of monomer is continuous addition.

After stirring evenly, the temperature of the oil bath was raised to 100°C. Then, 4 parts by weight of the polymerization initiator 2,2'-azobisazo-2-methylbutyronitrile (hereinafter referred to as AMBN) was dissolved in EEP, and five equal parts were added at intervals of one hour. into a four-necked Erlenmeyer flask.

The reaction temperature during the polymerization was maintained at 100°C. After 6 hours, the polymer product was taken out from the four-neck conical flask, and the solvent was devolatilized to obtain the first alkali-soluble resin in Synthesis Example A-1-1 (hereinafter referred to as A-1-1).

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

Synthesis Examples A-1-2 to A-1-14 use the same preparation method as that of the first alkali-soluble resin in Synthesis Example A-1-1, except that Synthesis Examples A-1-2 to A - 1-14 is to change the type and amount of raw materials in the first alkali-soluble resin and the polymerization conditions, and its formula and polymerization conditions are shown in Table 1, which will not be repeated here. In addition, in Table 1, "continuous addition" refers to the continuous addition of monomers for copolymerization to the reactor, continuous reaction and continuous discharge; and "one-time addition" refers to the complete addition of monomers for copolymerization to In the reactor, after the reaction is completed, the material is completely discharged again.

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

Synthesis Example A-2-1

First, 100 parts by weight of terpene epoxy compound (manufactured by Nippon Steel Chemical Co., Ltd., model ESF-300, and its epoxy equivalent is 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyl chloride Triethylammonium, 0.1 parts by weight of 2,6-di-tert-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were added to a 500 ml four-neck flask in a continuous manner. The feed rate was controlled at 25 parts by weight/min, and the temperature during the reaction was maintained at 100°C to 110°C. After reacting for 15 hours, a light yellow transparent mixed solution with a solid content concentration of 50% by weight can be obtained.

Then, 100 parts by weight of the above mixed solution was added to 25 parts by weight of ethylene glycol ether acetate, and 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of benzophenone tetracarboxylic dianhydride were added simultaneously. , and heated to 110°C to 115°C. After reacting for 2 hours, the second alkali-soluble resin of Synthesis Example A-2-1 (hereinafter referred to as A-2-1) can be prepared, with an acid value of 98 mgKOH/g and a weight average molecular weight of 2205.

Synthesis Example A-2-2

100 parts by weight of terpene epoxy compound (manufactured by Nippon Steel Chemical Co., the model is the commodity of ESF-300, and its epoxy equivalent is 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyl triethyl chloride Ammonium ammonium, 0.1 parts by weight of 2,6-di-tert-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were continuously added into a 500 ml four-necked flask. The feed rate was controlled at 25 parts by weight/min, and the temperature during the reaction was maintained at 100°C to 110°C. After reacting for 15 hours, a light yellow transparent mixed liquid with a solid content concentration of 50% by weight can be obtained.

Next, 100 parts by weight of the above mixed solution was dissolved into 25 parts by weight of ethylene glycol ether acetate, and 13 parts by weight of benzophenone tetracarboxylic dianhydride was added at the same time, and heated to 90°C to 95°C. After reacting for 2 hours, add 6 parts by weight of tetrahydrophthalic anhydride, and react at 90°C to 95°C for 4 hours to obtain the second alkali-soluble resin of Synthesis Example A-2-2 (hereinafter referred to as A-2-2), its acid value is 99.0mgKOH/g, and the weight average molecular weight is 2630.

Synthesis Example A-2-3

With 400 parts by weight of epoxy compound (manufactured by Nippon Kayaku Corporation, the model is NC-3000, and its epoxy equivalent is 288), 102 parts by weight of acrylic acid, 0.3 parts by weight of methoxyphenol (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 reacting for 9 hours, an intermediate product with an acid value of 2.2 mgKOH/g can be obtained. Next, add 151 parts by weight of tetrahydrophthalic anhydride (tetrahydrophthalicanhydride), and react at 95° C. for 4 hours to obtain the second alkali-soluble resin of Synthesis Example A-2-3 (hereinafter referred to as A- 2-3), its acid value is 102mgKOH/g, and its weight average molecular weight is 3200.

