KR20170014507A - Laminated substrate having colored photosensitive resin layer and silica doped base material - Google Patents

Abstract

The present invention relates to a stacked substrate comprising a colored photosensitive resin layer and a silica-doped polymer base material, wherein the colored photosensitive resin layer comprises: (A) a colorant; (B) an alkali soluble resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent, to a color filter manufactured by using the same and an image display device. According to the present invention, adhesiveness between a colored photosensitive resin layer and a silica-doped polymer is increased and transparency is also increased.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated substrate comprising a colored photosensitive resin layer and a silica-

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 laminated substrate, and an image display apparatus including the same.

BACKGROUND ART [0002] Color filters are widely used in various display devices such as an image pickup device and a liquid crystal display (LCD), and their application range is rapidly expanding. The color filter used in the image pickup device or the liquid crystal display device may be a color pattern of three colors of red, green and blue or a color pattern of three colors of yellow, magenta and cyan Cyan). In addition, in each pixel, a mixture of different colors is prevented or a black matrix is formed at a boundary portion between coloring layers of the respective colors. The black matrix BM is mainly formed of a black photosensitive resin composition.

The coloring pattern of each color filter is generally formed using a colored photosensitive resin composition comprising a coloring agent such as pigment or dye, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. The coloring pattern processing using the colored photosensitive resin composition is usually performed by a lithography process.

2. Description of the Related Art Recently, a plasma display panel (PDP), a liquid crystal display (LCD), an organic EL (Organic Light Emitting Diodes) OLED, and the like have been used as a display method in a conventional CRT (Cathode Ray Tube) In particular, development has been actively conducted to realize such a flat panel display as a flexible display. Therefore, development of a photosensitive resin composition, a base material, and the like that can impart characteristics that are excellent in flexibility and bending adhesion when forming a pattern or the like contained in color filters for various display devices is required.

As a substrate suitable for such a flat panel display, a glass substrate is mainly used, which is not suitable as a substrate for a flexible display due to its low flexibility. Therefore, a polymer substrate is used as a flexible display substrate, and polyimide or polycarbonate is mainly used. However, when a color filter is prepared using the above-mentioned polymer substrate, there is a problem that adhesion with the conventional colored photosensitive resin composition is poor, and a solution for this problem is required.

SUMMARY OF THE INVENTION The present invention has been made in order to solve the problems of the prior art,

And a silica-impregnated base excellent in adhesion to the colored photosensitive resin layer.

It is still another object of the present invention to provide a color filter manufactured using the above-described laminated substrate and an image display apparatus provided with the color filter.

According to the present invention,

A colored photosensitive resin layer and a silica-impregnated polymer substrate,

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) And a second substrate.

In addition,

And a color filter manufactured using the laminated substrate.

In addition,

And an image display device provided with the color filter.

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

Further, a color filter manufactured using the above-described laminated substrate and an image display apparatus having the same can be provided.

According to the present invention,

A colored photosensitive resin layer and a silica-impregnated polymer substrate,

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) And a second substrate.

The polymer base material contained in the laminated substrate of the present invention is characterized by incorporating silica.

The kind of the polymer is not particularly limited and a polymer resin which is generally used in the field of the present invention can be used. However, it is preferable to use at least one selected from a polyimide resin and a polycarbonate resin in order to realize a flexible property can do. More preferably, a polyimide resin is used.

Since the polymer base includes silica, it is possible to provide an effect of increasing the adhesion with the colored photosensitive resin layer. The silica has a silanol group (Si-OH) on its surface, and the hydroxyl group (-OH) of the silanol group plays a main role in improving the hydrophilicity and contributing to the improvement of adhesion with the colored photosensitive resin layer.

When the particle size of the silica is small, the effect of improving the adhesive strength may be excellent. In view of economical efficiency and practical improvement, the silica particles preferably have an average particle diameter of 5 to 30 nm, but are not limited thereto.

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

In the present invention, the thickness of the substrate is not particularly limited, and for example, about 5 to 200 μm may be used.

Hereinafter, each component constituting the colored photosensitive resin layer contained in the laminated substrate will be described in detail. The colored photosensitive resin layer can be formed by applying a colored photosensitive resin composition and then curing the colored photosensitive resin composition. That is, the colored photosensitive resin composition means un-cured, and the colored photosensitive resin layer means that its constituent components are cured.

(A) Colorant

The colorant (A) contained in the colored photosensitive resin composition of the present invention may be selected from one or more kinds selected from the pigment (a1) and the dye (a2).

(a1) pigment

The pigment (a1) which can be used as the colorant (A) may be an organic pigment or an inorganic pigment generally used in the art.

