KR102377139B1 - Laminated substrate having colored photosensitive resin layer and silica doped base material - Google Patents

Abstract

The present invention includes a colored photosensitive resin layer and a silica-containing polymer substrate, wherein the colored photosensitive resin layer includes (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) It relates to a laminated substrate, which is formed by curing a colored photosensitive resin composition containing a solvent, and a color filter and image display device manufactured using the same.

Description

Laminated substrate comprising a colored photosensitive resin layer and a silica-impregnated substrate {LAMINATED SUBSTRATE HAVING COLORED PHOTOSENSITIVE RESIN LAYER AND SILICA DOPED BASE MATERIAL}

The present invention relates to a laminated substrate including a colored photosensitive resin layer and a silica-impregnated substrate, a color filter manufactured using the same, and an image display device including the same.

Color filters are widely used in various display devices such as imaging devices and liquid crystal displays (LCDs), and their application range is rapidly expanding. The color filter used in the imaging device, liquid crystal display, etc. consists of a coloring pattern of three colors: red, green, and blue, or yellow, magenta, and cyan ( It consists of three coloring patterns: Cyan). In addition, mixing of different colors in each pixel is prevented, or a black matrix is formed at the boundary between the colored layers of each color, and this black matrix (BM) is mainly formed of a black photosensitive resin composition.

The colored pattern of each color filter is generally formed using a colored photosensitive resin composition containing a colorant such as a pigment or dye, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. Colored pattern processing using the colored photosensitive resin composition is typically performed through a lithography process.

Recently, display methods have changed from the conventional CRT (Cathode Ray Tube) to flat panel displays such as plasma displays (Plasma display panel, PDP), liquid crystal displays (LCD), and organic EL (Organic Light Emitting Diodes, OLED). In particular, development is active to realize these flat displays as flexible displays. Therefore, when forming patterns included in color filters for various display devices, there is a need for the development of photosensitive resin compositions and substrates that can provide excellent flexibility and bending adhesion.

A glass substrate is mainly used as a substrate suitable for the above-mentioned flat panel display, but it has a problem in that it is not suitable as a substrate for a flexible display due to its low flexibility. Therefore, polymer substrates are used as flexible display substrates, and polyimide or polycarbonate is mainly used. However, when color filters are manufactured using the polymer substrate, there is a problem of poor adhesion with conventional colored photosensitive resin compositions, and a solution to this problem is required.

The present invention was devised to solve the problems of the prior art,

The object is to provide a laminated substrate comprising a silica-impregnated base material having excellent adhesion to a colored photosensitive resin layer.

Additionally, the present invention aims to provide a color filter manufactured using the above-described laminated substrate and an image display device equipped with the color filter.

The present invention,

It includes a colored photosensitive resin layer and a silica-impregnated polymer base material.

The colored photosensitive resin layer is formed by curing a colored photosensitive resin composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent. A laminated substrate is provided.

In addition, the present invention

A color filter manufactured using the above laminated substrate is provided.

In addition, the present invention

An image display device equipped with the color filter is provided.

The laminated substrate of the present invention can relax the interface by increasing the adhesion between the colored photosensitive resin layer and the silica-containing polymer substrate, and the polymer substrate can provide an effect of increasing transparency by including silica.

In addition, a color filter manufactured using the above-mentioned laminated substrate and an image display device equipped with the same can be provided.

The present invention,

It includes a colored photosensitive resin layer and a silica-impregnated polymer base,

The colored photosensitive resin layer is formed by curing a colored photosensitive resin composition comprising (A) a colorant, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, and (E) a solvent. A laminated substrate is provided.

The polymer substrate included in the laminated substrate of the present invention is characterized by impregnating silica.

The type of the polymer is not particularly limited, and polymer resins commonly used in the field of the present invention can be used. However, it is preferable to use at least one selected from polyimide resin and polycarbonate resin in order to realize flexible properties. can do. More preferably, it is good to use polyimide resin.

By containing silica, the polymer substrate can provide the effect of increasing adhesion to the colored photosensitive resin layer. The silica has a silanol group (Si-OH) on the surface, and the hydroxyl group (-OH) of the silanol group plays a major role in improving hydrophilicity and improving adhesion with the colored photosensitive resin layer.

If the silica particles have a small particle size, the effect of improving adhesion can be excellent. In terms of improving economics and practicality, the average particle size is preferably 5 to 30 nm, but is not limited thereto.

The polymer substrate preferably contains 5 to 70% by weight of silica, more preferably 15 to 60% by weight, based on the total weight. When the silica content is within the above-mentioned range, there is an advantage in that hydrophilic properties can be imparted while maintaining the flexible properties of the polymer.

In the present invention, the thickness of the substrate is not particularly limited, and for example, it can be about 5 to 200 um.

Hereinafter, each component constituting the colored photosensitive resin layer included in the laminated substrate will be described in detail. The colored photosensitive resin layer can be formed by applying the colored photosensitive resin composition and then curing it. That is, the colored photosensitive resin composition means that it is uncured, and the colored photosensitive resin layer means that its constituents have been cured.

(A) Colorant

The colorant (A) contained in the colored photosensitive resin composition of the present invention can be used by selecting one or more types from pigment (a1) and dye (a2).

(a1) Pigment

Pigment (a1) that can be used as the colorant (A) can be an organic pigment or an inorganic pigment commonly used in the field.

The pigment may be a variety of pigments used in printing ink, inkjet ink, etc. Specifically, water-soluble azo pigment, insoluble azo pigment, phthalocyanine pigment, quinacridone pigment, isoindolinone pigment, isoindoline Pigment, perirene pigment, perrinone pigment, dioxazine pigment, anthraquinone pigment, dianthraquinonyl pigment, anthrapyrimidine pigment, anthanthrone pigment, indanthrone pigment, pravanthrone pigment, pyrantrone (pyranthrone) pigment, diketopyrroropyrrole pigment, etc.

Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts, and specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, titanium black, titanium oxide, and carbon. Oxides of metals, such as black, or complex metal oxides are mentioned. Among the inorganic pigments, carbon black is a black pigment that may be coated with resin. Coated carbon black may be more preferable because it has lower conductivity than uncoated carbon black and can provide excellent electrical insulation when forming a matrix or column spacer.

In particular, the pigment may be a compound classified as a pigment in the color index (published by The Society of Dyers and Colourists), and more specifically, pigments with the following color index (C.I.) numbers may be used. However, it is not necessarily limited to these.

Specific examples of preferred pigments (a1) that can be used in the present invention include

C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 63, 83, 86, 93, 94, 109, 110, 117, 125, 128. 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194 and 214, etc.;

C.I. Orange pigments such as Pigment Orange 13, 31, 38, 41, 42, 43, 51, 55, 59, 61, 64, 65, 71 and 73;

C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 209, 215, 216, 224, 242, 254, 264, and 265 ;

C.I. Blue pigments such as Pigment Blue 15, 15:3, 15:4, 15:6 and 60;

C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, and 38;

C.I. Green pigments such as Pigment Green 7, 36, and 58;

C.I. Brown pigments such as Pigment Brown 23 and 25;

C.I. Black pigments such as Pigment Black 1 and 7 may be included, but are not limited thereto.

The black pigment can be used without particular restrictions as long as it has light-blocking properties in visible light.

The above organic pigments and inorganic pigments can be used individually or in a mixture of two or more types.

(a2) dye

The dye (a2) can be used without limitation as long as it has solubility in organic solvents. However, it is preferable to use dye (a2) that has solubility in organic solvents and can ensure reliability such as heat resistance and solvent resistance. The dye includes compounds classified as dyes in the color index (published by The Society of Dyers and Colourists), and known dyes described in the dyeing notes (color dyeing yarn).

Specific examples of the dye include triarylmethane-based dyes, xanthene-based dyes including rhodamine-based dyes, flavin-based dyes, auramine-based dyes, safranin-based dyes, phloxine-based dyes, and methylene blue-based dyes.

Specific examples of triarylmethane dyes include C.I. Basic Violet 1 (methyl violet), C.I. Basic Violet 3 (crystal violet), and C.I. Basic Violet 14 (Magenta); C. I. Basic Blue 1 (Basic Cyanine 6G), C. I. Basic Blue 5 (Basic Cyanine EX), C. I. Basic Blue 7 (Victoria Pure Blue BO), and C.I. Basic Blue 26 (Victoria Blue B conc.); and C. I. Basic Green 1 (brilliant green GX) and C. I. Basic Green 4 (malachite green).

Additionally, rhodamine-based dyes include, for example, C.I. Basic Red 1 (Rhodamine 6G, 6GCP) and C.I. Basic Red 8 (Rhodamine G); and C. I. Basic Violet 10 (Rhodamine B). Additionally, examples of flavin-based dyes include C.I. Basic Yellow 1. Additionally, examples of auramin-based dyes include C.I. Basic Yellow 2 and C.I. Basic Yellow 3. Additionally, examples of safranin-based dyes include C.I. Basic Red 2. Additionally, examples of the phloxine-based dye include C.I. Basic Red 12. In addition, examples of methylene blue dyes include C.I. Basic Blue 9 (Methylene Blue FZ, Methylene Blue B), C.I. Basic Blue 25 (Basic Blue GO), and C.I. Basic Blue 24 (Newmethylene Blue NX). It is not limited to this.

In the present invention, the content of the colorant (A) is not particularly limited, and can be used by appropriately adjusting it to meet the required properties. Typically, the content is preferably 5 to 70% by weight, more preferably 25 to 40% by weight, based on the solid content in the colored photosensitive resin composition. When the content of the colorant (A) is contained within the above range, it is preferable because the color concentration is sufficient when made into a color filter and the coloring power can be expressed most efficiently.

(B) Alkali soluble resin

The alkali-soluble resin (B) contained in the colored photosensitive resin composition of the present invention is a component that provides solubility to the alkaline developer used in the development process. That is, the unexposed portion of the colored photosensitive resin layer formed using the colored photosensitive resin composition is made alkali soluble and acts as a dispersion medium for the pigment. In the present invention, the alkali-soluble resin is not particularly limited, but in order to dissolve in an alkaline developer, it is common to introduce an acid value by introducing a carboxyl group into the resin, but it is not limited to this.

The alkali-soluble resin can be manufactured by copolymerizing an ethylenically unsaturated monomer having a carboxyl group or by reacting an acid anhydride with a resin copolymer having a hydroxyl group to give an acid value, but is not limited thereto.

Specific examples of the ethylenically unsaturated monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; Examples include polymer mono(meth)acrylates having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono(meth)acrylate, with acrylic acid and methacrylic acid being preferred.

A method of imparting an acid value by reacting an acid anhydride to the resin copolymer having a hydroxyl group includes, but is not limited to, a method of imparting an acid value by additionally reacting an anhydride to a hydroxy(meth)acrylate copolymer. .

Specific examples of the hydroxy (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxy. -3-Phenoxypropyl (meth)acrylate, N-hydroxyethyl acrylamide, etc. may be mentioned, but are not limited thereto.

The alkali-soluble resin (B) can be prepared by additionally copolymerizing a copolymerizable unsaturated monomer.

