CN102736411A - Photosensitive resin composition, and color filter and liquid crystal display device using same - Google Patents

Abstract

A photosensitive resin composition and a color filter and a liquid crystal display device using the same are provided, wherein the alkali-soluble resin of the photosensitive resin composition comprises a first alkali-soluble resin, the first alkali-soluble resin is a polymerization reaction product of a mixture of a first unsaturated monomer containing a carboxylic group, a second unsaturated monomer containing an aromatic ring structure and a third unsaturated monomer containing an alicyclic structure, and the weight ratio of the second unsaturated monomer to the third unsaturated monomer is between 0.01 and 0.40. Therefore, the photosensitive resin composition has better developing performance in the photoetching process, the pixel coloring layer of the color filter has excellent sputtering resistance, and the liquid crystal display device has no bubble display defects.

Description

Photosensitive resin composition, color filter and liquid crystal display device using same

technical field

The present invention relates to a photosensitive resin composition, a color filter and a liquid crystal display device using the same, in particular to a photosensitive resin composition with excellent developability in the photolithography process, and a pixel coloring composition thereof. The layer is a color filter formed of the photosensitive resin composition and has excellent sputtering resistance, and a liquid crystal display device using the color filter and having no bubble display defect.

Background technique

As color filters have been widely used in color liquid crystal displays, color fax machines, color cameras and other applications, the production techniques of color filters are also quite diverse, such as dyeing, printing, electroplating, pigment dispersion, etc. Among them, the pigment dispersion method is the current mainstream.

The so-called pigment dispersion method to make color filters is usually to form a black matrix for light-shielding on a glass substrate with metals such as metal chromium/chromium oxide or photosensitive resin, and then disperse the red pigment. Photosensitive resin (or color photoresist) is coated on the glass substrate, followed by mask exposure, development and curing to form red sub-pixels, and repeat the same steps to successively form green sub-pixels on the glass substrate , blue sub-pixels, the red sub-pixels, green sub-pixels and blue sub-pixels are separated by the black matrix, so far a pixel coloring layer is formed on the glass substrate, and the pixel coloring layer can be formed on the pixel coloring layer as required Forming a protective film, then forming a transparent conductive film on the protective film, and finally cutting, the production of the color filter can be completed.

In the process of the above-mentioned pigment dispersion method, the photosensitive resin is generally composed of pigments, alkali-soluble resins, multifunctional monomers, photoinitiators and solvents, such as Japanese Patent No. 6-95211, Japanese Patent Japanese Patent Application Laid-Open No. 8-183819 and Japanese Patent Publication No. 9-311210 disclose that the alkali-soluble resin used is usually a copolymer made of (meth)acrylic acid as a monomer component.

However, in order to pursue simplification of the manufacturing process and high light transmittance of the color filter, omitting the protective film is a commonly used method in the industry. However, the accompanying problem is that due to the omission of the protective film, in the subsequent sputtering forming process of the transparent conductive film, the pixel colored layer is bound to be cracked because it cannot directly withstand the strong electron beam of the sputtering process .

In order to improve the above problems, as shown in Japanese Patent Application Laid-Open No. 2002-287352, the alkali-soluble resin component in the photosensitive resin composition used is polymerized by unsaturated monomers containing aromatic derivatives, Thereby, the properties such as resistance to dry etching and sputtering can be increased when the pixel colored layer of the color filter is formed with the photosensitive resin composition, but even so, the color filter made of the photosensitive resin composition However, when it is used to manufacture liquid crystal display devices, the problem of bubble-like display defects will occur.

Contents of the invention

The object of the present invention is to provide a photosensitive resin composition with excellent developability in the photolithography process, and a pixel coloring layer formed from the photosensitive resin composition and with excellent sputtering resistance. A color filter, and a liquid crystal display device using the color filter without bubble-like display defects.

The photosensitive resin composition of the present invention includes an alkali-soluble resin, an ethylenically unsaturated group-containing compound, a photoinitiator, an organic solvent, and a pigment, the alkali-soluble resin includes a first alkali-soluble resin, the first alkali-soluble resin It is a polymerization reaction product of a mixture of a first unsaturated monomer containing a carboxylic acid group, a second unsaturated monomer containing an aromatic ring structure, and a third unsaturated monomer containing an alicyclic structure. The weight ratio of the monomer to the third unsaturated monomer is between 0.01-0.40.

In the photosensitive resin composition of the present invention, the weight ratio of the second unsaturated monomer to the third unsaturated monomer is between 0.01-0.35.

In the photosensitive resin composition of the present invention, the weight ratio of the second unsaturated monomer to the third unsaturated monomer is between 0.01-0.30.

In the photosensitive resin composition of the present invention, based on the total weight of the mixture being 100 parts by weight, the total content of the second unsaturated monomer and the third unsaturated monomer is between 25 parts by weight and 60 parts by weight. between.

In the photosensitive resin composition of the present invention, the first unsaturated monomer is selected from acrylic acid, methacrylic acid, 2-methacryloylethoxysuccinate, crotonic acid, α-chloroacrylic acid, Ethacrylic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, or a combination of these.

In the photosensitive resin composition of the present invention, the second unsaturated monomer is selected from styrene, α-methylstyrene, vinyltoluene, p-chlorostyrene, divinylbenzene, benzylmethylbenzene phenyl acrylate, phenyl methacrylate, phenyl methacrylate, phenyl acrylate, 2-nitrophenyl acrylate, 4-nitrophenyl acrylate, 2-nitrobenzyl acrylate, 2-nitrobenzyl methacrylate, 2-nitrophenyl methacrylate, 2-chlorophenyl methacrylate, 4-chlorophenyl methacrylate, 2-chlorophenyl methacrylate , 4-chlorophenyl acrylate, phenoxyethyl methacrylate, phenoxy polyethylene glycol acrylate, phenoxy polyethylene glycol methacrylate, nonylphenoxy polyethylene glycol Acrylates, Nonylphenoxy polyethylene glycol methacrylate, Nitrogen-Phenylmaleimide, Nitrogen-o-Hydroxyphenylmaleimide, Nitrogen-m-Hydroxyphenylmaleimide Imine, nitrogen-p-hydroxyphenylmaleimide, nitrogen-o-methylphenylmaleimide, nitrogen-m-methylphenylmaleimide, nitrogen-p-methyl Phenylmaleimide, nitrogen-o-methoxyphenylmaleimide, nitrogen-m-methoxyphenylmaleimide, nitrogen-p-methoxyphenylmaleimide Imine, o-vinylphenol, m-vinylphenol, p-vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol, 2-vinyl-1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2-naphthol, 3-vinyl-2 -naphthol, 2-isopropenyl-1-naphthol, 3-isopropenyl-1-naphthol, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-methoxymethylstyrene, m-methoxymethylstyrene, p-methoxymethylstyrene, o-(vinylbenzyl)glycidyl ether, m-(vinyl Benzyl)glycidyl ether, p-(vinylbenzyl)glycidyl ether, indene, acetylnaphthalene, or a combination of these.

In the photosensitive resin composition of the present invention, the third unsaturated monomer is selected from unsaturated compounds having a dicyclopentyl group, unsaturated compounds having a dicyclopentenyl group, or a combination thereof.