The above-mentioned pigments can be used in various kinds of pigments used in printing ink, ink jet ink and the like. Specific examples thereof include water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, And an anthanthrone pigment, an anthanthrone pigment, a pravanthrone pigment, a pyranthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, an anthanthrone pigment, a pyranthrone pigment, pyranthrone pigments, diketopyrrolopyrrole pigments, and the like.

Specific examples of the inorganic pigments include metal compounds such as metal oxides and metal complex salts such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, titanium black, An oxide of a metal such as black or a composite metal oxide. The carbon black among the inorganic pigments may be one coated with a resin as a black pigment. The coated carbon black may be more preferable because it has a lower conductivity than that of uncoated carbon black and can give good electrical insulation when forming a matrix or a column spacer.

In particular, as the above-mentioned pigment, a compound classified as pigment in the color index (The Society of Dyers and Colourists) may be used, more specifically, a pigment having a color index (CI) number as follows However, the present invention is not limited thereto.

Specific examples of the preferable pigment (a1) which 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;

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. 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. Pigment Black 1 and Pigment Black 7, and the like, but the present invention is not limited thereto.

The black pigment is not particularly limited as long as it is shielding from visible light.

The above organic pigments and inorganic pigments may be used alone or in combination of two or more.

(a2) Dye

The dye (a2) may be used without limitation as long as it has solubility in an organic solvent. However, it is preferable to use a dye (a2) having solubility in an organic solvent and ensuring reliability such as heat resistance and solvent resistance. Such dyes include compounds classified as dyes in the color index (The Society of Dyers and Colourists), or known dyes described in the dyeing notes (color dyes).

Specific examples of the dye include trianti-methane-based dyes, xanthene-based dyes including rhodamine-based dyes, flaine dyes, aramine dyes, sapphanine dyes, flocine dyes and methylene blue dyes.

Specific examples of the 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 cyanide 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.); C. I. Basic Green 1 (Brilliant Green GX) and C. I. Basic Green 4 (Malachite Green).

Examples of rhodamine dyes include C. I. Basic Red 1 (Rhodamine 6G, 6GCP) and C. I. Basic Red 8 (Rhodamine G); And C. I. Basic violet 10 (rhodamine B). As the flavin-based dye, for example, C. I. Basic Yellow 1 can be mentioned. Examples of the oraminic dyes include C. I. Basic Yellow 2 and C. I. Basic Yellow 3. As the sapphanine dye, for example, C. I. Basic Red 2 can be mentioned. As the floc naphtho dye, for example, C. I. Basic Red 12 can be mentioned. Examples of methylene blue dyes include CI Basic Blue 9 (methylene blue FZ, methylene blue B), CI Basic Blue 25 (Basic Blue GO), and CI Basic Blue 24 (N-methylene Blue NX) But is not limited thereto

In the present invention, the content of the colorant (A) is not particularly limited, and it can be suitably adjusted so as to meet the required characteristics. Generally, the color photosensitive resin composition preferably contains 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 within the above-mentioned range, it is preferable since the color density is sufficient when being made into a color filter and the coloring power can be most efficiently expressed.

(B) an alkali-soluble resin

The alkali-soluble resin (B) contained in the colored photosensitive resin composition of the present invention is a component that imparts solubility to the alkali developing solution used in the developing process. That is, the unexposed portion of the colored photosensitive resin layer formed using the colored photosensitive resin composition is rendered alkali-soluble, and serves 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 developing solution, a carboxyl group is introduced into the resin to impart an acid value, but the present invention is not limited thereto.

The alkali-soluble resin can be produced 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 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; (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and acrylic acid and methacrylic acid are preferable.

As a method of reacting an acid anhydride with a resin copolymer having a hydroxyl group to give an acid value, there is a method of adding an acid anhydride to the hydroxy (meth) acrylate copolymer to give an acid value, but the method is not limited thereto .

Specific examples of the hydroxy (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl -3-phenoxypropyl (meth) acrylate, N-hydroxyethylacrylamide, and the like, but are not limited thereto.

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

As specific examples of the copolymerizable unsaturated monomer,

Styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethylether, m-vinylbenzylmethylether, p-vinyl Aromatic vinyl compounds such as benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether;

N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide-based compounds such as methylphenyl maleimide, Np-methylphenyl maleimide, No-methoxyphenyl maleimide, Nm-methoxyphenyl maleimide and Np-methoxyphenyl maleimide;

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; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- 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) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds, and the like. However, the present invention is not limited thereto, and at least one of them may be selected and used.