As a specific example of the copolymerizable unsaturated monomer,

Styrene, vinyl toluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinyl Aromatic vinyl compounds such as benzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether;

N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-o-hydroxyphenylmaleimide, N-m-hydroxyphenylmaleimide, N-p-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N-m -N-substituted maleimide compounds such as methylphenylmaleimide, N-p-methylphenylmaleimide, N-o-methoxyphenylmaleimide, N-m-methoxyphenylmaleimide, and N-p-methoxyphenylmaleimide;

Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, i-propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, Alkyl (meth)acrylates such as sec-butyl (meth)acrylate and t-butyl (meth)acrylate; Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6]decan-8-yl(meth)acrylate, 2- Alicyclic (meth)acrylates such as dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, and 3,4-epoxytricyclodecan-9-yl (meth)acrylate;

Aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate;

3-(methacryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyloxetane, 2-(methacryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, etc. Examples include, but are not limited to, unsaturated oxetane compounds, and one or more types may be selected and used therefrom.

The alkali-soluble resin preferably has a weight average molecular weight in terms of polystyrene in the range of 3,000 to 100,000, and more preferably in the range of 5,000 to 50,000. If the weight average molecular weight of the alkali-soluble resin is less than 3,000, the surface is not smooth because the molecular weight of the resin is too low, and if the molecular weight is more than 100,000, the development speed is slow during development.

The acid value of the alkali-soluble resin (B) is preferably 30 to 250 mgKOH/g, more preferably 30 to 200 mgKOH/g, and even more preferably 60 to 150 mgKOH/g, based on solid content. If the acid value of the alkali-soluble resin (B) is less than 30 mgKOH/g, it is difficult for the colored photosensitive resin composition to secure a sufficient development speed, and if the acid value is more than 250 mgKOH/g, adhesion to the substrate is reduced, causing the pattern to be damaged. It is undesirable because a short circuit is likely to occur, problems with compatibility with the colorant may occur and the colorant in the colored photosensitive resin composition may precipitate, or the storage stability of the colored photosensitive resin composition may decrease and the viscosity may increase. That is, when the acid value is within the above range, there are advantages of excellent developability against alkali phenomenon, suppressed residue generation, and improved pattern adhesion.

In addition, the alkali-soluble resin (B) is preferably 5 to 85% by weight, more preferably 5 to 70% by weight, and even more preferably 20 to 55% by weight, based on the solid content in the colored photosensitive resin composition. It's good to be included. If the content of the alkali-soluble resin (B) is within the above range, the solubility in the developer is sufficient, and the omission of non-pixel parts becomes good, so it is difficult to generate residues on the substrate and the film of the pixel part of the exposed area during development. This is desirable because reduction is prevented and pattern formation becomes easy.

(C) photopolymerizability compound

The photopolymerizable compound (C) contained in the colored photosensitive resin composition of the present invention is a compound that can be polymerized by active radicals, acids, etc. generated from the photopolymerization initiator (D) described later by light irradiation, and is polymerized by the action of the photopolymerization initiator. There is no particular limitation as long as it is a compound that contains an unsaturated group and is photosensitive. Preferably, a monofunctional monomer, a difunctional monomer, or a trifunctional or more multifunctional monomer may be used, and one or more monomers selected from these may be used.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, or N-vinylpy. Examples include Lolidon, and commercially available products include Aronix M-101 (Doagosei), KAYARAD TC-110S (Nippon Kayaku), or Viscot 158 (Osaka Yuki Kagaku High School), but are limited to these. That is not the case.

Specific examples of the difunctional monomer include 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. Latex, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, propylene glycol dimethacrylate, urethane (meth)acrylate Commercially available products include Aronics M-210, M-1100, 1200 (Toagosei), KAYARAD HDDA (Nippon Kayaku), Biscot 260 (Osaka Yuki Kagaku High School), AH-600, AT- 600 or UA-306H (Kyoeisha Chemical Co., Ltd.), etc., but are not limited thereto.

Specific examples of the trifunctional or more polyfunctional monomer include trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, and penta. Erythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol penta(meth)acrylate, ethoxylated Examples include dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol hexa(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and commercially available products include Aronics M-309. , TO-1382 (Toagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku), etc., but are not limited thereto.

Among the photopolymerizable compounds exemplified above, it is more preferable to use trifunctional or more polyfunctional monomers, and (meth)acrylates and urethane (meth)acrylates have excellent polymerizability and can improve strength. desirable.

The photopolymerizable compound (C) is preferably contained in an amount of 1 to 50% by weight, and more preferably in an amount of 3 to 35% by weight, based on the solid content in the colored photosensitive resin composition. It is preferable that the content of the photopolymerizable compound (C) is within the range of 1 to 50% by weight based on the above, because the strength and smoothness of the pixel portion are improved.

(D) light curing initiator

The photopolymerization initiator (D) contained in the colored photosensitive resin composition of the present invention can initiate polymerization of the photopolymerizable compound (C) described above by exposure to radiation such as visible light, ultraviolet rays, deep ultraviolet rays, electron beams, and X-rays. It is a compound that generates radicals.

The photopolymerization initiator is commonly used in the field as long as it does not impair the purpose of the present invention, and its type is not particularly limited as long as it can polymerize the alkali-soluble resin and the photopolymerizable compound. Representative examples include, but are limited to, oxime-based compounds, acetophenone-based compounds, benzoin-based compounds, benzophenone-based compounds, biimidazole-based compounds, triazine-based compounds, thioxanthone-based compounds, and anthracene-based compounds. This does not mean that one or more types can be selected and used. Among these, when considering polymerization characteristics, initiation efficiency, absorption wavelength, etc., it may be more preferable to use an oxime-based compound.

