Curable resin composition, color filter, production method for color filter, and liquid crystal display

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Technical field to which the invention belongs]

The present invention relates to a curable resin composition, a color filter, a method for manufacturing a color filter, and a liquid crystal display device. More specifically, in the step of applying the curable resin composition to the surface of the substrate, the curable resin composition which is hard to dry and aggregate and significantly reduces the generation of foreign substances, and the color filter using this curable resin composition. The present invention relates to a method for manufacturing this color filter and a liquid crystal display device using this color filter.

【0002】

[Conventional technology]

Conventionally, as a method for manufacturing a color filter used in a liquid crystal display device or the like, a pigment dispersion method, a dyeing method, an electrodeposition method, and a printing method are known. From the viewpoints of spectral characteristics, durability, pattern shape, accuracy, etc., the pigment dispersion method having excellent characteristics on average is most widely adopted.

【0003】

The outline of the pigment dispersion method will be described below. Usually, a photosensitive resin composition (color resist) in which a black matrix is first formed on a transparent support such as a glass substrate by a metal light-shielding film such as chromium or chromium oxide, and then a red pigment is dispersed, for example, is used. ) Is applied to the entire surface by a spin coating method or the like, and exposed through a mask. Development after exposure gives red pixels. For blue and green pixels, three color pixels are formed by the same method. Since the black matrix portion is dented between each pixel, the surface is covered with a protective film of a transparent resin such as epoxy resin or acrylic resin for smoothing, but this protective film is provided. It may not be there. Further, a transparent conductive film such as an ITO film is formed on the protective film by sputtering or vacuum deposition. Recently, the pigment dispersion method is often adopted when forming a black matrix. Specifically, it is produced by applying, exposing, and developing a photosensitive resin (black resist) in which a black pigment is dispersed.

【0004】

As with the trend of technological innovation in recent years, the performance required for liquid crystal display devices is also diversifying and becoming more sophisticated. Above all, color filters are required to have wider color reproducibility and higher transmittance than ever before. In order to meet these requirements by the above pigment dispersion method, a wide variety of new pigments have been developed, and photosensitive resin compositions (color resists) containing these new pigments in high concentrations have become mainstream. It's getting better. Further, not only the color resist but also the black resist described above is required to have a thin coating film and high light-shielding property, and there is a tendency to adopt a resist having a high pigment concentration.

【0005】

On the other hand, various new technologies have been developed for manufacturing methods of color filters. Among the pixel forming steps, for example, in the resist coating step, it has been the mainstream to drop a resist on the central portion of the substrate and make it uniform by a spin coating method. However, as the size of the substrate increases, the amount of resist used increases, and there are restrictions on the spin coater equipment (motor capacity, etc.). Therefore, a coating technology using the die coating method has recently been developed. , Partially put into practical use.

【0006】

[Problems to be Solved by the Invention]

Generally, the technique of applying a resist by the die coating method is used for manufacturing a floppy (registered trademark) disk or the like, and is usually suitable for continuously applying a coating liquid such as a resist to a medium such as a polymer film. Will be adopted. In the case of single-wafer coating such as a color filter, the resist coating method is intermittent coating, and the tip of the die lip is repeatedly wetted and dried. When a color resist or black resist in which a high-concentration pigment is dispersed is dried at the tip of a die lip, the pigment concentration rapidly increases, and agglomerates of the pigment may occur. These agglomerates adhere to the tip of the die lip, peel off from the tip of the lip when the resist is discharged again, and move onto the substrate. These agglomerates are not easily removed in the subsequent steps and remain on the substrate until the end. Such agglomerates become pixel defects of the color filter and cause poor quality. If this defective phenomenon occurs frequently, the yield of the product will decrease, so it is considered to be one of the phenomena that must be avoided.