The alkali-soluble resin preferably has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight of the alkali-soluble resin is less than 3,000, the shape of the surface is not smooth due to the molecular weight of the resin being too small. When the molecular weight is more than 100,000, the development speed is slow.

The acid value of the alkali-soluble resin (B) is preferably 30 to 250 mgKOH / g, more preferably 30 to 200 mgKOH / g, and still more preferably 60 to 150 mgKOH / g, based on the solid content. When the acid value of the alkali-soluble resin (B) is less than 30 mgKOH / g, it is difficult to secure a sufficient developing rate of the colored photosensitive resin composition. When the acid value exceeds 250 mgKOH / g, Short-circuiting is likely to occur, problems in compatibility with the coloring agent occur, coloring agents in the colored photosensitive resin composition are precipitated, storage stability of the colored photosensitive resin composition is lowered, and viscosity is increased. That is, when the acid value is within the above-mentioned range, the developability against the alkali development is excellent, the occurrence of the residue is suppressed, and the adhesion of the pattern is improved.

The alkali-soluble resin (B) is preferably contained in an amount of 5 to 85% by weight, more preferably 5 to 70% by weight, and still more preferably 20 to 55% by weight, based on the solid content in the colored photosensitive resin composition It should be included. When the content of the alkali-soluble resin (B) is within the above-mentioned range, solubility in a developing solution is sufficient, so that the absence of the non-pixel portion is improved, So that the pattern formation is facilitated.

(C) Photopolymerization  compound

The photopolymerizable compound (C) contained in the colored photosensitive resin composition of the present invention is a compound which can be polymerized by an active radical or an acid generated from a photopolymerization initiator (D) described below by light irradiation, And is not particularly limited as long as it contains an unsaturated group and is photosensitive. Preferably, monofunctional monomers, bifunctional monomers or trifunctional or more polyfunctional monomers can be used, and at least one monomer selected therefrom can be used.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate or N- Examples of commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nippon Kayaku), and Viscot 158 (Osaka Yuki Kagaku Kogyo). It is not.

Specific examples of the bifunctional monomer include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (Acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, propylene glycol dimethacrylate, urethane (meth) acrylate, AH-600, AT-1, and K-KAARAD HDDA (Nippon Kayaku), Viscoat 260 (Osaka Yuki Kagaku Kogyo Co., Ltd.) 600 or UA-306H (manufactured by Kyoeisha Chemical Co., Ltd.), but the present invention is not limited thereto.

Specific examples of the trifunctional or higher functional polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, penta (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol penta (meth) acrylate, ethoxylated (Meth) acrylate such as dipropylene glycol dimethacrylate, dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate and dipentaerythritol hexa (meth) acrylate. Commercially available products include Aronix M-309 , TO-1382 (Toagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku), but the present invention is not limited thereto .

Among the photopolymerizable compounds exemplified above, it is more preferable to use a multifunctional monomer having three or more functional groups. Since the (meth) acrylates and the urethane (meth) acrylates have excellent polymerizability and can improve the strength, desirable.

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

(D) Light curing Initiator

The photopolymerization initiator (D) contained in the colored photosensitive resin composition of the present invention initiates the polymerization of the photopolymerizable compound (C) by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam and X- Radicals and the like.

The photopolymerization initiator is not particularly limited so long as it can be polymerized with the alkali-soluble resin and the photopolymerizable compound, which is usually used in the art within the scope of not impairing the object of the present invention. Typical examples include oxime compounds, acetophenone compounds, benzoin compounds, benzophenone compounds, nonimidazole compounds, triazine compounds, thioxanthone compounds, and anthracene compounds. And it is possible to select at least one of them. Among them, when the polymerization characteristics, the initiation efficiency and the absorption wavelength are considered, it is more preferable to use an oxime compound.

Examples of the oxime compounds include o-ethoxycarbonyl- alpha -oximimino-1-phenylpropan-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- (Z) -2 - ((benzoyloxy) imino) -1- (4- (phenylthio) phenyl) octan-1-one, (E) -1- (((1- (9-ethyl-6- (2-methylbenzoyl) -9H-carbazol- (((1- (6- (4 - ((2,2-dimethyl-1,3-dioxolan-4- yl) methoxy) -2-methylbenzoyl) -9- -Yl) ethyl) amino) oxy) ethanone, and commercially available products include OXE-01 and OXE-02 manufactured by Ciba, but are not limited thereto.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2- (4-methylthioxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one, 1-one, and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the non-imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (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 them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis 4,4 ', 5,5'-tetraphenylbiimidazole or 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl- And the like.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) (Trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- .

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, etc. .