Examples of the oxime-based compounds include o-ethoxycarbonyl-α-oxymino-1-phenylpropan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl]-ethanone-1-(O-acetyloxime), (Z)-2-((benzoyloxy)imino)-1-(4-(phenylthio)phenyl)octan-1-one, (E)-1-(((1-(9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)ethylidin)amino)oxy)ethanone and (E)-1- (((1-(6-(4-((2,2-dimethyl-1,3-dioxolan-4-yl)methoxy)-2-methylbenzoyl)-9-ethyl-9H-carbazole-3 -yl)ethylidine)amino)oxy)ethanone, etc., and commercially available products include Ciba's OXE-01 and OXE-02, but are not limited thereto.

Examples of the acetophenone-based compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1-[4-(2- Hydroxyethoxy)phenyl]-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan- 1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one, etc. are mentioned.

Examples of the benzoin-based compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone-based compounds include benzophenone, 0-benzoylmethylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra ( tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

Examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2, 3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) Biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, 2,2-bis(2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4',5,5' position is substituted with a carboalkoxy group. Among these, more preferably 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)- 4,4',5,5'-tetraphenylbiimidazole or 2,2-bis(2,6-dichlorophenyl)-4,4'5,5'-tetraphenyl-1,2'-biimidazole etc. can be mentioned.

Examples of the triazine-based compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)- 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4- Bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2 -yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-tri Azine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloro and methyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine.

Examples of the thioxanthone-based compounds include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone. can be mentioned.

Examples of the anthracene-based compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, etc. can be mentioned.

The photopolymerization initiator (D) is preferably included in an amount of 0.5 to 10% by weight, more preferably 0.5 to 5% by weight, based on the solid content in the colored photosensitive resin composition. When the content of the photopolymerization initiator is within the above range, it is preferable because the coloring photosensitive resin composition becomes highly sensitive and the exposure time is shortened, thereby improving productivity. In addition, it is preferable because the strength of the pixel portion formed using the colored photosensitive resin composition of the present invention and the smoothness on the surface of the pixel portion can be improved.

Meanwhile, according to one embodiment of the present invention, the photopolymerization initiator (D) may further include a photopolymerization initiation aid (d1) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. The colored photosensitive resin composition according to the present invention is preferred because it contains a photopolymerization initiation auxiliary, which further increases sensitivity and improves productivity.

The photopolymerization initiation aid (d1) may preferably be, for example, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds, and organic sulfur compounds having a thiol group.

It is preferable to use an aromatic amine compound as the amine compound, specifically, aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Isoamyl dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (common name: Michler's ketone) ), 4,4'-bis(diethylamino)benzophenone, etc. can be used.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, and dimethoxyphenylthioacetic acid. Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

Specific examples of the organic sulfur compounds having the thiol group include 2-mercaptobenzothiazole, 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyl) rate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. You can.

(E) Solvent

The solvent (E) according to the present invention can be used without particular limitation as long as it is effective in dissolving other components included in the colored photosensitive resin composition. As a specific example, the solvent may be selected from the group consisting of ethers, acetates, aromatic hydrocarbons, ketones, alcohols, esters, and amides, but is not limited thereto.

The ether solvent specifically includes ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether;

Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; etc. can be mentioned.

The acetate solvent specifically includes alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. ;

Alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate; etc. can be mentioned.

Specific examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

Specific examples of the ketone solvent include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone.

Specific examples of the alcoholic solvent include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

The ester solvent specifically includes cyclic esters such as γ-butyrolactone;

Examples include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and ethyl 3-ethoxypropionate.

Specific examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

The solvent (E) is preferably an organic solvent having a boiling point of 100 to 200° C. in terms of coating and drying properties, and more preferably alkylene glycol alkyl ether acetate; ketones; esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, and 3-ethoxypropionic acid. Ethyl, methyl 3-methoxypropionate, etc. are mentioned. These solvents can be used individually or in combination of two or more.

The solvent (E) is preferably contained in an amount of 60 to 90% by weight, and more preferably in an amount of 70 to 85% by weight, based on the total weight of the colored photosensitive resin composition. When the solvent (E) is contained within the above-mentioned range, the applicability becomes good when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes called a die coater), and inkjet. It can provide an effect.

(F) Additives

In addition to the above components, the colored photosensitive resin composition of the present invention may further contain an additive (F) according to the needs of those skilled in the art, within a range that does not impair the purpose of the present invention.

Specific examples of the additive (F) include, but are not limited to, silane coupling agents, pigment dispersants, surfactants, antioxidants, and anti-aggregation agents.

The silane coupling agent is intended to increase adhesion to the substrate, and may be a silane coupling agent having one or more reactive substituents selected from carboxyl group, methacryloyl group, isocyanate group, and epoxy group. Specific examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxy silane, vinyltriacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, and r-glycidox. Cypropyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. can be mentioned, and one or more types can be selected and used.

The silane coupling agent is preferably included in an amount of 0.35 to 5 parts by weight, more preferably 0.45 to 3 parts by weight, based on 100 parts by weight of the solid content of the colorant (A) used. If the content of the silane coupling agent is less than 0.35 parts by weight based on the above standards, it may cause problems with peeling of the resin layer due to lack of adhesion to the substrate, and if it exceeds 5 parts by weight, the photocuring properties of the photosensitive resin composition may decrease. It is not desirable because it happens.

The pigment dispersant is a component that can be added to deagglomerate and maintain stability of pigment (a1). As an example of a method for uniformly dispersing the particle size of the pigment (a1), there is a method of dispersing by adding a pigment dispersant, through which a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

The pigment dispersant commonly used in the field may be used without limitation. Preferably, an acrylate-based dispersant (hereinafter also referred to as ‘acrylic dispersant’) containing butyl methacrylate (BMA) or N,N-dimethylaminoethyl methacrylate (DMAEMA) can be used. Commercially available products of the acrylate-based dispersant include DISPER BYK-163, DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070, DISPER BYK-2150, and DISPER BYK LPN-6919. The acrylic dispersants exemplified above can be used individually or in combination of two or more types.