In the photosensitive resin composition of the present invention, the third unsaturated monomer is selected from dicyclopentyl (meth)acrylate, dicyclopentyl oxide ethyl (meth)acrylate, dicyclopentene (meth)acrylate ester, dicyclopentene oxide ethyl (meth)acrylate, or a combination of these.

In the photosensitive resin composition of the present invention, the mixture further has a fourth unsaturated monomer.

In the photosensitive resin composition of the present invention, the fourth unsaturated monomer is selected from nitrogen-cyclohexylmaleimide, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, acrylic acid n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxyacrylate Hydroxybutyl Acrylate, 4-Hydroxybutyl Acrylate, Allyl Acrylate, Triethylene Glycol Methoxy Acrylate, Nitrogen, Nitrogen-Dimethylaminoethylacrylate, Nitrogen, Nitrogen-Diethylaminopropylacrylate, Nitrogen , nitrogen-dibutylaminopropyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate , isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, methyl 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate, allyl methacrylate, triethylene glycol methoxy methacrylate, dodecyl methacrylate methacrylate, myristyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, eicosyl methacrylate, behenyl methacrylate, methyl Nitrogen, nitrogen-dimethylaminoethyl acrylate, nitrogen, nitrogen-dimethylaminopropyl methacrylate, nitrogen-iso-butylaminoethyl methacrylate, glycidyl methacrylate, acetic acid Vinyl ester, vinyl propionate, vinyl butyrate, vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methallyl glycidyl ether, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, vinylidene cyanide, acrylamide, methacrylamide, α-chloroacrylamide, nitrogen-hydroxyethylacrylamide, nitrogen-hydroxyethylmethacrylamide, 1,3-butadiene , isopentene, chlorinated butadiene, or a combination of these.

In the photosensitive resin composition of the present invention, based on the total weight of the mixture being 100 parts by weight, the content of the first unsaturated monomer is between 20 parts by weight and 60 parts by weight, and the content of the second unsaturated monomer is The content of the unsaturated monomer is between 0.5 parts by weight and 20 parts by weight, the content of the third unsaturated monomer is between 20 parts by weight and 50 parts by weight, and the content of the fourth unsaturated monomer is between 0 parts by weight and Between 15 parts by weight.

In the photosensitive resin composition of the present invention, the alkali-soluble resin further includes a second alkali-soluble resin, and the second alkali-soluble resin includes a monomer having a structure of formula (1):

式(1)

Formula 1)

In the formula, R ¹ and R ² respectively represent a hydrogen atom, a C ₁ -C ₅ linear or branched alkyl group, a phenyl group, or a halogen atom.

In the photosensitive resin composition of the present invention, based on the total weight of the alkali-soluble resin being 100 parts by weight, the content of the first alkali-soluble resin is between 30 parts by weight and 90 parts by weight.

In the photosensitive resin composition of the present invention, based on the total weight of the alkali-soluble resin being 100 parts by weight, the content of the second alkali-soluble resin is between 10 parts by weight and 70 parts by weight.

In the photosensitive resin composition of the present invention, based on 100 parts by weight of the alkali-soluble resin, the content of the ethylenically unsaturated group-containing compound is between 10 parts by weight and 500 parts by weight. The content of the agent is between 2 parts by weight and 200 parts by weight, the content of the organic solvent is between 500 parts by weight and 5000 parts by weight, and the content of the pigment is between 100 parts by weight and 800 parts by weight.

In the photosensitive resin composition of the present invention, the ethylenically unsaturated group-containing compound is selected from the first compound, the second compound, or a combination of these, the first compound is a polyol modified by caprolactone And (meth)acrylic acid reaction derived.

According to the photosensitive resin composition of the present invention, the first compound has a structure shown in formula (2):

式(2)

Formula (2)

In the formula, R ⁹ and R ¹⁰ respectively represent hydrogen or methyl, m is an integer of 1-2, a+b=2-6, a is an integer of 1-6, and b is an integer of 0-5.

In the photosensitive resin composition of the present invention, the second compound has a functional group as shown in formula (3):

式(3)

Formula (3)

In the formula, R ¹¹ represents hydrogen or methyl, respectively.

The color filter of the present invention includes a pixel colored layer formed by photolithography processing of the photosensitive resin composition.

The liquid crystal display device of the present invention includes the color filter.

The effect of the present invention is that the photosensitive resin composition is the mixture obtained by mixing the first unsaturated monomer, the second unsaturated monomer and the third unsaturated monomer, and then copolymerized to form the first base For the soluble resin, based on 100 parts by weight of the mixture, the weight ratio of the second unsaturated monomer to the third unsaturated monomer is between 0.01-0.40. Therefore, the photosensitive resin composition will have better developability in the photolithography process, so that the color filter using the photosensitive resin composition to form the pixel colored layer can have a very good pixel colored layer. Good sputtering resistance, and further, the liquid crystal display device made by using the color filter is completely free from bubble-like display defects.

Detailed ways

First of all, in this article, the (meth)acrylate "(meth)acrylate" means acrylate (acrylate) and/or methacrylate (methacrylate), while the (meth)acrylate group "(meth) )acryloxy” is also known as (meth)acryloyloxy.

The photosensitive resin composition of the present invention includes an alkali-soluble resin, an ethylenically unsaturated group-containing compound, a photoinitiator, an organic solvent, and a pigment.

Wherein, the alkali-soluble resin includes a first alkali-soluble resin, the first alkali-soluble resin has a first unsaturated monomer containing a carboxylic acid group, a second unsaturated monomer containing an aromatic ring structure, and an alicyclic structure-containing The polymerization reaction product of the mixture of the third unsaturated monomer, the weight ratio of the second unsaturated monomer to the third unsaturated monomer is between 0.01-0.40.

If the weight ratio of the second unsaturated monomer to the third unsaturated monomer is less than 0.01, the photosensitive resin composition will suffer from poor developability when undergoing exposure and development processes. If the second unsaturated monomer If the weight ratio of the third unsaturated monomer to the third unsaturated monomer is greater than 0.40, the liquid crystal display device will have bubble-like display defects. Preferably, the weight ratio of the second unsaturated monomer to the third unsaturated monomer is between 0.01-0.35; more preferably, the weight ratio of the second unsaturated monomer to the third unsaturated monomer The weight ratio is between 0.01 and 0.30.

In this way, in the process of using the photosensitive resin composition to manufacture the color filter of the present invention, the photosensitive resin composition will have better developability when exposed and developed, and the photosensitivity After the resin composition passes through the photolithography process, it can form a pixel coloring layer with excellent sputtering resistance. Furthermore, when the color filter is used to manufacture the liquid crystal display device of the present invention, the liquid crystal display can be The device was completely free of blister defects.

The so-called first unsaturated monomer is selected from acrylic acid, methacrylic acid, 2-methacryloylethoxysuccinate, crotonic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid, maleic acid , maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, or a combination of these. Preferably, the first unsaturated monomer is selected from acrylic acid, methacrylic acid, 2-methacryloylethoxysuccinate, or a combination thereof.

Based on the total weight of the mixture as 100 parts by weight, the content of the first unsaturated monomer is between 20 parts by weight and 60 parts by weight, preferably 22 parts by weight and 58 parts by weight, so that the photosensitivity The resin composition has better developability when performing photolithography processes such as exposure and development.