The photopolymerization initiator (D) is preferably contained 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-mentioned range, the colored photosensitive resin composition is highly sensitized and the exposure time is shortened, thereby improving productivity. Further, it is preferable since 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 initiator (d1) 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 preferable because it contains a photopolymerization initiation auxiliary agent to increase the sensitivity and improve the productivity.

As the photopolymerization initiation assistant (d1), for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound and an organic sulfur compound having a thiol group can be preferably used.

As the amine compound, an aromatic amine compound is preferably used. Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone ), 4,4'-bis (diethylamino) benzophenone, and the like.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, and more specifically, it is preferably an aromatic heteroaromatic acid such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

Specific examples of the organic sulfur compound having a 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) -thione, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexacis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate) .

(E) Solvent

The solvent (E) according to the present invention is not particularly limited so long as it is effective in dissolving the other components contained in the colored photosensitive resin composition. Specific examples of the solvent include, but are not limited to, ethers, acetates, aromatic hydrocarbons, ketones, alcohols, esters, amides and the like.

Specific examples of the ether solvents include 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; And the like.

Examples of the acetate solvents include alkylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate ;

Alkoxyalkyl acetates such as methoxybutyl acetate and methoxypentyl acetate; And the like.

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 alcohol solvents include ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

Specific examples of the ester solvents include cyclic esters such as? -Butyrolactone;

Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate and the like.

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 DEG C in terms of coating property and dryness, more preferably alkylene glycol alkyl ether acetates; Ketones; Ethoxypropionate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and more preferred examples thereof include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxypropionic acid Ethyl, 3-methoxypropionate, and the like. These solvents may be used alone 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 70 to 85% by weight based on the total weight of the colored photosensitive resin composition. When the solvent (E) is contained in the above-mentioned range, when the solvent (E) is coated by a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater Effect can be provided.

(F) Additive

The colored photosensitive resin composition of the present invention may further contain additives (F) according to the needs of those skilled in the art, so long as the objects of the present invention are not impaired, in addition to the above components.

Specific examples of the additive (F) include, but are not limited to, a silane coupling agent, a pigment dispersant, a surfactant, an antioxidant and an anti-aggregation agent.

The silane coupling agent may be a silane coupling agent having at least one reactive substituent selected from a carboxyl group, a methacryloyl group, an isocyanate group and an epoxy group to improve adhesion to a substrate. Specific examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane, r-glycidoxine, (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like, and at least one of them can be selected and used.

The silane coupling agent is preferably contained 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) to be used. If the content of the silane coupling agent is less than 0.35 parts by weight, the resin layer may be peeled off due to insufficient adhesion to the substrate. When the amount of the silane coupling agent exceeds 5 parts by weight, the photocuring property of the photosensitive resin composition may decrease It is not desirable because it happens.

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

The pigment dispersant may be any of those generally used in the art. An acrylate-based dispersant (hereinafter also referred to as an " acrylic dispersant ") containing butyl methacrylate (BMA) or N, N-dimethylaminoethyl methacrylate (DMAEMA) may be used. Examples of commercially available acrylate dispersants 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 may be used alone or in combination of two or more.

As the pigment dispersant, other resin type pigment dispersants other than the acrylate dispersant may be used. The other resin type pigment dispersing agent may be a known resin type pigment dispersing agent, especially a polycarboxylic acid ester such as polyurethane, polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) An amine salt of a polycarboxylic acid, an alkylamine salt of a polycarboxylic acid, a polysiloxane, a long chain polyaminoamide phosphate salt, an ester of a hydroxyl group-containing polycarboxylic acid and a modified product thereof, Oil-based pigment dispersants such as amides formed by reaction of a polyester having a carboxyl group with poly (lower alkyleneimine) or salts thereof; Soluble resin or water-soluble polymer compound such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidone; Polyester; Modified polyacrylates; Adducts of ethylene oxide / propylene oxide, and phosphate esters.

DISPER BYK-161, DISPER BYK-162, DISPER BYK-163, DISPER BYK-164, DISPER BYK-160, DISPER BYK- 166, DISPER BYK-171, DISPER BYK-182, DISPER BYK-184; EFKA-4060, EFKA-4060, EFKA-4055, EFKA-4055, EFKA-4055, EFKA-4020, EFKA-4015, EFKA-4060, EFKA- 4330, EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800; SOLSPERS-5000, SOLSPERS-24000, SOLSPERS-32550, NBZ-4204/10 from Lubirzol; Hinoact T-6000, Hinoact T-7000, Hinoact T-8000; available from Kawaken Fine Chemicals; AJISPUR PB-821, Ajisper PB-822, Ajisper PB-823 manufactured by Ajinomoto; FLORENE DOPA-17HF, fluorene DOPA-15BHF, fluorene DOPA-33, and fluorene DOPA-44 are trade names of Kyoeisha Chemical Co.,

The surface active agent has a function of improving the coating property. Specific examples of the surfactant include BM-1000, BM-1100 (BM Chemie), Proride FC-135 / FC-170C / FC-430 (Sumitomo 3M) 28PA / -190 / SZ-6032 (Doresilicon Co., Ltd.), and the like, but the present invention is not limited thereto.