【0007】

An object of the present invention is to solve the above-mentioned problems in the prior art, and even when a high-concentration resist is used as the coating liquid, it is possible to suppress the generation of dry agglomerates at the tip of the die lip, and foreign matter on the substrate. It is an object of the present invention to provide a curable resin composition, a color filter, a method for manufacturing a color filter, and a liquid crystal display device, which can obtain a high-quality product with minimal adhesion.

【0008】

[Means for solving problems]

As a result of diligent research to achieve the above object, the present inventors have obtained the following findings. That is, in a curable resin composition used for a resin composition for a color filter or the like, which contains a coloring material such as a pigment, a solvent component, a binder resin and / or a monomer thereof, the solvent component is an alcohol and / or an alkyl alcohol. It has been found that the use of ethers significantly suppresses the generation of pixel defects mainly due to agglomerates generated during coating, and the present invention has been reached. In particular, when applied by the die coating method, drying is promoted at the tip of the die lip, so that agglomerates are likely to occur. However, when the curable resin composition is used, the agglomerates are suppressed from remaining on the substrate surface. We found that the incidence of defective products could be significantly reduced.

【0009】

In order to solve the above problems, in the first invention, the coloring material {(a) component}, the solvent component {(b) component}, the binder resin {(c1) component} and / or its monomer {(c2) A curable resin composition containing a component}, wherein the solvent component {(b) component} contains alcohols (b1) and / or alkyl alcohol ethers (b2). The composition is provided.

【0010】

The second invention provides a color filter having pixels formed by the curable resin composition according to the first invention.

【0011】

In the third invention, the pixels are subjected to a coating step of applying the curable resin composition for a color filter according to the first invention on a substrate for a color filter, an exposure step of exposing the coating step, and a development step of developing the curable resin composition after exposure. Provided is a method for manufacturing a color filter to be formed, wherein the coating step is a die coating method.

【0012】

The fourth invention provides a liquid crystal display device obtained by using the color filter according to the second invention.

【0013】

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail. The curable resin composition according to the present invention includes a coloring material {hereinafter, simply abbreviated as (a) component}, a solvent component {hereinafter, simply abbreviated as (b) component}, and a binder resin {hereinafter, simply (c1). It may be abbreviated as a component} and / or its monomer {hereinafter, simply abbreviated as (c2) component}, and if necessary, further, a photopolymerization initiator system {hereinafter, simply abbreviated as (d) component}. , (A) component or other additives other than (d) component {hereinafter, simply abbreviated as (e) component} and the like may be blended.

【0014】

The component (a) refers to a component that colors the curable resin composition according to the present invention. (a) Ingredients include red, green, and blue dyes / pigments and yellow for toning, violet dyes / pigments, carbon black, etc. In addition, metal powders and white pigments that can be blended as needed, Fluorescent pigments and the like can be mentioned. The pigment may be either an inorganic pigment or an organic pigment. Examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, chromium oxide, carbon black and the like.

【0015】

Examples of the organic pigment include the following. The types of component (a) such as the following dyes and pigments are described by CI (color index) number. Yellow pigments include CI Pigment Yellow 1, 3, 4, 5, 6, 12, 13, 14, 16, 17, 18, 20, 24, 55, 65, 73, 74, 81, 83, 86, 87, 93, 94, 95, 97, 98, 100, 101, 108, 109, 110, 113, 116, 117, 120, 123, 125, 128, 129, 133, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 156, 166, 168, 169, 170, 171, 172, 173, 175 and so on.

【0016】

Orange pigments include CI Pigment Orange 1, 2, 5, 13, 15, 16, 17, 18, 19, 31, 34, 36, 38, 40, 42, 43, 51, 52, 55, 59, 60, 61, 62, etc. As red pigments, CI Pigment Red 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 17, 18, 22, 23, 31, 37, 38, 41, 42, 48: 1, 48: 2, 48: 3, 49, 50, 52, 53, 54, 57, 58, 60, 63, 64, 68, 81, 88, 90, 97, 112, 114, 115, 122, 123, 133, 139, 144, 146, 147, 149, 150, 151, 166, 168, 170, 171, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 194, 202, 207, 208, 209, 214, 215, 216, 217, 220, 221, 223, 224, 226, 227, 228, 240, 242, 243, 245, 246, 247, 254 and the like.