In addition to the acrylate-based dispersant described above, other resin-type pigment dispersants may be used. The other resin-type pigment dispersants include known resin-type pigment dispersants, especially polyurethanes, polycarboxylic acid esters represented by polyacrylates, unsaturated polyamides, polycarboxylic acids, and (partially) of polycarboxylic acids. Amine salts, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyaminoamide phosphate salts, esters of hydroxyl group-containing polycarboxylic acids and their modified products, or free Oily pigment dispersants such as amides or salts thereof formed by the reaction of polyester having a carboxyl group and poly(lower alkyleneimine); Water-soluble resins or water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymer, (meth)acrylic acid-(meth)acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, or polyvinyl pyrrolidone; Polyester; modified polyacrylate; Examples include adducts of ethylene oxide/propylene oxide and phosphate esters.

Commercially available products of the pigment dispersant of the above-described resin type include, for example, BYK-Chemistry's brand names: DISPER BYK-160, DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK- 166, DISPER BYK-171, DISPER BYK-182,DISPER BYK-184; BASF's product names: EFKA-44, EFKA-46, EFKA-47, EFKA-48, EFKA-4010, EFKA-4050, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA-4300, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; Brand names from Lubirzol: SOLSPERS-5000, SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10; Kawaken Fine Chemical's product names: HINOACT T-6000, HINOACT T-7000, HINOACT T-8000; Ajinomoto's product names: AJISPUR PB-821, AJISPUR PB-822, AJISPUR PB-823; Product names of Kyoeisha Chemical Co., Ltd.: FLORENE DOPA-17HF, FLORENE DOPA-15BHF, FLORENE DOPA-33, FLORENE DOPA-44, etc. are mentioned.

The surfactant serves to improve coating properties, and specific examples include BM-1000, BM-1100 (BM Chemie), Prolide FC-135/FC-170C/FC-430 (Sumitomo 3M Co., Ltd.), SH- Fluorine-based surfactants such as 28PA/-190/SZ-6032 (Dore Silicone Co., Ltd.) may be included, but are not limited thereto.

As specific examples of the antioxidant, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate, 2-[1-(2-hydroxy -3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenylacrylate, 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)prop Poxy]- 2,4,8,10 -tetra-tert-butyldibenz[d,f][1,3,2]dioxaphosphepine, 3,9-bis[2-{3-(3-tert -Butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 2,2'-methylenebis( 6-tert-butyl-4-methylphenol), 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(2-tert-butyl-5- methylphenol), 2,2'-thiobis(6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate , distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3-lauryl thiopropionate), 1,3,5-tris (3,5-di-tert-butyl- 4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 3,3',3'',5,5',5''- Hexa-tert-butyl-a,a',a''-(mesitylene-2,4,6-triyl)tri-p-cresol, pentaerythritol tetrakis[3-(3,5-di-tert -butyl-4-hydroxyphenyl)propionate], 2,6-di-tert-butyl-4-methylphenol and 2,2'-thiobis(4-methyl-6-t-butylphenol), 2 ,6-di-t-butyl-4-methylphenol, etc., but is not limited thereto.

Specific examples of the anti-agglomeration agent include sodium polyacrylate, but are not limited thereto.

That is, the present invention provides a colored photosensitive resin composition with the composition and content of the above-described components, and can be cured to form a colored photosensitive resin layer.

Additionally, a laminated substrate including the colored photosensitive resin layer and the above-described silica-impregnated polymer substrate is provided.

In the silica-containing polymer substrate included in the laminated substrate of the present invention, the polymer is not particularly limited, but one or more types selected from polyimide resin and polycarbonate resin can be used.

As an example of the present invention, a silica-impregnated polyimide substrate can be manufactured through a method including the following steps.

(A1) providing a poly(amic acid) solution;

(B1) preparing a solution containing particles or micelles of the silica portion from a monomer of a silane compound;

⁽ _C1 ⁾ Chemical formula ( ^{R 1} ₎ adding monomers of kenoxy or aryloxy, and

(D1) mixing the solutions from steps (A1) and (C1) above, wherein the silica portion carries a photo-polymerizable unsaturated group; and

(E1) Adding a monomer of the formula R ³ N(R ⁴ ) ₂ (wherein R ³ is a photo-polymerizable unsaturated terminal group and R ⁴ is an alkyl group of C1 to C6) to the solution obtained from step (D1) above. , forming a precursor solution for a photo-polymerizable silica-containing polyimide substrate by allowing the poly(amic acid) to carry a photo-polymerizable unsaturated group; It provides a method for producing a precursor solution for a silica-containing polyimide substrate comprising a.

The above-mentioned method for preparing a precursor solution for a silica-impregnated polyimide substrate involves adding to the solution obtained from step (A1) a compound of the formula H ₂ NR ⁵ -Si(R ² ) ₃ (where R ⁵ is one of C1 to C6). It may further include adding an amino coupling agent of alkylene or arylene, R ⁶ may be the same or different and each represents an alkoxy group of C1 to C6, and then mixing with the solution obtained from step (D1). there is.

The present invention also includes the steps of coating the solution obtained in (E1) through the above-mentioned steps, removing the solvent by evaporation, exposing the coating agent to energy rays, and baking the coating agent to form a silica-impregnated polyimide base film. A method for manufacturing a silica-impregnated polyimide substrate comprising the step of forming can be provided, through which a method for forming the colored substrate of the present invention can be provided.