The so-called second unsaturated monomer is selected from styrene, α-methylstyrene, vinyl toluene, p-chlorostyrene, divinylbenzene, benzyl methacrylate, benzyl methacrylate, benzene methacrylate, phenyl acrylate, 2-nitrophenyl acrylate, 4-nitrophenyl acrylate, 2-nitrobenzyl methacrylate, 2-nitrobenzyl methacrylate , 2-nitrophenyl methacrylate, 2-chlorophenyl methacrylate, 4-chlorophenyl methacrylate, 2-chlorophenyl acrylate, 4-chlorophenyl acrylate, phenoxy Ethyl methacrylate, phenoxy polyethylene glycol acrylate, phenoxy polyethylene glycol methacrylate, nonylphenoxy polyethylene glycol acrylate, nonylphenoxy polyethylene glycol acrylate Alcohol methacrylate, nitrogen-phenylmaleimide, nitrogen-o-hydroxyphenylmaleimide, nitrogen-m-hydroxyphenylmaleimide, nitrogen-p-hydroxyphenylmaleimide Toimide, nitrogen-o-methylphenylmaleimide, nitrogen-m-methylphenylmaleimide, nitrogen-p-methylphenylmaleimide, nitrogen-o- -Methoxyphenylmaleimide, nitrogen-m-methoxyphenylmaleimide, nitrogen-p-methoxyphenylmaleimide, o-vinylphenol, m- Vinylphenol, p-vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol Phenylphenol, 2-vinyl-1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2-naphthol, 3-vinyl-2-naphthol, 2-isopropenyl-1 -naphthol, 3-isopropenyl-1-naphthol, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-methoxymethylstyrene, m- -Methoxymethylstyrene, p-methoxymethylstyrene, o-(vinylbenzyl)glycidyl ether, m-(vinylbenzyl)glycidyl ether, p- - (vinylbenzyl)glycidyl ether, indene, acetylnaphthalene, or a combination of these. Wherein, the second unsaturated monomer is represented by styrene, α-methylstyrene, phenyl methacrylate, phenyl acrylate, nitrogen-phenylmaleimide, nitrogen-o-hydroxyphenylmaleimide Preferable are imide, nitrogen-m-hydroxyphenylmaleimide and nitrogen-p-hydroxyphenylmaleimide.

Based on the total weight of the mixture being 100 parts by weight, the content of the second unsaturated monomer is between 0.5 parts by weight and 20 parts by weight, preferably 0.8 parts by weight to 18 parts by weight, so that the photosensitive resin can be After the composition passes through the photolithography process, the pixel coloring layer formed can exhibit excellent sputtering resistance.

The third unsaturated monomer is selected from unsaturated compounds having a dicyclopentanyl group, unsaturated compounds having a dicyclopentenyl group, or a combination thereof.

Specifically, the third unsaturated monomer can be dicyclopentyl acrylate, dicyclopentyl ethoxy acrylate, dicyclopentenyl acrylate, dicyclopentenyl ethoxy acrylate, dicyclopentyl methyl Acrylate, Dicyclopentylethoxymethacrylate, Dicyclopentenylmethacrylate, Dicyclopentenylethoxymethacrylate, or a combination of these.

Based on the total weight of the mixture of 100 parts by weight, the content of the third unsaturated monomer is between 20 parts by weight and 50 parts by weight, which can make the pixel colored layer of the color filter formed have excellent durability. Sputtering properties.

Preferably, the total content of the second unsaturated monomer and the third unsaturated monomer is between 25 parts by weight and 60 parts by weight, which can be used to form the pixel colored layer of the color filter with extremely Good sputter resistance.

The mixture used for polymerization to form the first alkali soluble resin also has a fourth unsaturated monomer.

The so-called fourth unsaturated monomer is selected from nitrogen-cyclohexylmaleimide, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, S-butyl acrylate, tert-butyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, 4-hydroxybutyl acrylate Ester, Allyl Acrylate, Triethylene Glycol Methoxy Acrylate, Nitrogen, Nitrogen-Dimethylaminopropyl Acrylate, Nitrogen, Nitrogen-Diethylaminopropyl Acrylate, Nitrogen, Nitrogen-Dibutylaminopropyl Acrylate ester, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methyl sec-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, methyl 3-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl methacrylate, triethylene glycol methoxy methacrylate, dodecyl methacrylate, tetradecyl methacrylate Cetyl methacrylate, Cetyl methacrylate, Octadecyl methacrylate, Eicosyl methacrylate, Behenyl methacrylate, Nitrogen methacrylate, Nitrogen-dimethyl Amino ethyl ester, nitrogen, nitrogen-dimethylaminopropyl methacrylate, nitrogen-iso-butylamino ethyl methacrylate, glycidyl methacrylate, vinyl acetate, vinyl propionate, butyl Acrylic acid vinyl ester, vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methallyl glycidylether, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile , vinylidene cyanide, acrylamide, methacrylamide, α-chloroacrylamide, nitrogen-hydroxyethylacrylamide, nitrogen-hydroxyethylmethacrylamide, 1,3-butadiene, isopentene, Chlorinated butadiene, or a combination of these, in which methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert- Butyl, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, Isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, vinyl acetate Esters, acrylonitrile, methacrylonitrile, 1,3-butadiene, and isopentene are preferred.

Based on the total weight of the mixture being 100 parts by weight, the content of the fourth unsaturated monomer is between 0 parts by weight and 15 parts by weight, preferably 0 parts by weight and 12 parts by weight, which will make the photosensitivity The developability of the resin composition is good.

Based on the total weight of the alkali-soluble resin being 100 parts by weight, the content of the first alkali-soluble resin is between 30 parts by weight and 90 parts by weight, preferably 35 parts by weight and 85 parts by weight, so that the liquid crystal display device Absolutely free from vesicular defects.

The alkali-soluble resin also includes a second alkali-soluble resin, and the second alkali-soluble resin includes a monomer having a structure of formula (1):

Formula 1)

In the formula (1), R ¹ and R ² respectively represent a hydrogen atom, a C ₁ -C ₅ linear or branched alkyl group, a phenyl group, or a halogen atom.

The monomer having the structure of formula (1) is obtained by reacting the compound having the structure of formula (1) with other copolymerizable compounds.

Wherein, the compound containing the structure of formula (1) can be a bisphenol fluorene (bisphenol fluorene) type compound containing epoxy (epoxy) shown in formula (1-1), or a compound shown in formula (1-2) Hydroxy-containing bisphenol fluorene compounds.

Formula (1-1)

In formula (1-1), R ³ is the same as R ¹ in formula (1), and R ⁴ is the same as R ² in formula (1).

式(1-2)

Formula (1-2)

In formula (1-2), R ⁵ is the same as R ¹ in formula (1), R ⁶ is the same as R ² in formula (1); R ⁷ and R ⁸ represent C ₁ -C ₂₀ alkylene or alkylene respectively Alicyclic group; k and l are integers between 1 and 4 respectively.