【0017】

Violet pigments include CI Pigment Violet 1, 2, 3, 5, 19, 23, 29, 30, 31, 32, 33, 36, 37, 38, 39, 40, 43 and 50. Blue pigments include CI Pigment Blue 1, 17, 19, 22, 56, 60, 61, 64 and the like. Examples of green pigments include CI Pigment Green 2, 8 and 10. Examples of Braun pigments include CI Pigment Brown 5, 23, 25, 26 and 32. Examples of the black pigment include CI Pigment Black 7.

【0018】

Examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

【0019】

Examples of azo dyes include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, and CI Direct. Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Dis Perth Blue 165, CI Basic Blue 41, CI Basic Red 18, CI Moldant Red 7, CI Moldant Yellow 5, CI Moldant Black 7, etc.

【0020】

Examples of anthraquinone dyes include CI Bat Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Reactive Blue 49, CI Disperse Red 60, CI Disperse Blue 56, and CI Disperse Blue. 60 and so on.

【0021】

In addition, phthalocyanine dyes such as CI Pad Blue 5 and quinone imine dyes such as CI Basic Blue 3 and CI Basic Blue 9 as quinoline dyes such as CI Solvent Yellow 33 and CI Acid Yellow 3, CI Disperse Yellow 64 and the like, and examples of the nitro dye include CI Acid Yellow 1, CI Acid Orange 3, CI Disperse Yellow 42 and the like.

【0022】

Specific examples of carbon black and dyes / pigments other than those described above include the following. Mitsubishi Carbon Black M1000, Mitsubishi Carbon Black MA-100, Mitsubishi Carbon Black # 40, Victoria Pure Blue (42595), Auramin O (41000), Cachiron Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170) ), Sakuranin OK 70: 100 (50240), Eriograusin X (42080), NO.120 / Rhodamine Yellow (21090), Rhodamine Yellow GRO (21090), Shimura First Yellow GRO (21090), Shimura First Yellow 8GF ( 21105), Benzijin Yellow 4J-564D (21095), Simler First Red 4015 (12355), Lionor Red 7B4401 (15850), Firstgen Blue JGR-L (74160), Lionor Blue SM (26150), Lionor Blue ES (Pigment Blue 15: 6, Pigment Blue 1536), Rio Nogen Red GD (Pigment Red 168, Pigment Red 108), Lionol Green 2YS (Pigment Green 36), etc.

【0023】

In the curable resin composition according to the present invention, the proportion of the component (a) is usually preferably selected in the range of 1 to 70% by weight with respect to the total solid content in the curable resin composition. Within this range, 10 to 70% by weight is more preferable, and 20 to 60% by weight is particularly preferable. In the present invention, the "solid content" means all components other than the component (b) (solvent component) described later.

【0024】

In the curable resin composition according to the present invention, the component (b) dissolves or disperses the components (a) and (C), as well as the components (d) and (e), which may be blended in some cases, and has a viscosity. Functions to adjust. As the solvent constituting the component (b), alcohols {hereinafter, abbreviated as (b1) component}, alkyl alcohol ethers {hereinafter, abbreviated as (b2) component}, alkyl alcohol ether acetates {hereinafter, ( b3) Abbreviated as a component}, a solvent component other than the (b1) component or (b3) component having a boiling point (meaning the boiling point under the condition of pressure 1013.25 [hPa]; hereinafter, the same meaning) of 150 ° C or more. {Hereafter, abbreviated as (b4) component}, solvent component other than (b1) component or (b4) component {hereinafter, abbreviated as (b5) component} and the like can be mentioned.