In addition, in the present invention, in manufacturing a silica-containing polymer substrate, a soluble polymer such as polycarbonate can be used as the polymer substrate. In this case, the polymer is mixed with a solvent to prepare a solution. The ratio of each polymer can be appropriately adjusted depending on the molecular weight of the polymer, and is generally prepared at a concentration of about 10% by weight. A silica-impregnated polymer substrate can be manufactured by adding calculated silica particles to the prepared polymer solution, coating it on release paper, and slowly raising the temperature to remove the solvent.

The laminated substrate of the present invention can be manufactured through the following method.

The introduction of the colored photosensitive resin composition can form a pattern by coating and then patterning through a photolithography method. The photolithography method is not particularly limited in the present invention and a conventional method can be applied.

As an example, the patterned colored photosensitive pattern may be

a) applying a colored photosensitive resin composition to the surface of a silica-impregnated polymer substrate;

b) drying the solvent by pre-cure (pre-bake);

c) placing a photo mask on the obtained film and curing the exposed area by irradiating actinic light;

d) performing a development process to dissolve the unexposed area using an aqueous alkaline solution; and

e) It can be obtained through drying and post-baking steps.

Examples of the polymer substrate include, but are not limited to, polyimide and polycarbonate.

At this time, the application can be done through a wet coating method using application devices such as roll coater, spin coater, slit and spin coater, slit coater (sometimes called die coater), and inkjet to obtain the desired thickness.

Prebaking is performed by heating using an oven, hot plate, etc. The heating temperature and heating time in prebaking are appropriately selected depending on the solvent used, and are performed, for example, at a temperature of 80 to 150°C for 1 to 30 minutes.

Additionally, exposure performed after prebaking is performed by an exposure machine and exposed through a photo mask to expose only the portion corresponding to the pattern. At this time, the light irradiated may be, for example, visible light, ultraviolet rays, X-rays, and electron beams.

Alkaline development after exposure is performed for the purpose of removing the resist from the non-removable portion of the unexposed portion, thereby forming a desired pattern. As a developing solution suitable for this alkaline development, for example, an aqueous solution of carbonate of an alkali metal or alkaline earth metal can be used. In particular, using an aqueous alkaline solution containing 1 to 3% by weight of carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate, using a developer or ultrasonic cleaner at a temperature of 10 to 50°C, preferably 20 to 40°C. Perform.

Post-baking is performed to increase the adhesion between the patterned resin pattern and the substrate, and is performed through heat treatment at 80 to 220°C for 10 to 120 minutes. Postbake, like prebake, is performed using an oven, hot plate, etc.

The colored photosensitive resin pattern obtained through this method has a sufficient size to maintain high light sensitivity and enable excellent fine pattern formation, and has a thickness of several to several thousand micrometers, preferably 0.1 to 100 μm, and more preferably 1 to 50 μm. It is formed by

This colored photosensitive resin pattern not only secures the required adhesion, but also has excellent heat resistance and solvent resistance, thereby improving the reliability of the display device.

<Color Filter>

The present invention provides a color filter manufactured using the above laminated substrate. That is, the color filter of the present invention can be manufactured using a laminated substrate including a colored photosensitive resin layer and a silica-containing polymer substrate. The color filter includes a colored pattern prepared using the colored photosensitive resin composition of the present invention to display a desired pattern.

The color filter may be manufactured using a conventional method well known in the field.

<Image display device>

Additionally, the present invention provides an image display device including the color filter. Specific examples of the image display device include liquid crystal displays (LCDs), organic EL displays (organic EL displays), liquid crystal projectors, displays for game machines, displays for portable terminals such as mobile phones, and displays for digital cameras. Devices, display devices such as car navigation display devices, etc. may be mentioned, but are not limited thereto.

The image display device of the present invention may be manufactured by a method commonly known in the technical field of the present invention, except that it is provided with the color filter.

Hereinafter, the present invention will be described in more detail using examples and comparative examples. However, the following examples are for illustrating the present invention, and the present invention is not limited by the following examples, and may be variously modified and changed within the scope of the present invention. The scope of the present invention will be determined by the technical spirit of the claims described later.

< Manufacturing example >

Manufacturing example 1. Preparation of alkali-soluble resin

A flask equipped with a stirrer, thermometer reflux cooling pipe, dropping lot, and nitrogen introduction pipe was prepared. As a monomer dropping lot, a mixture of 3,4-epoxytricyclodecan-8-yl(meth)acrylate and 3,4-epoxytricyclodecan-9-yl(meth)acrylate at a molar ratio of 50:50 40 Parts by weight, 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyl toluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA). Addition was prepared for stirring. As a chain transfer agent dropping tank, 6 parts by weight of n-dodecanethiol and 24 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) were added and stirred.

Afterwards, 395 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added to the flask, the atmosphere in the flask was changed from air to nitrogen, and the temperature of the flask was raised to 90° C. while stirring. Next, the monomer and chain transfer agent were started dropwise from the dropping lot. Dropping was carried out for 2 hours while maintaining 90°C, and after 1 hour, the temperature was raised to 110°C and maintained for 5 hours to obtain a resin with a solid acid value of 100 mgKOH/g. The prepared resin was kept in an oven at 120°C for 50 hours to prepare a solvent-free resin.

The weight average molecular weight in terms of polystyrene measured by GPC was 17,000, and the molecular weight distribution (Mw/Mn) was 2.3.

Measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of the alkali-soluble resin was performed using the GPC method under the following conditions, and the ratio of the obtained weight average molecular weight and number average molecular weight was calculated as the molecular weight distribution (Mw). /Mn).