Other copolymerizable compounds referred to include: acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid and other unsaturated monocarboxylic acids; maleic acid, itaconic acid, etc. acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid (methylendo -methylene tetrahydro phthalic acid), chlorendic acid, glutaric acid and other dicarboxylic acids and their anhydrides; 1,2,4-benzenetricarboxylic acid (trimellitic acid) and other tricarboxylic acids and their anhydrides; And 1,2,4,5-pyromellitic acid, benzophenonetetracarboxylic acid, biphenyl tetracarboxylic acid, biphenylether tetracarboxylic acid Tetracarboxylic acids and their anhydrides.

More specifically, the second alkali-soluble resin is manufactured by Nippon Steel Chemicals, and its product names are V259ME, V301ME and other products.

Based on the total weight of the alkali-soluble resin being 100 parts by weight, the content of the second alkali-soluble resin is between 10 parts by weight and 70 parts by weight, preferably 15-65 parts by weight, which can make the liquid crystal display device less Blisters show defects.

The ethylenically unsaturated group-containing compound is selected from the first compound, the second compound, or a combination thereof.

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

The caprolactone-modified polyol is prepared by reacting the caprolactone with a polyol having more than 4 functional groups, wherein the caprolactone can be γ-caprolactone, δ-caprolactone , or ε-caprolactone, and preferably ε-caprolactone. The polyol having four or more functional groups may be pentaerythritol, di-trimethylolpropane, dipentaerythritol, or the like. Preferably, the content of the caprolactone ranges from 1 to 12 moles based on the content of the polyol having more than 4 functional groups as 1 mole.

Specific examples of the first compound: tetra(meth)acrylate compounds modified by pentaerythritol caprolactone, tetra(meth)acrylate compounds modified by di-trimethylolpropane caprolactone, dipentaerythritol Caprolactone-modified multi-(meth)acrylate compounds, etc., wherein the dipentaerythritol-caprolactone-modified multi-(meth)acrylate-based compounds can be dipentaerythritol-caprolactone-modified bis(methyl) base) acrylate compounds, dipentaerythritol caprolactone modified tri(meth)acrylate compounds, dipentaerythritol caprolactone modified tetra(meth)acrylate compounds, dipentaerythritol caprolactone modified Penta(meth)acrylate compounds, dipentaerythritol caprolactone-modified hexa(meth)acrylate compounds, etc.

Further, the structure of the above-mentioned dipentaerythritol caprolactone modified multi-(meth)acrylates can be represented by formula (2):

Formula (2)

In formula (2), R ⁹ and R ¹⁰ represent hydrogen or methyl respectively; m is an integer of 1 to 2; a is an integer of 1 to 6, and b is an integer of 0 to 5, wherein, a+b=2 to 6. Preferably a+b=3-6, more preferably a+b=5-6, most preferably a+b=6.

DPCA-20、DPCA-30、DPCA-60、DPCA-120等产品。More specifically, the first compound is manufactured by Nippon Kayaku Co., Ltd., product name

DPCA-20, DPCA-30, DPCA-60, DPCA-120 and other products.

The second compound has a functional group represented by formula (3).

式(3)

Formula (3)

In formula (3), R ¹¹ represents hydrogen or methyl, respectively.

Examples of the second compound include: 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, dicyclopentenyloxyethylene (meth)acrylate Esters, dicyclopentenyl (meth)acrylate, nitrogen, nitrogen-dimethyl (meth)acrylamide, tetrachlorophenyl (meth)acrylate, 2-tetrachlorophenoxy (meth)acrylate Ethyl ester, tetrahydrofurfuryl (meth)acrylate, tetrabromophenyl (meth)acrylate, 2-tetrabromophenoxyethyl (meth)acrylate, 2-trichlorobenzene (meth)acrylate Oxyethyl ester, tribromophenyl (meth)acrylate, 2-tribromophenoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-(meth)acrylate -Hydroxypropyl ester, vinyl caprolactam, nitrogen-vinylpyrrolidone, phenoxyethyl (meth)acrylate, pentachlorophenyl (meth)acrylate, pentabromophenyl (meth)acrylate, polymono(meth)acrylate base) ethylene glycol acrylate, polypropylene glycol mono(meth)acrylate, bornyl (meth)acrylate, ethylene glycol di(meth)acrylate, dicyclopentenyl di(meth)acrylate, tri Glycol diacrylate, Tetraethylene glycol di(meth)acrylate, Tris(2-hydroxyethyl)isocyanate di(meth)acrylate, Tris(2-hydroxyethyl)isocyanate tri(meth)acrylate , caprolactone-modified tris(2-hydroxyethyl)isocyanate tri(meth)acrylate, trimethylolpropyl tri(meth)acrylate, ethylene oxide (hereinafter referred to as EO) modified three Trimethylolpropyl (meth)acrylate, trimethylolpropyl tri(meth)acrylate modified by propylene oxide (hereinafter referred to as PO), triethylene glycol di(meth)acrylate, neopentyl diacrylate Alcohol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra (meth)acrylate, polyester di(meth)acrylate, polyethylene glycol di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, di Pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, tetra(meth)acrylate ditrihydroxy Methyl propyl ester, EO modified bisphenol A di(meth)acrylate, PO modified bisphenol A di(meth)acrylate, EO modified hydrogenated bisphenol A di(meth)acrylate , PO-modified hydrogenated bisphenol A di(meth)acrylate, PO-modified tripropionate, EO-modified bisphenol F di(meth)acrylate, phenolic polyglycidyl ether (methyl ) acrylate, etc.

Preferably, the second compound is selected from trimethylolpropyl triacrylate, EO-modified trimethylolpropyl triacrylate, PO-modified trimethylolpropyl triacrylate, pentaerythritol triacrylate , pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, dipentaerythritol hexaacrylate modified by caprolactone, ditrimethylolpropyl tetraacrylate, PO modified Glycerin tripropionate, TO-1382 manufactured by Toagosei Co., Ltd., or a combination of these.

Based on 100 parts by weight of the alkali-soluble resin, the content of the first compound is between 35 parts by weight and 100 parts by weight, preferably 38 parts by weight to 95 parts by weight, more preferably 40 parts by weight to 90 parts by weight. parts by weight, through the caprolactone structure of the first compound, the liquid crystal display device can be relatively free from foam display defects.

Based on 100 parts by weight of the alkali-soluble resin, the content of the second compound is between 45 parts by weight and 90 parts by weight, preferably 48 parts by weight to 85 parts by weight, more preferably 50 parts by weight to 80 parts by weight. parts by weight, so that the photosensitive resin composition exhibits excellent developability.

Based on the total weight of the alkali-soluble resin as 100 parts by weight, the content of the ethylenically unsaturated group-containing compound is between 10 parts by weight and 500 parts by weight, preferably 20 parts by weight to 450 parts by weight, and 30 parts by weight. More preferably, the weight part to 400 parts by weight can make the photosensitive resin composition have good developability.

The photoinitiator of the present invention may be selected from acetophenone, biimidazole, acyloxime, or a combination thereof.