【0025】

As the component (b1) and the component (b2), those having a monovalent to divalent alcoholic hydroxyl group are preferable. Specifically, aliphatic alcohols such as propanol, butanol, propylene glycol and butanediol, aromatic alcohols such as benzyl alcohol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol mono-n-butyl ether and propylene glycol methyl. Examples thereof include glycol ethers such as ether and diethylene glycol monoethyl ether. Of these, alkyl alcohol ethers are preferable, and glycol mono ethers are particularly preferable. The component (b) may be either the component (b1) or the component (b2), or may be a mixture of both. Further, each of the component (b1) and the component (b2) may be one kind or a mixture of two or more kinds.

【0026】

Among the components (b1) and (b2), those having a boiling point of 50 to 300 ° C are preferable. If the boiling point is lower than 50 ° C, drying is promoted in the coating process and the like, so that the effects of adding the components (b1) and (b2) may be offset. When the boiling point is higher than 300 ° C, the effect of suppressing the drying property of the curable resin composition is high, but a large amount of residual solvent is present in the coating film even after heat firing, which may cause quality problems. The preferred range of boiling points for component (b1) and component (b2) is 100 to 250 ° C.

【0027】

In the curable resin composition according to the present invention, the ratio of the component (b2) to the component (b) is preferably in the range of 1 to 70% by weight. More preferably, it is 10 to 40% by weight, and particularly preferably 20 to 40% by weight.

【0028】

The component (b3) can be used by further mixing the component (b1) and / or the component (b2). By further mixing the component (b1) and / or the component (b2) with the component (b3), the solubility of the component dissolved in the component (b) is improved, and the dispersibility of the dispersed component is improved. Stabilize. Specific examples of the component (b3) include propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether acetate. Of these, propylene glycol monomethyl ether acetate is also preferable. The ratio of the component (b3) to the component (b) is not particularly limited, but is preferably selected in the range of 30 to 90% by weight. More preferably, it is 50 to 80% by weight. The component (b3) may be one kind or a mixture of two or more kinds.

【0029】

The component (b3) preferably has a boiling point higher than that of the component (b1) or the component (b2). If the boiling point of the component (b3) is extremely low, the component (b1) or the component (b3) may volatilize before the component (b2) as the drying progresses, causing agglomeration of the coloring material in the concentrate. , Not preferable. In addition, when a plurality of (b1) components are used as solvent components, when a plurality of (b2) components are used, and when a (b1) component and a (b2) component are used in combination, all of these are ( b3) It is preferable that the temperature is lower than the boiling point of the component.

【0030】

The (b4) component has a boiling point of 150 ° C or higher, and the (b1) component or the solvent component other than the (b3) component} is a solvent mixture containing the (b1) component and / or the (b2) component, and in some cases, the (b3) component. By mixing with, the drying of the component (b) is suppressed.

【0031】

Specific examples of the component (b4) include ethyl 3-ethoxypropionate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, diethiolene glycol dimethyl ether, and diethylene glycol diethyl ether. Examples thereof include ethylene glycol diacetate. Of these, ethyl 3-ethoxypropionate and diethylene glycol monoethyl ether acetate are preferable. The ratio of the component (b4) to the component (b) is not particularly limited, but is preferably selected in the range of 1 to 60% by weight. More preferably, it is 10 to 30% by weight. The component (b4) may be one kind or a mixture of two or more kinds.

【0032】

The component (b5) {the solvent component other than the component (b1) or the component (b4)} is used for adjusting the viscosity of the curable resin composition according to the present invention, and the component (d) (photopolymerization initiator system) described later, ( e) It functions to uniformly dissolve or disperse the component {(a) component or other additives other than the component (d)}.