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (serial connection)

Column temperature: 40℃

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 mL/min

Injection volume: 50 μl

Detector: RI

Measured sample concentration: 0.6% by weight (solvent = tetrahydrofuran)

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

Manufacturing example 2. Preparation of polymer substrate

(1) Description 1

8mM 4,4'-oxydianiline (ODA) was dissolved in dimethylacetamide (DMAc), 10mM pyromellitic dianhydride (PMDA) was slowly added and mixed, and nitrogen was passed through. By reacting at room temperature for 24 hours, a transparent and sticky poly(amic acid) (PAA) solution was obtained. 4mM 3-aminopropyltriethoxysilane (APrTEOS) was added here, and then reacted at room temperature for 4 hours. Afterwards, 8.21mM tetramethoxysilane (TMOS) was added and mixed for 30 minutes, and then 1.67mM distilled water was added and reacted at room temperature for 24 hours. Afterwards, 5.61mM 2-methylpropenyloxyethyltriethoxysilane (MPTES) was added, mixed, and reacted at room temperature for 4 hours. Afterwards, 0.24 mM bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide was added as a photoinitiator and mixed for 30 minutes for dissolution and uniform dispersion to form a photosensitive silica-impregnated polyimide called “solution (α)”. A precursor solution for a substrate was obtained.

Solution (α) was spin-coated onto a 4-inch silicon wafer for 30 seconds at a speed of 1500 rpm, then soft-baked on a hot plate for 4 minutes at a temperature of 120°C, and a 365 nm wafer with a blank mask and exposure energy of 1800 mJ/cm ² Exposure was performed using an ultraviolet light source of different wavelengths. After exposure, it was baked on a hot plate at a temperature of 120°C for 10 minutes. Afterwards, a series of hard-bakes for curing were performed on a hot plate. The relevant curing temperatures and times are: 30 minutes at 150°C; 30 minutes at 200℃; 30 minutes at 250℃; and 30 minutes at 300°C. A silica-impregnated polyimide-based film was obtained. The average silica particle diameter of the manufactured silica-impregnated polyimide base film was 15 nm, and the silica content was 15% by weight based on the total weight of the base material.

(2) Description 2

Except for adding 6mM of 3-aminopropyltriethoxysilane (APrTEOS), 10mM of tetramethoxysilane (TMOS), and 9mM of 2-methylpropenyloxyethyltriethoxysilane (MPTES) and reacting for 10 hours. and proceeded in the same manner as the manufacturing method of Substrate 1 above. The average silica particle diameter of the prepared silica-impregnated polyimide base film was 28 nm, and the silica content was 50% by weight based on the total weight of the base material.

(3) Description 3

After preparing a solution of LG Chemical Co., Ltd.'s polycarbonate LD7890H product dissolved in chloroform solvent at a concentration of 5%, Tego's Evonic's Nanopol C764 product was added to make up 20% by weight of the total weight based on silica and mixed evenly for 3 hours. Stir to mix. The stirred solution was spin-coated onto a 4-inch silicon wafer for 30 seconds at a speed of 1000 rpm, followed by a primary process of removing the solvent on a hot plate for 30 minutes at a temperature of 100°C, and then vacuumed at a temperature of 130°C for 30 minutes. The residual solvent was removed in an oven to obtain a silica-impregnated polyimide-based film. The average particle diameter of silica in the manufactured silica-impregnated polyimide base film was 15 nm, and the content was 20% by weight based on the total weight of the base material.

(4) Listing 4

After preparing a solution of LG Chemical Co., Ltd.'s polycarbonate LD7890H product dissolved in chloroform solvent at a concentration of 5%, Tego's Evonic's Nanopol C764 product was added to make up 40% by weight of the total weight based on silica and mixed evenly for 3 hours. Stir to mix. The stirred solution was spin-coated onto a 4-inch silicon wafer for 30 seconds at a speed of 1000 rpm, followed by a primary process of removing the solvent on a hot plate for 30 minutes at a temperature of 100°C, and then vacuumed at a temperature of 130°C for 30 minutes. The residual solvent was removed in an oven to obtain a silica-impregnated polyimide-based film. The average particle diameter of silica in the manufactured silica composite material was 15 nm, and the content was 40% by weight based on the total weight of the substrate.

(5) List 5

After preparing a solution of LG Chemical Co., Ltd.'s polycarbonate LD7890H product dissolved in chloroform solvent at a concentration of 5%, Tego's Evonic's Nanopol C764 product was added to make up 80% by weight of the total weight based on silica and mixed evenly for 3 hours. Stir to mix. The stirred solution was spin-coated onto a 4-inch silicon wafer for 30 seconds at a speed of 1000 rpm, followed by a primary process of removing the solvent on a hot plate for 30 minutes at a temperature of 100°C, and then vacuumed at a temperature of 130°C for 30 minutes. The residual solvent was removed in an oven to obtain a silica-impregnated polycarbonate-based film. The average particle diameter of silica in the manufactured silica composite material was 15 nm, and the content was 80% by weight based on the total weight of the substrate.

(6) List 6

After preparing a solution of LG Chemical's polycarbonate LD7890H product dissolved in a chloroform solvent at a concentration of 5%, the solution was spin-coated on a 4-inch silicon wafer for 30 seconds at a speed of 1000 rpm, and then heated on a hot plate at a temperature of 100°C for 30 minutes. After going through the first process of removing the solvent, the remaining solvent was removed in a vacuum oven at a temperature of 130°C for 30 minutes to obtain a polycarbonate film.

Manufacturing example 2. Preparation of colored photosensitive resin composition

Colored photosensitive resin compositions having the composition and content shown in Table 1 below were prepared, and each was applied to the corresponding substrate.