The acetophenone compounds referred to are: p-dimethylamino-acetophenone (p-dimethylamino-acetophenone), α, α'-dimethoxyazoxy-acetophenone (α, α'-dimethoxyazoxy-acetophenone) , 2,2'-dimethyl-2-phenylacetophenone (2,2'-dimethyl-2-phenyl-acetophenone), p-methoxy-acetophenone (p-methoxy-acetophenone), 2-methyl Base-1-(4-methylthiophenyl)-2-morpholino-1-propanone[2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone], 2-benzyl -2-nitrogen, nitrogen-dimethylamino-1-(4-morpholinophenyl)-1-butanone [2-benzyl-2-N, N-dimethylamino-1-(4-morpholinophenyl)-1- butanone].

The diimidazole compounds referred to are: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole [2,2'-bis(o-chlorophenyl) -4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-fluorophenyl)-4,4',5,5'-tetraphenylbiimidazole[2,2' -bis(o-fluorophenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyl Diimidazole [2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-methoxyphenyl)-4,4 ', 5,5'-tetraphenylbiimidazole [2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(o-methoxyphenyl) phenyl)-4,4',5,5'-tetraphenylbiimidazole [2,2'-bi s(o-ethylphenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2 , 2'-bis(p-methoxyphenyl)-4,4',5,5'-tetraphenyldiimidazol[2,2'-bi s(p-methoxyphenyl)-4,4',5, 5'-tetraphenyl-biimidazole], 2,2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole[2 , 2'-bis(2,2',4,4'-tetramethoxyphenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(2-chlorophenyl)-4, 4',5,5'-tetraphenylbiimidazole [2,2'-bi s(2-chlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole], 2,2'-bis(2 ,4-dichlorophenyl)-4,4',5,5'-tetraphenyldiimidazol[2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl -biimidazole] etc.

The acyloxime compounds referred to are: ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9 hydrogen-carbazole-3-substituent]-, 1-(oxygen -acetyl oxime) [Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-y1]-, 1-(O-acetyl oxime), as produced by Ciba Specialty Chemicals under the trade name CGI -242, its structure is shown in formula (4)], 1-(4-phenyl-thio-phenyl)-octane-1,2-dione 2-oxime-oxygen-benzoic acid ester [ [ , Ethanone, 1-[9-ethyl-6-(2-chloro-4-benzyl-thio-benzoyl)-9 hydrogen-carbazole-3-substituent]-, 1-( Oxygen-acetyl oxime) [Ethanone, 1-[9-ethyl-6-(2-cholro-4-benzyl-thio-benzoyl)-9H-carbazole-3-y1]-, 1-(O-acetyl oxime), Made by Asahi Denka Co., Ltd., its structure is shown in formula (6)].

式(4)

Formula (4)

Formula (5)

式(6)

Formula (6)

Preferably, the photoinitiator is 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-acetone, 2-benzyl-2-nitrogen, nitrogen-dimethyl Amino-1-(4-morpholinophenyl)-1-butanone, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, ethyl Alkanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9hydro-carbazole-3-substituent]-, 1-(oxy-acetyloxime), or a combination of these .

The photoinitiator of the present invention can further add following compounds: thioxanthone (thioxanthone), 2,4-diethyl-thioxanthanone (2,4-diethyl-thioxanthanone), thioxanthone-4-sulfone ( thioxanthone-4-sulfone), benzophenone (benzophenone), 4,4'-bis(dimethylamino)benzophenone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis( Diethylamino) benzophenone [4,4'-bis (diethylamino) benzophenone] and other benzophenone (benzophenone) compounds; benzil, acetyl (acetyl) and other α-diketones (α -diketone); benzoin and other ketone alcohols (acyloin); benzoin methylether, benzoinethylether, benzoin isopropyl ether, etc. Keto alcohol ether (acyloin ether); 2,4,6-trimethylbenzoyl diphenylphosphine oxide (2,4,6-trimethyl-benzoyl-diphenyl-phosphineoxide), bis-(2,6- Acyl phosphine such as methoxybenzoyl)-2,4,4-trimethylbenzylphosphine oxide [bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethyl-benzyl-phosphineoxide] Oxide (acylphosphineoxide); anthraquinone (anthraquinone), 1,4-naphthoquinone (1,4-naphthoquinone) and other quinones (quinone); phenacyl chloride (phenacyl chloride), tribromomethyl phenyl sulfone ( tribromomethyl-phenylsulfone), tris(trichloromethyl)-s-triazine [tris(trichloromethyl)-s-triazine] and other halides; and di-tertbutylperoxide and other peroxides. Among them, benzophenone (benzophenone) compounds are preferred, especially 4,4'-bis(diethylamino)benzophenone.

Based on 100 parts by weight of the alkali-soluble resin, the content of the photoinitiator is between 2 parts by weight and 100 parts by weight, preferably 3 parts by weight to 75 parts by weight, more preferably 5 parts by weight to 50 parts by weight.

The organic solvent of the present invention can dissolve the alkali-soluble resin, the ethylenically unsaturated group-containing compound and the photoinitiator without reacting with them, and has appropriate volatility.

The more commonly used organic solvents are, for example: 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, three 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, tripropylene glycol monomethyl ether Monomethyl ether), tripropylene glycol monoethyl ether (tripropylene glycol monoethyl ether) and other (poly) alkylene glycol monoalkyl ethers; ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate (poly)alkylene glycol monoalkyl ether acetates such as esters and propylene glycol ether acetates; diglyme, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers; methyl ethyl ketone, cyclic Ketones such as hexanone, 2-heptanone, and 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; methyl 2-hydroxy-2-methylpropionate, Ethyl 2-Hydroxy-2-methylpropionate, Methyl 3-Methoxypropionate, Ethyl 3-Methoxypropionate, Methyl 3-Ethoxypropionate, 3-Ethoxypropionate ethyl ester, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3 -Methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, propyl n-butyl butyrate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, acetyl Other esters such as ethyl acetate and ethyl 2-oxybutyrate; aromatic hydrocarbons such as toluene and xylene; and nitrogen-methylpyrrolidone, nitrogen, nitrogen-dimethylformamide, nitrogen, nitrogen- Carboxylic acid amides such as dimethylacetamide, etc.

Preferably, the organic solvent is selected from propylene glycol methyl ether acetate and ethyl 3-ethoxy propionate or used in combination.

Based on 100 parts by weight of the alkali-soluble resin, the content of the organic solvent is between 500 parts by weight and 5000 parts by weight, preferably 800 parts by weight and 4000 parts by weight.

The pigment can be an inorganic pigment, an organic pigment, or a combination of these.

The inorganic pigments are metal compounds such as metal oxides and metal complex salts, for example: oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, plumbous, antimony, and the aforementioned metals of composite oxides.

The organic pigments can be used alone or in combination with one of the following: C.I. Pigment Yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175; 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 average particle diameter of the primary particles of the pigment is preferably 10 nm to 200 nm, more preferably 20 nm to 150 nm, most preferably 30 nm to 130 nm.

If necessary, the pigment (E) can also be accompanied by a dispersant such as cationic, anionic, nonionic, amphoteric, polysiloxane-based, fluorine-based and other surfactants.