【0033】

Specific examples of the component (b5) include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprilate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, and the like. Diisobutylene, amyl acetate, butyl acetate, apcosiner, butyl ether, diisobutyl ketone, methylcyclohexene, methylnonylketone, propyl ether, dodecane, socal solvent No.1 and No.2, amylformate, dihexyl ether, diisopropylketone, solvesso # 150, (n, sec, t-) Butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amylketone, ethylbenzoate, amilk lolide, ethylene glycol diethyl ether, ethyl orthoformate, methoxymethylpentanone, methylbutyl Ketone, methylhexylketone, methylisobutyrate, benzonitrile, ethylpropionate, methylisoamylketone, methylisobutylketone, propylacetate, amylacetate, amylformate, bicyclohexyl, dipentene, methoxymethylpentanol, methylamylketone , Methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, diglime, ethylene glycol acetate, ethyl carbitol, Examples thereof include butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether and 3-methyl-3-methoxybutyl acetate. The component (b5) may be one kind or a mixture of two or more kinds.

【0034】

The content of the component (b) composed of the above components (b1) to (b5) in the entire curable resin composition according to the present invention is not particularly limited, but is usually a curable resin composition. The ratio to the whole thing shall be 99% by weight or less. If the component (b) exceeds 99% by weight, the components (a) and (c) are too small to form a coating film, and even if the component (b) is too small, the viscosity becomes high. It becomes too high and unsuitable for application. The ratio of the component (b) to the entire curable resin composition is preferably 50 to 90% by weight, and particularly preferably 60 to 85% by weight.

【0035】

The curable resin composition according to the present invention is suitably used as a coating liquid when applied to a transparent substrate to produce a color filter. Hereinafter, a case where the composition is used as a curable composition for a color filter will be described as an example. When the component (c1) (binder resin) is used alone, the component (c1) of the type suitable for it is appropriately selected in consideration of the formability and performance of the target pixel image, the manufacturing method to be adopted, and the like. When the component (c1) is used in combination with the component (c2), the physical properties of the curable resin composition for a color filter after modification and curing (particularly after photocuring), for example, compatibility with component (b) and curing. The film-forming property of the sex resin composition on the substrate, the adhesiveness with the substrate, the developability of the coating film, and the like are improved.

【0036】

Specific examples of the component (c1) include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylamide, maleic acid, (meth) acrylonitrile, styrene, vinyl acetate, vinylidene chloride, maleimide, and the like alone. Examples include polymers or copolymers containing these monomers, polyethylene oxide, polyvinylpyrrolidone, polyamide, polyurethane, polyester, polyether, polyethylene terephthalate, acetyl cellulose, novolak resin, resole resin, polyvinylphenol, polyvinyl butyral and the like. Be done. In the present invention, "(meth) acrylic acid" means that both acrylic acid and methacrylic acid are contained, and (meth) acrylate, (meth) acryloyl group and the like have the same meaning. ) Polymer means that it contains both a homopolymer and a copolymer. Further, in the present invention, the "acrylic resin" means a (co) polymer containing (meth) acrylic acid and a (co) polymer containing a (meth) acrylic acid ester having a carboxyl group.

【0037】

Among the components (c1) listed above, an acrylic resin containing a monomer having a carboxyl group or a phenolic hydroxyl group in the side chain or main chain is preferable. When an acrylic resin having these functional groups is used as the component (c1), the obtained color filter can be developed with an alkaline solution. Of these, acrylic resins having a carboxyl group that can be developed in a highly alkaline solution, such as an acrylic acid (co) polymer, a styrene-maleic anhydride resin, and an acid anhydride-modified resin of novolak epoxy acrylate, are preferable. Is. Of these, a (co) polymer containing (meth) acrylic acid or a (co) polymer containing a (meth) acrylic acid ester having a carboxyl group is particularly preferable. This is because these acrylic resins are excellent in developability, transparency, etc., and can be combined with various monomers to obtain copolymers having different performances, and the production method is easy to control.