Specific examples of the antioxidant include 2-tert-butyl-6- (3- tert -butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- -3,5-di-tert-butylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3- 3-tert-butyldibenz [d, f] [1,3,2] dioxaphosphepin, 3,9-bis [2- {3- -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- Methylphenol), 2,2'-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate , Distearyl 3,3'-thiodipropionate, pentaerythrityl tetrakis (3-laurylthiopropionate), 1,3,5-tris (3,5 (3H, 3H, 5H) -triene, 3,3 ', 3 ", 5,5-dihydroxybenzyl) -1,3,5-triazine- 5 ', 5' '- hexa-tert-butyl-a, a', a '' - (mesitylene-2,4,6-triyl) tri- Butylphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and 2,2'-thiobis (4-methyl- butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like, but are not limited thereto.

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

That is, the present invention can provide a colored photosensitive resin composition with the composition and content of the above-mentioned components, and cure the colored photosensitive resin composition to form a colored photosensitive resin layer.

Also provided is a laminated substrate comprising the colored photosensitive resin layer and the silica-impregnated polymeric substrate described above.

In the silica-impregnated polymer substrate included in the laminated substrate of the present invention, the polymer is not particularly limited, but at least one selected from a polyimide resin and a polycarbonate resin can be used.

In one embodiment of the present invention, the silica-incorporated polyimide substrate can be produced by a method comprising the following steps.

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

(B1) a step of preparing a solution containing a particulate silica or a micelle from the monomer of the silane compound;

(C1) the formula _{^{(R 1) x Si (R}} 2) (4-x) ( wherein, R ¹ is a photo-polymerizable unsaturated group end-groups, R ² is halogen, alkoxy of C1 ~ C6, Al C2 ~ C6 (B) adding a monomer of formula (Ib) to the solution obtained from (B1) to carry a silica addition photo-polymerizable unsaturated group;

(D1) mixing the solution from steps (A1) and (C1), wherein the silica moiety carries a photo-polymerizable unsaturated group; And

(E1) A monomer of the formula R ³ N (R ⁴ ) ₂ , wherein R ³ is a photo-polymerizable unsaturated end group and R ⁴ is a C1 to C6 alkyl group, is added to the solution obtained from the step (D1) , The poly (amic acid) carrying a photo-polymerizable unsaturated group to form a photo-polymerizable silica-incorporated polyimide substrate precursor solution; Based precursor solution for a silica-incorporated polyimide substrate.

The above-mentioned method for preparing a silica-impregnated polyimide-based precursor solution comprises adding to the solution obtained from step (A1) a compound of the formula H ₂ NR ⁵ -Si (R ² ) ₃ wherein R ⁵ is C 1 -C 6 Alkylene or arylene, R < ⁶ > may be the same or different and each represents a C1-C6 alkoxy group), and then mixing with the solution obtained from step (D1) have.

The present invention also relates to a process for preparing a silica-embedded polyimide base film (E1), comprising the steps of coating the solution obtained in (E1) above, removing the solvent by evaporation and then exposing the coating to an energy beam, To form a silica-incorporated polyimide base material, thereby providing a method of forming the colored substrate of the present invention.

The present invention can also use a soluble polymer such as polycarbonate as a polymer substrate in the preparation of a silica-impregnated 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 according to the molecular weight of the polymer, and is generally prepared at a concentration of about 10% by weight. The silica-impregnated polymer substrate can be prepared by charging the prepared silica particles into the prepared polymer solution, coating the resulting silica particles on the release paper, slowly raising the temperature, and removing the solvent.

The laminated substrate of the present invention can be produced by the following method.

The introduction of the colored photosensitive resin composition can be performed by patterning through a photolithography method after the coating, and the photolithography method is not particularly limited in the present invention, and a usual method can be applied.

In one example, the patterned colored photosensitive pattern

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

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

c) curing the exposed portion by irradiating actinic light onto the resulting film with a photomask;

d) performing a developing step of dissolving the unexposed portion using an aqueous alkali solution; And

e) drying and post-baking.

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

At this time, a wet coating method using a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (which may be referred to as a die coater), an ink jet or the like is possible so as to obtain a desired thickness.