Composition (parts by weight) Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 coloring agent A-1 4.25 4.21 4.41 4.10 4.68 4.51 Alkali soluble resin B-1 6.26 7.3 8.34 3.16 9.91 5.74 photopolymerizable compound C-1 4.17 3.13 2.09 6.45 0.52 4.69 photopolymerization initiator D-1 0.47 0.47 0.47 0.47 0.47 0.47 solvent E-1 51 52 53 50 55 45 additive F-1 0.085 0.0842 0.0882 0.082 0.0936 0.0902 write List 1 List 2 List 3 List 4 List 5 List 6 1) A-1: Pigment Red 254 (BT-CF. manufactured by Ciba)
2) B-1: Resin prepared in Preparation Example 1
3) C-1: KAYARAD DPHA Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
4) D-1: Irgacure OXE-02 Ethanone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyloxybenzoyl)-9H-carbazol-3-yl]-1-( O-acetyloxime) (manufactured by Ciba Specialty Chemical)
5) E-1: Propylene glycol monomethyl ether acetate
6) F-1: γ-methacryl oxypropyl trimethoxy silane

< Experiment example >

Experiment example One. bending evaluation

Bending evaluation was performed using the colored substrate of the manufacturing example manufactured using Examples 1 to 5 and Comparative Example 1. The bending characteristics of the obtained pattern were evaluated using a bending tester (cyclic bending testet, Kobo Technology). The measurement was based on 100,000 measurements, and the number of patterns with no abnormalities for 100 patterns was judged based on the bending evaluation criteria below. The evaluation results are listed in Table 2 below.

<Bending evaluation criteria>

◎: Maintain more than 95 patterns

○: Maintain 90 to 94 patterns

△: Maintain 60 to 89 patterns

X: Maintain 0 to 59 patterns

Experiment example 2. Adhesion evaluation

As in Experimental Example 1, using a bending measuring device, after bending 100,000 times, the adhesion of the bent portion was measured and evaluated. The measurement method was conducted according to JIS K5600. A cut was made using a cross cutter to form a 10x10ea square on the surface. Afterwards, Japan's Nichiban CT-24 tape was attached to the surface of 10x10ea and then removed. The adhesion results were confirmed by looking at the number of squares remaining on the separated surface and are listed in Table 2 below.

<Adhesion evaluation criteria>

◎: Maintain more than 90 patterns

○: Maintain 80 to 89 patterns

△: Maintain 60 to 79 patterns

X: Maintain 0 to 59 patterns

Experiment example 3. contact angle evaluation

Contact angle evaluation was performed to determine the relative amount of hydroxy groups introduced into the substrates 1 to 6 prepared above. Since the hydroxyl group is hydrophilic, it can be determined that the lower the contact angle, the more silica containing the hydroxyl group is introduced into the polymer substrate.

Contact angle evaluation was performed on the substrates 1 to 6 used in Examples 1 to 5 and Comparative Example 1, and was conducted by forming distilled water into drops and measuring the contact angle with the substrate using a DSA100 instrument manufactured by KRUSS, Germany. . The measurement results are shown in Table 2 below.

Experiment example 4. Transparency evaluation

The transparency of Examples 1 to 5 and Comparative Example 1 using each of the above substrates 1 to 6 was measured and listed in Table 2. Transparency was recorded by measuring luminance, and the relative luminance was measured using a 0.5T thick glass substrate as 100, and the results are listed in Table 2 below.

item Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Bending evaluation ◎ ○ ○ △ X X Adhesion evaluation ◎ ○ △ ○ △ X Contact angle evaluation 55 42 46 43 41 78 Transparency evaluation 99.1 98.2 97.5 97.3 96.5 95.6

As can be seen from the results in Table 2, the adhesion between the substrate and the colored photosensitive resin layer in the laminated substrate manufactured using a silica-impregnated polymer substrate is significantly superior to that of Comparative Example 1 using a polymer substrate that does not contain silica. confirmed. In addition, the bending evaluation results also confirmed that Examples 1 to 5 had superior properties compared to Comparative Example 1.

In the contact angle evaluation, Examples 1 to 5 showed a lower contact angle than Comparative Example 1, which can be judged to be due to the hydrophilic nature of the hydroxy group (-OH) introduced on the silica surface. In other words, hydroxy groups can be introduced by incorporating silica into the polymer substrate, and this can be judged to have the function of improving adhesion with the colored photosensitive resin layer and relieving the interface.

Claims (9)

It includes a colored photosensitive resin layer and a silica-impregnated polymer base,
The colored photosensitive resin layer is formed by curing a colored photosensitive resin composition containing (A) a colorant, (B) alkali-soluble resin, (C) a photopolymerizable compound, (D) a photopolymerization initiator, a silane coupling agent, and (E) a solvent. It will be,
The silane coupling agent is trimethoxysilyl benzoic acid, γ-methacryl oxypropyl trimethoxy silane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanate propyl triethoxysilane, and r-glycidoxy propyl. A laminate substrate comprising at least one selected from the group consisting of trimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. In claim 1,
A laminated substrate, characterized in that the polymer is at least one selected from polyimide and polycarbonate. In claim 1,
The silica is a laminate substrate characterized in that the average particle diameter of the particles is 5 to 30 nm. In claim 1,
A laminated substrate comprising 5 to 70% by weight of silica based on the total weight of the substrate. delete In claim 1,
A laminate substrate, wherein the silane coupling agent is contained in an amount of 0.35 to 5 parts by weight based on 100 parts by weight of the solid content of the colorant. In claim 1,
The colored photosensitive resin composition,
As a weight fraction based on the solid content in the colored photosensitive resin composition, 5 to 70% by weight of colorant (A), 5 to 85% by weight of alkali-soluble resin (B), 1 to 50% by weight of photopolymerizable compound (C), and photopolymerization initiator (D) ) 0.5 to 10% by weight;
A laminated substrate comprising 60 to 90% by weight of solvent (E) based on the total weight of the colored photosensitive resin composition. A color filter manufactured using the laminated substrate of claim 1. An image display device equipped with the color filter of claim 8.