Described tensio-active agent can be used alone or mixed multiple use from the following enumeration: polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether polyethylene oxide alkyl ethers; polyethylene oxide octylphenyl ether, polyethylene oxide nonylphenyl ether and other polyethylene oxide alkyl phenyl ethers; polyethylene glycol dilaurate Polyethylene glycol diesters such as polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid modified polyesters; tertiary amine modified polyurethanes; Shin-Etsu Chemical Industry KP product manufactured by Toray Dow Corning Silicon, SF-8427 product manufactured by Toray Dow Corning Silicon, Polyflow product manufactured by Kyoeisha Oleochemical Industry, Aifu manufactured by Tochem Products Co., Ltd. F-Top products, Megafac products manufactured by Dainippon Ink Chemical Industries, Fluorade products manufactured by Sumitomo 3M, Asahi Guard products manufactured by Asahi Glass , A product of Surflon manufactured by Asahi Glass.

Based on 100 parts by weight of the alkali-soluble resin, the content of the pigment is between 100 parts by weight and 500 parts by weight, preferably 120 parts by weight and 450 parts by weight. The photosensitive resin composition of the present invention is based on the aforementioned alkali-soluble resin, the ethylenically unsaturated group-containing compound, the photoinitiator, the organic solvent, and the pigment as essential components, and may be further added as required. Substances, such as: surfactants, fillers, polymer compounds (referring to those other than the alkali-soluble resin), adhesion promoters, antioxidants, ultraviolet absorbers, anti-coagulation agents, etc.

Wherein, the said surfactant can improve the applicability of the present invention, and its specific example is the surfactant used with the aforementioned pigment; the total weight of the alkali-soluble resin is 100 parts by weight, and the surfactant The content is between 0 parts by weight to 6 parts by weight, preferably 0 parts by weight to 4 parts by weight, more preferably 0 parts by weight to 3 parts by weight.

Furthermore, the filler can be glass, aluminum; the macromolecular compound can be polyvinyl alcohol, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate; the adhesion promoter can be vinyltrimethoxysilane, Vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, nitrogen-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, nitrogen-(2- Aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidylpropyltrimethoxysilane, 3-glycidylpropylmethyldimethoxysilane Methoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methoxysilane Acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; the antioxidant can be 2,2-thiobis(4-methyl-6-tert-butylphenol), 2 , 6-di-tert-butylphenol; the UV absorber can be 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorophenyl azide, alkoxybenzophenone ; The anti-coagulation agent can be sodium polyacrylate.

Based on 100 parts by weight of the total weight of the alkali-soluble resin, the content of fillers, polymer compounds other than the alkali-soluble resin, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomeration agents and the like is between 0 Between parts by weight and 10 parts by weight, preferably 0 parts by weight to 6 parts by weight, more preferably 0 parts by weight to 3 parts by weight.

The photosensitive resin composition of the present invention is prepared by mixing and dissolving the alkali-soluble resin, the ethylenically unsaturated group-containing compound, the photoinitiator, etc. in the organic solvent, and then adding the pigment, if necessary In addition, additives such as surfactants and adhesion promoters are added for uniform mixing to prepare the photosensitive resin composition in a solution state.

The color filter of the present invention includes a pixel colored layer formed by photolithography processing of the photosensitive resin composition.

During the production and molding of the color filter, the above-mentioned photosensitive resin composition of the present invention in a solution state is coated on the substrate by a coating method such as rotary coating, casting coating or roll coating. The substrate can be alkali-free glass, soda-lime glass, hard glass (Pileus glass), quartz glass, and these glasses with a transparent conductive film attached to a liquid crystal display device, or it can be used in a photoelectric conversion device (such as solid-state photography device) substrate (such as: silicon substrate); and, before the photosensitive resin composition is coated on the substrate, the black matrix for shading that can isolate the colored layers of pixels such as red, green, blue, etc. (black matrix) is processed and formed on the substrate.

After coating, most of the organic solvent contained in the photosensitive resin composition is removed by drying under reduced pressure, and then the residual organic solvent is completely removed by pre-bake to form a pre-bake coating film. During the process, the operating conditions of vacuum drying and pre-baking are different according to the types and mixing ratios of the ingredients. Usually, vacuum drying is carried out at a pressure of 0 mmHg to 200 mmHg for 1 second to 60 seconds, while pre-baking is Carry out at a temperature of 70° C. to 110° C. for 1 minute to 15 minutes.

After pre-baking, the pre-baked coating film is exposed with a mask having a specific pattern. The light used in the exposure process is preferably ultraviolet rays such as g-line, b-line, and i-line, and the equipment used to emit ultraviolet rays can be (ultra) high-pressure mercury lamps and metal halide lamps.

After exposure, immerse the pre-baked coating film in a developer at a temperature of 23±2°C, and develop it for about 15 seconds to 5 minutes to remove unnecessary parts of the pre-baked coating film and place it on the substrate Form a predetermined pattern.

The developing solution used 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, diethylamine, Methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, or bases such as 1,8-diazabicyclo-(5,4,0)-7-undecene The alkaline aqueous solution composed of neutral compounds generally has a concentration between 0.001% by weight and 10% by weight, preferably between 0.005% by weight and 5% by weight, and more preferably between 0.01% by weight and 1% by weight.

Afterwards, wash the pattern on the substrate with water, then air-dry the pattern with compressed air or compressed nitrogen, and finally perform post-bake on the pattern with a heating device such as a hot plate or an oven, and set the heating temperature Between 150° C. and 250° C., the heating time is 5 minutes to 60 minutes when using a hot plate, and 15 minutes to 150 minutes when using an oven, so as to fix and form the pattern into a pixel colored layer.

By repeating the above steps, red, green, blue and other pixel coloring layers can be sequentially formed on the substrate.

Next, in a vacuum environment with a temperature between 220° C. and 250° C., an ITO protective film is formed by sputtering on the surface of the pixel colored layer. If necessary, the ITO protective film is etched and wired, and then the ITO is formed. Coating the alignment film on the surface of the protective film can make and shape the color filter.

The liquid crystal display device of the present invention includes the color filter.

Further, as far as the manufacture of the liquid crystal display device (such as a liquid crystal panel) is concerned, another glass substrate inlaid with a thin film transistor (Thin Film Transistor, TFT) and coated with an alignment film is taken. The liquid crystal display device can be manufactured by placing a gap opposite to the glass substrate, injecting liquid crystal molecules into the gap, and attaching polarizing plates to the outer surfaces of the color filter and the glass substrate respectively.

The present invention will be further described with reference to the following examples, but it should be understood that the examples shown are for illustrative purposes only and should not be construed as limitations on the practice of the present invention.

[Synthesis Examples 1 to 12 of the First Alkali-Soluble Resin]

On the four-necked conical flask with a volume of 1000 milliliters, a nitrogen gas inlet, a stirrer, a heater, a condenser tube and a thermometer are arranged, and according to the composition type and the usage ratio shown in Table 1, prepare the required for the synthesis of the alkali-soluble resin Components such as the first unsaturated monomer, the second unsaturated monomer, the third unsaturated monomer, the fourth unsaturated monomer, a polymerization initiator, and a solvent.

When performing polymerization, the first unsaturated monomer, the second unsaturated monomer, the third unsaturated monomer and the fourth unsaturated monomer are continuously added into the four-necked conical flask, and Stir and mix, while raising the temperature of the oil bath of the four-necked conical flask to 100°C; in addition, dissolve the initiator in the solvent, and divide it into five equal amounts, and add an equal amount to the four-necked conical flask at intervals of one hour in the bottle. The reaction temperature during the whole polymerization process is maintained at 100° C., and the polymerization time lasts for 6 hours. After the polymerization is completed, the polymerization product is taken out from the four-necked conical flask, and the solvent is devolatilized to obtain the first alkali-soluble resin.