Prebaking is performed by heating with an oven, a hot plate or the like. The heating temperature and the heating time in the prebaking are appropriately selected depending on the solvent to be used and are, for example, from 80 to 150 DEG C for 1 to 30 minutes.

The exposure performed after the pre-baking is performed by an exposure machine and is exposed through a photomask to thereby sensitize only the portion corresponding to the pattern. The light to be irradiated may be, for example, visible light, ultraviolet light, X-ray, electron beam, or the like.

The alkali development after the exposure is performed for the purpose of removing the resist in the unremoved portion of the non-exposed portion, thereby forming a desired pattern. As a developer suitable for this alkali development, for example, an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal can be used. Particularly, an alkali aqueous solution containing 1 to 3% by weight of a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate is used in a temperature range of 10 to 50 ° C, preferably 20 to 40 ° C, using a developing machine or an ultrasonic cleaner .

The post-baking is performed in order to improve the adhesion between the patterned resin pattern and the substrate, and is performed by heat treatment at 80 to 220 DEG C for 10 to 120 minutes. Post-baking is performed by using an oven, a hot plate, or the like as in pre-baking.

The colored photosensitive resin pattern obtained by such a method has a sufficient size, several thousands to several thousands of micrometers, preferably 0.1 to 100 μm, more preferably 1 to 50 μm, so as to maintain a high photosensitivity and enable formation of fine patterns. .

Such a colored photosensitive resin pattern not only secures the adhesion force required for all of these colored photosensitive resin patterns, but also has excellent heat resistance and solvent resistance and can improve 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 produced by using a laminated substrate including a colored photosensitive resin layer and a silica-containing polymer substrate. The color filter includes a coloring pattern produced using the colored photosensitive resin composition of the present invention so as to exhibit a desired pattern.

The color filter may be manufactured by a conventional method well known in the art.

<Image Display Device>

The present invention also provides an image display device including the color filter. Specific examples of the image display device include a liquid crystal display (LCD), an organic EL display (organic EL display), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone, A display device such as a display device for car navigation, and the like, but is not limited thereto.

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

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, it should be understood that the following examples are illustrative of the present invention, and the present invention is not limited by the following examples, and various modifications and changes may be made without departing from the scope of the present invention. The scope of the present invention will be determined by the technical idea of the following claims.

< Manufacturing example >

Manufacturing example  1. Preparation of alkali-soluble resin

A flask equipped with a stirrer, a thermometer reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared. As a monomer dropping lot, a mixture 40 of 3,4-epoxytricyclodecan-8-yl (meth) acrylate and 3,4-epoxytricyclodecan-9-yl (meth) acrylate in a molar ratio of 50:50 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyltoluene, 4 parts by weight of t-butylperoxy-2-ethylhexanoate, and 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) And stirring was prepared. As a chain transfer agent, 6 parts by weight of n-dodecanethiol and 24 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) were added and stirred.

Then, 395 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) was added to the flask, and the atmosphere in the flask was replaced with nitrogen in air, and the temperature of the flask was raised to 90 DEG C with stirring. The monomer and the chain transfer agent were then added dropwise from the dropping funnel. The mixture was allowed to stand at 90 DEG C for 2 hours, elevated to 110 DEG C after 1 hour, and maintained for 5 hours to obtain a resin having a solid acid value of 100 mgKOH / g. The prepared resin was held in an oven at 120 ° C for 50 hours to prepare a resin from which the solvent had been removed.

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

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the alkali-soluble resin were measured by the GPC method under the following conditions, and the ratio of the weight average molecular weight to the number average molecular weight / Mn).

Apparatus: HLC-8120GPC (manufactured by TOSOH CORPORATION)

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

Column temperature: 40 DEG C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection amount: 50 μl

Detector: RI

Measurement 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 CORPORATION)

Manufacturing example  2. Preparation of polymer substrate

(1) Substrate 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. And reacted at room temperature for 24 hours to obtain a transparent and sticky poly (amic acid) (PAA) solution. 4 mM 3-aminopropyltriethoxysilane (APrTEOS) was added thereto, followed by reaction at room temperature for 4 hours. Thereafter, 8.21 mM tetramethoxysilane (TMOS) was added and mixed for 30 minutes. Then, 1.67 mM distilled water was added thereto and reacted at room temperature for 24 hours. Then, 5.61 mM 2-methylpropenyloxyethyltriethoxysilane (MPTES) was added, mixed, and reacted at room temperature for 4 hours. Thereafter, 0.24 mM bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide was added as a photoinitiator and mixed for dissolution and uniform dispersion for 30 minutes to form a photosensitive silica-impregnated polyimide To obtain a precursor solution for a substrate.