【0038】

The acrylic resin as the component (c1) is, for example, a (co) polymer containing the following monomers as a main component. Examples of the monomer include (meth) acrylic acid, succinic acid (2- (meth) acryloyloxyethyl) ester, adipic acid (2-acryloyloxyethyl) ester, and phthalic acid (2- (meth) acryloyloxy). Ethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) ester, maleic acid (2- (meth) acryloyloxyethyl) ester, succinic acid (2- (meth) acryloyloxypropyl) ester , Adiponic acid (2- (meth) acryloyloxypropyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxypropyl) ester, phthalic acid (2- (meth) acryloyloxypropyl) ester, maleic acid (2- (meth) acryloyloxypropyl) ester, succinic acid (2- (meth) acryloyloxybutyl) ester, adipic acid (2- (meth) acryloyloxybutyl) ester, hexahydrophthalic acid (2-) For hydroxyalkyl (meth) acrylates such as (meth) acryloyloxybutyl ester, phthalic acid (2- (meth) acryloyloxybutyl) ester, maleic acid (2- (meth) acryloyloxybutyl) ester, etc. Examples thereof include compounds to which an acid (anhydrous) such as (anhydrous) succinic acid, (anhydrous) phthalic acid, and (anhydrous) maleic acid is added.

【0039】

Examples of the monomer that can be copolymerized with the above-mentioned monomer include styrene-based monomers such as styrene, α-methylstyrene, and vinyltoluene, lauric acid, maleic acid, fumaric acid, maleic anhydride, and itacon. Unsaturated group-containing carboxylic acids such as acids, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl Esters of (meth) acrylic acid such as (meth) acrylate, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, ε- to (meth) acrylic acid Compounds to which lactones such as caprolactone, β-propiolactone, γ-butyrolactone and δ-valerolactone are added, acrylonitrile such as acrylonitrile and metaacrylonitrile, (meth) acrylamide, N-methylol acrylamide, N, N- Acrylamides such as dimethylacrylamide, N-methacryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethylacrylamide, vinyl acetate, vinyl versatic acid, vinyl propionate, vinyl cinnate, pivalic acid Examples include vinyl acids such as vinyl.

【0040】

The components (c1) preferable for improving the strength of the coating film on the substrate are at least one of the following (c11) monomer groups and at least one of the following (c12) monomer groups. Examples thereof include copolymerized acrylic resins. The (c11) monomer group includes styrene, α-methylstyrene, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, hydroxyphenyl (meth) acrylamide, and hydroxyphenyl (meth) acrylic. Examples thereof include monomers having a phenyl group such as sulfoamide. The (c12) monomer group includes (meth) acrylic acid, succinic acid (2- (meth) acryloyloxyethyl) ester, adipic acid (2-acryloyloxyethyl) ester, and phthalic acid (2-). It has a carboxyl group such as (meth) acryloyloxyethyl) ester, hexahydrophthalic acid (2- (meth) acryloyloxyethyl) ester, and maleic acid (2- (meth) acryloyloxyethyl) ester (meth). Acrylic acid ester and the like can be mentioned. The copolymer contains 10 to 98 mol% of the (c11) monomer group, preferably 20 to 80 mol%, more preferably 30 to 70 mol%, and 2 to 90 mol% of the (c12) monomer group. , Preferably 20 to 80 mol%, more preferably 30 to 70 mol%.

【0041】

Further, the acrylic resin as the component (c1) preferably has an ethylenic double bond in the side chain. When an acrylic resin having an ethylenic double bond in the side chain is used as the component (c1), the photocurability of the curable resin composition for a color filter according to the present invention is improved. Therefore, the color filter according to the second invention. The resolution and adhesion to the substrate can be further improved.

【0042】

As a method for introducing an ethylenic double bond into the side chain of the component (c1), for example, the methods described in Japanese Patent Publication No. 50-34443, Japanese Patent Publication No. 50-34444, etc., that is, (1) acrylic type Examples include a method of reacting a carboxyl group of a resin with a compound having a glycidyl group or an epoxycyclohexyl group and a (meth) acryloyl group, and (2) a method of reacting a hydroxyl group of an acrylic resin with an acrylic acid chloride or the like. Be done.