[Examples 1 to 8 of the photosensitive resin composition, and Comparative Examples 1 to 8]

According to the type of ingredients and the usage ratio shown in Table 2, prepare the alkali-soluble resin (comprising the first alkali-soluble resin and the second alkali-soluble resin) and the ethylenically unsaturated group-containing resin required for synthesizing the photosensitive resin composition. Compound (including the first compound and the second compound), photoinitiator, organic solvent, pigment and other components.

After adding the alkali-soluble resin, the ethylenically unsaturated group-containing compound, the photoinitiator and the pigment into the organic solvent, they are dissolved and mixed with a shaking agitator to prepare the photosensitive resin composition, and then The characteristics were measured by the evaluation method described later, and the obtained evaluation results are shown in Table 2.

[Evaluation method]

1. Sputtering resistance

的ITO薄膜，溅镀温度为220℃，以制得该彩色滤光片。然后，利用100倍的光学显微镜分别观察该彩色滤光片的红、蓝、绿等像素着色层的表面状况，并根据下列标准进行评价：Utilize the prepared photosensitive resin composition to form a pixel colored layer on a glass substrate, and then sputter on the pixel colored layer to form a film with a resistance value of 14.6Ω/sq and a film thickness of

The ITO film is sputtered at a temperature of 220°C to produce the color filter. Then, utilize a 100-fold optical microscope to observe the surface conditions of the red, blue, green and other pixel colored layers of the color filter respectively, and evaluate according to the following criteria:

○: No cracks or scratches

△: A few cracks and surface scratches

×: Many cracks and surface scratches

2. Bubble display defects

The liquid crystal display device prepared by using the color filter is placed in an environment with a temperature of 100°C and a humidity of 95RH%, and the time t1 at which bubble-like display defects appear is observed with the naked eye, and evaluated according to the following criteria:

◎: t1＞500 hours

○: 300 hours<t1≤500 hours

△: 100 hours <t1≤300 hours

×: t1<100 hours

3. Developability (or developing speed)

The prepared photosensitive resin composition was coated on a glass substrate of 100mm×100mm by spin coating, firstly dried under reduced pressure at a pressure of 100mmHg for 30 seconds, and then dried at a temperature of 80°C. 1. Pre-baking for 3 minutes to form a pre-baking coating film with a film thickness of 1.0 μm.

Then, get 2% by weight potassium hydroxide aqueous solution 2ml, drop on this pre-bake coating film, measure the time t2 required for this pre-bake coating film to dissolve, promptly be equivalent to developing time, and evaluate according to following standard:

○: t2≤10 seconds

×: t2>10 seconds

[Result analysis]

From the results in Table 2, it can be seen that, as in Examples 1-8, the total weight of the alkali-soluble resin is 100 parts by weight, the weight of the first alkali-soluble resin is between 30 and 90 parts by weight, and the weight of the first alkali-soluble resin is between 30 and 90 parts by weight. The total weight of the mixture formed by the first to fourth unsaturated monomers is 100 parts by weight, and the weight ratio and the total weight of the second unsaturated monomer to the third unsaturated monomer are respectively between 0.01 and 0.40 Between 25 and 60 parts by weight, the prepared photosensitive resin composition can indeed exhibit quite excellent sputtering resistance and developability during the process of forming the pixel colored layer of the color filter. , At the same time, the liquid crystal display device made of this color filter will not produce bubble-like display defects at all.

In contrast, as in Comparative Examples 2-5, the first alkali-soluble resin used (i.e. Synthesis Examples 7-9), the weight ratio of the second unsaturated monomer to the third unsaturated monomer is greater than 0.40, and then As in Comparative Examples 1, 7, and 8, the first alkali-soluble resin used (i.e. Synthesis Examples 10-12), the weight ratio of the second unsaturated monomer to the third unsaturated monomer is less than 0.01, and not Containing the second unsaturated monomer or the third unsaturated monomer, the prepared photosensitive resin composition is used in the process of forming the pixel coloring layer of the color filter, in terms of sputtering resistance and developability, etc. At the same time, the liquid crystal display device manufactured with this color filter will produce more serious bubble-shaped display defects.

In summary, the photosensitive resin composition of the present invention, the color filter and the liquid crystal display device using the same, control the first alkali-soluble resin used in the photosensitive resin composition, the second unsaturated monounsaturated resin The weight ratio of the monomer to the third unsaturated monomer is between 0.01-0.40, so that the photosensitive resin composition can exhibit excellent developability in the photolithography process, and the color filter can be The pixel colored layer formed by using the photosensitive resin composition can exhibit excellent sputtering resistance, and at the same time, the liquid crystal display device made by using the color filter is completely free from bubble-like display defects.

Claims (20)

1. photosensitive resin composition comprises alkali soluble resin, contains compound, light trigger, the organic solvent of ethene property unsaturated group, and pigment; It is characterized in that,

This alkali soluble resin comprises first alkali soluble resin; This first alkali soluble resin is to have first unsaturated monomer that contains the carboxylic acid group, second unsaturated monomer that contains aromatic ring structure; And the polymeric reaction product of potpourri that contains the 3rd unsaturated monomer of alicyclic structure, the weight ratio of this second unsaturated monomer and the 3rd unsaturated monomer is between 0.01～0.40.

2. photosensitive resin composition according to claim 1 is characterized in that, the weight ratio of this second unsaturated monomer and the 3rd unsaturated monomer is between 0.01～0.35.

3. photosensitive resin composition according to claim 1 is characterized in that, the weight ratio of this second unsaturated monomer and the 3rd unsaturated monomer is between 0.01～0.30.

4. photosensitive resin composition according to claim 1 is characterized in that, is 100 weight portions in this mixture total weight, and the content summation of this second unsaturated monomer and the 3rd unsaturated monomer is between 25 weight portions～60 weight portions.

5. photosensitive resin composition according to claim 1; It is characterized in that; This first unsaturated monomer is selected from acrylic acid, methacrylic acid, 2-methacryl ethoxy succinate, butenoic acid, α-Lv Bingxisuan, ethylacrylic acid, cinnamic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, or these a combination.