Was spin-coating the solution (α) a 4-inch silicon wafer for 30 seconds at a speed of 1500rpm, at a hot plate for 4 minutes at a temperature of 120 ℃ after soft-been-baked, 365nm with a blank mask with exposure energy 1800mJ / cm ² And exposed using an ultraviolet light source of wavelength. After exposure, the substrate was baked at 120 DEG C for 10 minutes on a hot plate. A series of hard-baking for curing was then carried out on a hot plate. The relevant curing temperatures and times are: 30 minutes at 150 占 폚; 30 minutes at 200 占 폚; 30 minutes at 250 占 폚; And 300 &lt; 0 &gt; C for 30 minutes. A silica-impregnated polyimide-based film was obtained. The prepared silica-impregnated polyimide-based film had an average silica particle diameter of 15 nm and a content of 15% by weight based on the total weight of the substrate.

(2) Substrate 2

Except that 3 mM aminopropyltriethoxysilane (APrTEOS) was added to 6 mM of tetramethoxysilane (TMOS) and 10 mM of 2-methylpropenyloxyethyltriethoxysilane (MPTES) for 10 hours And proceeded in the same manner as the above-mentioned production method of the substrate 1. The prepared silica-impregnated polyimide base film had an average silica particle diameter of 28 nm and a content of 50% by weight based on the total weight of the substrate.

(3) Substrate 3

A solution obtained by dissolving a polycarbonate LD7890H product of LG Chemical Co., Ltd. in a chloroform solvent at a concentration of 5% was prepared. Then, a Nanopol C764 product of Ebonic Co., Ltd. of Tejosha Co., Ltd. was added in an amount of 20% by weight based on the total weight of silica. Stir in the mix. The stirred solution was spin coated with a 4 inch silicon wafer for 30 seconds at a rate of 1000 rpm and then subjected to a primary process of removing the solvent from the hot plate at a temperature of 100 &lt; 0 &gt; C for 30 minutes, The residual solvent was removed from the oven to obtain a silica-impregnated polyimide-based film. The prepared silica-impregnated polyimide base film had an average silica particle diameter of 15 nm and a content of 20% by weight based on the total weight of the substrate.

(4) Substrate 4

A solution obtained by dissolving a polycarbonate LD7890H product of LG Chemical Co., Ltd. in a chloroform solvent at a concentration of 5% was prepared. Then, Nanopol C764 product of Ebonic Co., Ltd. of Tejosha Co., Stir in the mix. The stirred solution was spin coated with a 4 inch silicon wafer for 30 seconds at a rate of 1000 rpm and then subjected to a primary process of removing the solvent from the hot plate at a temperature of 100 &lt; 0 &gt; C for 30 minutes, The residual solvent was removed from the oven to obtain a silica-impregnated polyimide-based film. The prepared silica composite material had an average particle diameter of 15 nm and a content of 40% by weight based on the total weight of the substrate.

(5) Substrate 5

A solution obtained by dissolving a polycarbonate LD7890H product of LG Chemical Co., Ltd. in a chloroform solvent at a concentration of 5% was prepared. Then, Nanopol C764 product of Ebonic Co., Ltd. of Tejosha Co., Ltd. was added to 80% by weight of the total weight of silica, Stir in the mix. The stirred solution was spin coated with a 4 inch silicon wafer for 30 seconds at a rate of 1000 rpm and then subjected to a primary process of removing the solvent from the hot plate at a temperature of 100 &lt; 0 &gt; C for 30 minutes, The residual solvent was removed from the oven to obtain a silica-entangled polycarbonate-based film. The prepared silica composite material had an average particle diameter of 15 nm, and the content of silica was 80% by weight based on the total weight of the substrate.

(6) Substrate 6

A solution of 5% concentration of polycarbonate LD7890H manufactured by LG Chemical Co., Ltd. in 5% concentration was prepared. The solution was spin-coated on a 4-inch silicon wafer for 30 seconds at a speed of 1000 rpm and then heated at 100 ° C for 30 minutes on a hot plate After the primary step of removing the solvent, the residual solvent was removed in a vacuum oven at a temperature of 130 DEG C for 30 minutes to obtain a polycarbonate film.

Manufacturing example  2. Preparation of colored photosensitive resin composition

Colored photosensitive resin compositions having the compositions and contents shown in Table 1 were prepared and applied to the corresponding substrates respectively.