Preparation of photosensitive resin composition

The photosensitive resin compositions of Examples 1-12 and Comparative Examples 1-8 are prepared according to Table 2 and Table 3 as follows.

Example 1

100 parts by weight of the first alkali-soluble resin (A-1-1), 40 parts by weight of dipentaerythritol hexaacrylate (hereinafter referred to as B-1), 3 parts by weight of 2-methyl-1-(4- Methylthiophenyl)-2-morpholino-1-propanone (hereinafter referred to as C-1), 3 parts by weight of 2,2'-bis(2,4-dichlorophenyl)-4,4 ',5,5'-tetraphenyldiimidazole (hereinafter referred to 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 C.I.PigmentR254/C.I.PigmentY139=80/20, and hereinafter referred to as E-1) and 0.1 part by weight of 2,2-thiobis(4-methyl-6-tert-butyl Phenol) (hereinafter referred to as G-2) is added to 500 parts by weight of ethyl 3-ethoxypropionate (hereinafter referred to as D-1), and after stirring evenly with a shaking type stirrer (shaking typestirrer), you can The photosensitive resin composition of Example 1 was prepared. Table 2 shows the results obtained by evaluating the obtained photosensitive resin composition by the following evaluation methods of alkali solution resistance, voltage retention ratio and contrast ratio.

Examples 2 to 12 and Comparative Examples 1 to 8

Examples 2 to 12 and Comparative Examples 1 to 8 use the same preparation method as that of the photosensitive resin composition of Example 1, the difference is that Examples 2 to 12 and Comparative Examples 1 to 8 change the photosensitivity The types and usage amounts of the raw materials in the resin composition, and their formulations and evaluation results are shown in Table 2 and Table 3, respectively, and will not be repeated here.

Evaluation method

1. Alkali resistance

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

Next, the above-mentioned prebaked coating film was irradiated with ultraviolet light of 100 millijoules/square centimeter (mJ/cm ² ) using an exposure machine (manufactured by Canon, model number PLA-501F). After exposure, bake at 235° C. for 30 minutes to form a photosensitive resin layer with 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, the concentration of which is 0.5% by weight) at 23°C. After 60 minutes, the chromaticity was measured again, and the alkali-resistant color difference (ΔEab*) of the photosensitive resin layer was calculated by the following formula (X), and evaluated according to the following criteria:

ΔEab*＝[(ΔL) ² +(Δa) ² +(Δb) ² ] ^1/2 formula (X)

☆: ΔEab*<1.

◎: 1≦ΔEab*<2.

○: 2≦ΔEab*<4.

Δ: 4≦ΔEab*<6.

╳: 6≦ΔEab*.

2. Voltage retention

A SiO ₂ film for preventing the dissolution of sodium ions is formed, and further, an indium tin oxide (InidiumTinOxide; ITO) electrode with a predetermined pattern is vapor-deposited on the soda-lime glass substrate. The photosensitive resin compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 8 were coated on 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 with a film thickness of 2.0 μm. Next, without covering the mask, the aforementioned prebaked coating film was irradiated with light of 700 J/m ² . The exposed coating film was dipped in a developing solution with a temperature of 23° C. and a concentration of 0.04 weight percent potassium hydroxide. After 1 min, wash with ultrapure water and air dry. Then, the developed coating film was post-baked at a temperature of 230° C. for 30 minutes to form a cured coating film.

Next, the pixel substrate formed by the aforementioned cured coating film and the ITO electrode having been vapor-deposited in a predetermined pattern were bonded with a sealing agent, and glass beads with a particle diameter of 1.8 mm were placed between them. A liquid crystal material (manufactured by Merck, model number MLC6608) was injected into the gap between the sealing agent, the pixel substrate and the ITO electrodes to form a liquid crystal cell.