6. photosensitive resin composition according to claim 1; It is characterized in that; This second unsaturated monomer be selected from styrene, AMS, vinyltoluene, to chlorostyrene, divinylbenzene, benzyl methacrylate, benzyl acrylic ester, phenyl methyl acrylic ester, phenyl acrylate, 2-nitrobenzophenone acrylic ester, 4-nitrobenzophenone acrylic ester, 2-nitrobenzene methyl acrylic ester, 2-nitrobenzoyl ylmethyl acrylic ester, 2-nitrobenzophenone methacrylate, 2-Chlorophenylmethyl acrylic ester, 4-Chlorophenylmethyl acrylic ester, 2-chlorphenyl acrylic ester, 4-chlorphenyl acrylic ester, phenoxy group ethyl-methyl acrylic ester, phenoxy group polyethylene glycol acrylate, phenoxy group polyethylene glycol methacrylate-styrene polymer, Nonylphenoxy polyethylene glycol acrylate, Nonylphenoxy polyethylene glycol methacrylate-styrene polymer, nitrogen-phenyl maleimide, nitrogen-neighbour-hydroxy phenyl maleimide, nitrogen--hydroxy phenyl maleimide, nitrogen-right-hydroxy phenyl maleimide, nitrogen-neighbour-aminomethyl phenyl maleimide, nitrogen--aminomethyl phenyl maleimide, nitrogen-right-aminomethyl phenyl maleimide, nitrogen-neighbour-methoxyphenyl maleimide, nitrogen--methoxyphenyl maleimide, nitrogen-right-methoxyphenyl maleimide, neighbour-vinylphenol ,-vinylphenol, right-vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, neighbour-isopropenyl phenol ,-isopropenyl phenol, right-isopropenyl phenol, 2-vinyl-1-naphthols, 3-vinyl-1-naphthols, 1-vinyl-beta naphthal, 3-vinyl-beta naphthal, 2-isopropenyl-1-naphthols, 3-isopropenyl-1-naphthols, neighbour-methoxy styrene ,-methoxy styrene, p-methoxystyrene, neighbour-methoxy styrene ,-methoxy styrene, right-methoxy styrene, neighbour-(vinyl benzene methyl) glycidyl ethers ,-(vinyl benzene methyl) glycidyl ethers, right-(vinyl benzene methyl) glycidyl ethers, indenes, acetyl group naphthalene, or these a combination.

7. photosensitive resin composition according to claim 1 is characterized in that, the 3rd unsaturated monomer is selected from the unsaturated compound with dicyclo amyl group, the unsaturated compound with double cyclopentenyl, or these a combination.

8. photosensitive resin composition according to claim 7; It is characterized in that; The 3rd unsaturated monomer is selected from (methyl) acrylic acid dicyclo pentyl ester, (methyl) acrylic acid dicyclo amyl group oxidation ethyl ester, (methyl) acrylic acid dicyclopentenyloxyethyl methacrylate, (methyl) acrylic acid dicyclo amylene oxidation ethyl ester, or these a combination.

9. photosensitive resin composition according to claim 1 is characterized in that this potpourri also has the 4th unsaturated monomer.

10. photosensitive resin composition according to claim 9; It is characterized in that; The 4th unsaturated monomer is selected from nitrogen-cyclohexyl maleimide, methyl acrylate, ethyl acrylate, acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, acrylic acid 2-hydroxy methacrylate, acrylic acid 2-hydroxy propyl ester, acrylic acid 3-hydroxy propyl ester, acrylic acid 2-hydroxyl butyl ester, acrylic acid 3-hydroxyl butyl ester, acrylic acid 4-hydroxyl butyl ester, allyl acrylate, acrylic acid triethylene glycol methoxyethoxy ester, nitrogen; Nitrogen-dimethylamino ethyl acrylate, nitrogen; Nitrogen-diethylamino propyl acrylate, nitrogen; Nitrogen-dibutylamino propyl acrylate, acrylic acid epoxy propyl diester, methyl methacrylate, Jia Jibingxisuanyizhi, n propyl methacrylate, isopropyl methacrylate, n-BMA, isobutyl methacrylate, the secondary butyl ester of methacrylic acid, metering system tert-butyl acrylate, 2-hydroxyethyl methacrylate, methacrylic acid 2-hydroxy propyl ester, methacrylic acid 3-hydroxy propyl ester, methacrylic acid 2-hydroxyl butyl ester, methacrylic acid 3-hydroxyl butyl ester, methacrylic acid 4-hydroxyl butyl ester, allyl methacrylate, methacrylic acid triethylene glycol methoxyethoxy ester, lauryl methacrylate, methacrylic acid myristyl ester, methacrylic acid cetyl ester, methacrylic acid stearyl, methacrylic acid eicosyl ester, methacrylic acid docosyl ester, methacrylic acid nitrogen; Nitrogen-dimethylamino ethyl ester, nitrogen; Nitrogen-dimethylaminomethyl propyl acrylate, nitrogen-different-butyl amino methyl ethyl acrylate, methacrylic acid glycidyl ester, vinyl acetate, propionate, vinyl butyrate, methoxy ethylene, ethyl vinyl ether, allyl glycidyl ethers, methylallyl glycidyl ethers, vinyl cyanide, methacrylonitrile, α-Lv Bingxijing, the inferior ethene of cyaniding, acrylic amide, Methacrylamide, α-chloropropene acid amides, nitrogen-hydroxyethyl acrylic amide, nitrogen-hydroxyethyl methacrylamide, 1; 3-butadiene, isopentene, chlorination butadiene, or these a combination.

11. photosensitive resin composition according to claim 9; It is characterized in that; In this mixture total weight is 100 weight portions, and the content of this first unsaturated monomer is between 20 weight portions～60 weight portions, and the content of this second unsaturated monomer is between 0.5 weight portion～20 weight portions; The content of the 3rd unsaturated monomer is between 20 weight portions～50 weight portions, and the content of the 4th unsaturated monomer is between 0 weight portion～15 weight portions.

12. photosensitive resin composition according to claim 1 is characterized in that, this alkali soluble resin also comprises second alkali soluble resin, and this second alkali soluble resin comprises the monomer of (1) structure that has formula:

formula (1)

In the formula, R ¹And R ²Represent hydrogen atom, C respectively ₁～C ₅Alkyl, the phenyl of straight or branched, or halogen atom.

13. photosensitive resin composition according to claim 12 is characterized in that, is 100 weight portions in this alkali soluble resin gross weight, the content of this first alkali soluble resin is between 30 weight portions～90 weight portions.

14. photosensitive resin composition according to claim 12 is characterized in that, is 100 weight portions in this alkali soluble resin gross weight, the content of this second alkali soluble resin is between 10 weight portions～70 weight portions.

15. photosensitive resin composition according to claim 1; It is characterized in that; In this alkali soluble resin gross weight is 100 weight portions, and this content of compound that contains ethene property unsaturated group is between 10 weight portions～500 weight portions, and the content of this light trigger is between 2 weight portions～200 weight portions; The content of this organic solvent is between 500 weight portions～5000 weight portions, and the content of this pigment is between 100 weight portions～800 weight portions.

16. photosensitive resin composition according to claim 1; It is characterized in that; This compound that contains ethene property unsaturated group is selected from first compound, second compound, or these a combination, and this first compound is got with the reaction of (methyl) acrylic acid by the polyvalent alcohol of caprolactone upgrading.

17. photosensitive resin composition according to claim 16 is characterized in that, this first compound has suc as formula structure shown in (2),

formula (2)

In the formula, R ⁹And R ¹⁰Represent hydrogen or methyl respectively, m is 1～2 integer, a+b=2～6, and a is 1～6 integer, b is 0～5 integer.

18. photosensitive resin composition according to claim 16 is characterized in that, this second compound has suc as formula functional group shown in (3).

formula (3)

In the formula, R ¹¹Represent hydrogen or methyl respectively.

19. a colored filter comprises by according to the formed pixel dyed layer after photoetching treatment of arbitrary described photosensitive resin composition in the claim 1 to 18.

20. a liquid crystal indicator comprises colored filter according to claim 19.