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 materials Substrate 1 Substrate 2 Base 3 Base 4 Substrate 5 Substrate 6 1) A-1: Pigment Red 254 (BT-CF, manufactured by Ciba)
2) B-1: The resin prepared in Production Example 1
3) C-1: KAYARAD DPHA Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)
4) D-1: Irgacure OXE-02 Etenan-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9H-carbazol- O-acetyloxime) (manufactured by Ciba Specialty Chemical)
5) E-1: Propylene glycol monomethyl ether acetate
6) F-1:? -Methacryloxypropyltrimethoxysilane

< Experimental Example >

Experimental Example  One. Bending  evaluation

The bending evaluation was carried out using the colored substrate of the above-mentioned production example manufactured by using the above-mentioned Examples 1 to 5 and Comparative Example 1. [ The obtained patterns were evaluated for bending properties using a cyclic bending test (Cobo technique). The measurement was based on a measurement of 100,000 times, and the number of patterns having no abnormality with respect to 100 patterns was judged as the following bending evaluation standard. The evaluation results are shown in Table 2 below.

<Bending Evaluation Standard>

◎: Maintain more than 95 patterns

?: Maintains 90 to 94 patterns

DELTA: Maintain 60 to 89 patterns

X: Maintain 0 to 59 patterns

Experimental Example  2. Adhesion Evaluation

After the bending of 100,000 times using the bending measuring machine as in the case of Experimental Example 1, the adhesion measurement of the bent portions was carried out. The measurement was carried out in accordance with JIS K5600. The sheath was cut with a cross cutter so that a square of 10 x 10 ea was formed on the surface. Then, a Nichiban CT-24 tape of Japan was affixed to the surface of 10 x 10 ea and then peeled off. The number of squares remaining on the peeled surface was observed, and the adhesion result was confirmed and shown in Table 2 below.

<Adhesion Evaluation Standard>

◎: Maintains more than 90 patterns

?: Maintains 80 to 89 patterns

DELTA: Maintains 60 to 79 patterns

X: Maintain 0 to 59 patterns

Experimental Example  3. Contact angle  evaluation

A contact angle evaluation was conducted to determine the relative amount of hydroxyl groups introduced into the substrates 1 to 6 prepared above. Since the hydroxy group is hydrophilic, it can be judged that the silica having a hydroxy group is introduced into the polymer substrate more as the contact angle is lower.

The contact angle evaluation was carried out on the substrates 1 to 6 used in Examples 1 to 5 and Comparative Example 1, and distilled water was formed into droplets using a DSA100 instrument manufactured by KRUSS, Germany to measure the contact angle with the substrate . The measurement results are shown in Table 2 below.

Experimental Example  4. Evaluation of transparency

The transparency of Examples 1 to 5 and Comparative Example 1 using the respective substrates 1 to 6 was measured and described in Table 2. The transparency was measured and recorded. The relative luminance was measured with a glass substrate of 0.5T thickness as 100, and the results are shown in Table 2 below.

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

As can be seen from the results of Table 2, the adhesion between the base material and the colored photosensitive resin layer in the laminated substrate prepared using the silica-impregnated polymer base material was much superior to that of Comparative Example 1 using the polymer base material not containing silica Respectively. It is also confirmed that the bending evaluation results are also superior to those of Comparative Example 1 in Examples 1 to 5.

In the contact angle evaluation, Examples 1 to 5 show lower contact angles than Comparative Example 1, which can be judged to be due to the hydrophilicity of the hydroxyl group (-OH) introduced onto the silica surface. That is, it is possible to introduce a hydroxy group by incorporating silica into the polymer substrate, which can be judged to improve adhesion to the colored photosensitive resin layer and alleviate the interface.

Claims (9)

A colored photosensitive resin layer and a silica-impregnated polymer substrate,
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) . The method according to claim 1,
Wherein the polymer is at least one selected from polyimide and polycarbonate. The method according to claim 1,
Wherein the silica has an average particle diameter of 5 to 30 nm. The method according to claim 1,
And 5 to 70% by weight of the silica with respect to the total weight of the substrate. The method according to claim 1,
Wherein the colored photosensitive resin composition further comprises a silane coupling agent. The method of claim 5,
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. The method according to claim 1,
The colored photosensitive resin composition may contain,
5 to 70% by weight of a colorant (A), 5 to 85% by weight of an alkali-soluble resin (B), 1 to 50% by weight of a photopolymerizable compound (C) and a photopolymerization initiator (D) in a weight fraction of the solid content in the colored photosensitive resin composition ) 0.5 to 10% by weight;
And the solvent (E) is contained in an amount of 60 to 90% by weight based on the total weight of the colored photosensitive resin composition. A color filter produced using the laminated substrate of claim 1. An image display apparatus comprising the color filter of claim 8.