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

The aforementioned voltage retention rate represents a value, and this value represents (the potential difference of the liquid crystal cell after 16.7 milliseconds/the voltage applied by the liquid crystal cell at 0 milliseconds). When the voltage retention rate of the liquid crystal cell does not exceed 90%, the prepared liquid crystal cell cannot stably maintain the voltage within 16.7 milliseconds, so that the liquid crystal molecules in the liquid crystal cell are prone to the defect of afterimage. The voltage retention measured in the aforementioned Examples 1 to 12 and Comparative Examples 1 to 8 is evaluated according to the following criteria:

◎: 95%<Voltage retention rate≦100%.

○: 90%<Voltage holding rate≦95%.

△: 80%<Voltage retention rate≦90%.

╳: Voltage retention rate≦80%.

3. Contrast

The photosensitive resin compositions prepared in Examples 1 to 12 and Comparative Examples 1 to 8 were coated on a glass substrate with a size of 100 mm×100 mm by spin coating. Then, drying under reduced pressure was performed at a pressure of 100 mmHg for 30 seconds. Next, a pre-baking process is performed at a temperature of 80° C. for 2 minutes to form a pre-baked coating film with a film thickness of 2.5 μm. After the pre-baking process, irradiate the pre-baked coating film with an energy of 100mJ/cm ² of ultraviolet light (exposure machine CanonPLA-501F), and immerse the exposed pre-baked coating film in a developer solution at 23°C. After 1 minute, the coating film was washed with pure water, and a post-baking process was performed at 235°C. After 30 minutes, a photosensitive resin layer with a film thickness of 2.0 μm was formed on the glass substrate.

The photosensitive resin layer with a film thickness of about 2.0 μm was used to measure the luminance value of the photosensitive resin layer with the detection device shown in FIG. 1 and FIG. 2 , and the ratio of the luminance was calculated. In the detection device 100 of FIG. 1, the above-mentioned photosensitive resin layer 110 is arranged between two polarizers 120 and 130, and the light emitted from the light source 140 passes through the polarizer 120, the photosensitive The resin layer 110 and the polarizer 130 . Then, the luminance value (cd/cm ² ) of the light passing through the polarizing plate 130 was measured with a luminance meter 150 (manufactured by Topcon Corporation, model number: BM-5A).

Wherein, the polarization direction 120 a of the polarizer 120 is parallel to the polarization direction 130 a of the polarizer 130 , and the luminance value measured by the device 100 in FIG. 1 is A. The detection device 200 shown in FIG. 2 is substantially the same as the detection device 100 shown in FIG. 1, except that the polarization direction 220a of the polarizer 220 in the detection device 200 is perpendicular to the polarization direction 230a of the polarizer 230, and The luminance value measured by the device 200 is B.

Then, the following formula (XI) calculates the contrast of the photosensitive resin composition, and evaluates according to the following criteria:

◎: 1500≦contrast.

○: 1200≦contrast<1500.

△: 900≦contrast<1200.

╳: Contrast <900.

From the results of Table 2 and Table 3, it can be seen that when the first alkali-soluble resin (A-1) of the alkali-soluble resin (A) uses an ethylenically unsaturated monomer (a1-1) with a hindered amine structure as a copolymerizable monomer , the prepared photosensitive resin composition has good voltage retention.

Secondly, when the first alkali-soluble resin (A-1) of the alkali-soluble resin (A) uses an ethylenically unsaturated monomer (a1-2) having an oxetanyl group as a copolymerizable monomer, the obtained The 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 shown in formula (II), the prepared photosensitive resin composition has Better alkali resistance.

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

In addition, when the photosensitive resin composition of the present invention contains the dye (F), the prepared photosensitive resin composition has better contrast.

It should be added that although the present invention uses specific compounds, compositions, reaction conditions, manufacturing processes, analysis methods or specific instruments as examples to illustrate the photosensitive resin composition for color filters of the present invention and its application, the present invention belongs to Anyone with ordinary knowledge in the technical field will know that the present invention is not limited thereto. Without departing from the spirit and scope of the present invention, the photosensitive resin composition for the color filter of the present invention and its application can also use other compounds , composition, reaction conditions, process, analytical methods or instruments.

Although the present invention has been disclosed above in terms of implementation, it is not intended to limit the present invention. Anyone with ordinary knowledge in the technical field of the present invention can make various changes without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention should be defined by the appended claims.

Table 2

Abbreviated Chinese name

B-1 dipentaerythritol hexaacrylate (manufactured by Toa Gosei)

B-2 Ethoxylated pentaerythritol tetraacrylate

B-3KAYARADDPCA-20 (manufactured by Nippon Kayaku Co., Ltd.)

C-12-Methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone

C-22,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole

C-34,4'-bis(diethylamine)benzophenone

C-41-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-benzoyl oxime)

Ethyl D-13-ethoxypropionate

D-2 Propylene Glycol Methyl Ether Acetate

E-1C.I.PigmentR254/C.I.PigmentY139＝80/20

E-2C.I.PigmentG36/C.I.PigmentY150＝60/40

E-3C.I.PigmentB15:6

F-1C.I. Acid Blue 25

F-2C.I. Acid Red 289

F-3C.I. Acid Green 5

G-13-Mercaptopropyltrimethoxysilane

G-22, 2-thiobis(4-methyl-6-tert-butylphenol)

G-3 Glycidyl methacrylate

G-41,2,2,6,6-Pentamethyl-piperidinyl acrylate methyl ester

G-53-(methacryloylmethoxy)-3-methyloxetane

table 3

Abbreviated Chinese name

B-1 dipentaerythritol hexaacrylate (manufactured by Toa Gosei)

B-2 Ethoxylated pentaerythritol tetraacrylate

B-3KAYARADDPCA-20 (manufactured by Nippon Kayaku Co., Ltd.)

C-12-Methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone

C-22,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazole

C-34,4'-bis(diethylamine)benzophenone

C-41-[4-(phenylthio)phenyl]-octane-1,2-dione-2-(O-benzoyl oxime)

Ethyl D-13-ethoxypropionate

D-2 Propylene Glycol Methyl Ether Acetate

E-1C.I.PigmentR254/C.I.PigmentY139＝80/20

E-2C.I.PigmentG36/C.I.PigmentY150＝60/40

E-3C.I.PigmentB15:6

F-1C.I. Acid Blue 25

F-2C.I. Acid Red 289

F-3C.I. Acid Green 5

G-13-Mercaptopropyltrimethoxysilane

G-22, 2-thiobis(4-methyl-6-tert-butylphenol)

G-3 Glycidyl methacrylate

G-41,2,2,6,6-Pentamethyl-piperidinyl acrylate methyl ester

G-53-(methacryloylmethoxy)-3-methyloxetane

Claims (14)

1. 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);

an organic solvent (D); and

pigment (E), and

wherein the alkali-soluble resin (A) contains a first alkali-soluble resin (A-1), the first alkali-soluble resin (A-1) is obtained by polymerizing a first mixture, and the first mixture at least contains an ethylenically unsaturated monomer (a1-1) having a hindered amine structure, an ethylenically unsaturated monomer (a1-2) having an oxetanyl group, and an ethylenically unsaturated monomer (a1-3) having a carboxylic acid group.

2. The photosensitive resin composition for a color filter according to claim 1, wherein the ethylenically unsaturated monomer having a hindered amine structure (a1-1) comprises an unsaturated monomer having a structure represented by the following formula (I):

in the formula (I), X₁Represents hydrogen atom, C1-18 linear alkyl group, C3-18 branched alkyl group, C3-18 cycloalkyl group, C6-20 aryl group, C7-12 arylalkyl group, acyl group, oxygen radical or-OX₄；X₄Represents a hydrogen atom, a straight-chain alkyl group having 1 to 18 carbon atoms, a branched-chain alkyl group having 3 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms or an arylalkyl group having 7 to 12 carbon atoms, an acyl group; x₂And X₃Each independently represents methyl, ethyl, phenyl, or X₂And X₃Bonded to each other to form an aliphatic ring having 4 to 12 carbon atoms; represents a covalent bond.

3. The photosensitive resin composition for a color filter according to claim 1, wherein the ethylenically unsaturated monomer having an oxetanyl group (a1-2) comprises an unsaturated monomer having a structure represented by the following formula (II):

in formula (II), Y₁Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; y is₂Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; y is₃、Y₄、Y₅And Y₆Each 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 a represents an integer of 1 to 6.

4. The photosensitive resin composition for a color filter according to claim 1, wherein the first mixture comprises the ethylenically unsaturated monomer having a hindered amine structure (a1-1), the ethylenically unsaturated monomer having an oxetanyl group (a1-2), and the ethylenically unsaturated monomer having a carboxylic acid group (a1-4) which is copolymerizable with the monomer other than the ethylenically unsaturated monomer having a carboxylic acid group (a 1-3).

5. The photosensitive resin composition for a color filter according to claim 4, wherein the amount of the ethylenically unsaturated monomer with a hindered amine structure (a1-2) used is from 5 to 50 parts by weight, the amount of the ethylenically unsaturated monomer with a hindered amine structure (a1-1) used is from 10 to 60 parts by weight, the amount of the ethylenically unsaturated monomer with a carboxylic acid group (a1-3) used is from 10 to 40 parts by weight, based on 100 parts by weight of the total amount of the ethylenically unsaturated monomer with a hindered amine structure (a1-1), the ethylenically unsaturated monomer with an oxetanyl group (a1-2), the ethylenically unsaturated monomer with a carboxylic acid group (a1-3) used, the ethylenically unsaturated monomer with a hindered amine structure (a1-3) used, and the other copolymerizable ethylenically unsaturated monomer (a1-4) used, and the other copolymerizable ethylenically unsaturated monomer (a1-4) is used in an amount of 5 to 75 parts by weight.

6. 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), the second alkali-soluble resin (a-2) being obtained by reacting a second mixture, wherein the 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.

7. 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 a compound having a structure represented by the following formula (III), a compound having the following formula (IV), or a combination of one of the two:

in the formula (III), R₁、R₂、R₃And R₄Each independently represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group having 1 to 5 carbon atoms, or an aryl group or an aralkyl group having 6 to 12 carbon atoms; in the formula (IV), R₅To R₁₈Each independently represents 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.

8. The photosensitive resin composition for a color filter according to claim 6, wherein the amount of the second alkali-soluble resin (A-2) is 30 to 70 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resins (A).

9. The photosensitive resin composition for a color filter according to claim 1, further comprising a dye (F).

10. The photosensitive resin composition for a color filter according to claim 9, wherein the dye (F) is used in an amount of 4 to 40 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (A).

11. The photosensitive resin composition for a color filter according to claim 1, wherein the amount of the first alkali-soluble resin (a-1) used is 30 to 100 parts by weight, the amount of the compound (B) having an ethylenically unsaturated group used is 40 to 400 parts by weight, the amount of the photoinitiator (C) used is 10 to 100 parts by weight, the amount of the organic solvent (D) used is 500 to 5000 parts by weight, and the amount of the pigment (E) used is 30 to 300 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resins (a) used.

12. A method for manufacturing a color filter, wherein a pixel layer is formed using the photosensitive resin composition for a color filter according to any one of claims 1 to 11.

13. A color filter produced by the method according to claim 12.

14. A liquid crystal display comprising the color filter according to claim 13.