【0043】

More specifically, acrylic resins having a carboxyl group or a hydroxyl group include (meth) glycidyl acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, (iso) glycidyl crotonate ether, (3). , 4-Epoxycyclohexyl) Methyl (meth) acrylate, (meth) acrylic acid chloride, (meth) allyl chloride, etc. are reacted to obtain an acrylic resin having an ethylenic double bond group in the side chain. Can be done. Among them, a resin obtained by reacting an acrylic resin having a carboxyl group or a hydroxyl group with an alicyclic epoxy compound such as (3,4-epoxycyclohexyl) methyl (meth) acrylate is particularly preferable.

【0044】

As described above, in order to introduce an ethylenic double bond into an acrylic resin having a carboxylic acid group or a hydroxyl group in advance, 2 to 50 mol%, preferably 5 to 40 mol% of the carboxyl group or hydroxyl group of the acrylic resin is used. It is preferable to use a method of binding a compound having an ethylenic double bond. The preferable content of the carboxyl group is in the range of 5 to 200 as the acid value. If the acid value is 5 or less, it becomes insoluble in an alkaline developer, and if it exceeds 200, the development sensitivity may decrease, which is not preferable.

【0045】

These acrylic resins preferably have a weight average molecular weight (Mw) in the range of 1,000 to 100,000 as measured by GPC. If the weight average molecular weight is 1,000 or less, it is difficult to obtain a uniform coating film, and if it exceeds 100,000, the developability tends to decrease, which is not preferable.

【0046】

The ratio of the component (c1) is preferably selected in the range of 10 to 80% by weight, particularly preferably 20 to 70% by weight, based on the total solid content in the curable resin composition according to the present invention. A silane coupling agent can be added for the purpose of improving the affinity of the interface between the component (a) and the component (c1). The proportion of the silane coupling agent is preferably selected in the range of 1 to 10% by weight in the solid content.

【0047】

The component (c2) is not particularly limited as long as it is a polymerizable low molecular weight compound, but an addition-polymerizable compound having at least one ethylenic double bond (hereinafter, abbreviated as ethyleney compound) is preferable. .. The ethylenic compound is ethylene such that when the curable resin composition according to the present invention is irradiated with active light, it is addition-polymerized and cured by the action of the component (d) (photopolymerization initiator system) described later. It is a compound having a sex double bond. In the present invention, the term "monomer" means a so-called polymer substance, and includes a dimer, a trimer, an oligomer, etc. in addition to a monomer in a narrow sense.

【0048】

Examples of the ethylenic compound of the component (c2) include unsaturated carboxylic acid, esters of the monohydroxy compound, esters of aliphatic polyhydroxy compound and unsaturated carboxylic acid, and aromatic polyhydroxy compound and unsaturated. Esters obtained by esterification with carboxylic acids, unsaturated carboxylic acids and polyvalent carboxylic acids, and polyvalent hydroxy compounds such as the above-mentioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds, polyisocyanates. Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting a compound with a (meth) acryloyl-containing hydroxy compound.

【0049】

Examples of the esters of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethanetriacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. Examples thereof include acrylic acid esters such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. Further, the acrylic acid moiety of these acrylates is replaced with a methacrylic acid ester instead of a methacrylic acid moiety, an itaconic acid ester substituted with an itaconic acid moiety, a crotonic acid ester substituted with a crotonic acid moiety, or a maleic acid substituted with a maleic acid moiety. Esters and the like can be mentioned.

【0050】

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.

【0051】

The esters obtained by the esterification reaction of the unsaturated carboxylic acid with the polyvalent carboxylic acid and the polyvalent hydroxy compound do not necessarily have to be a single substance, but may be a mixture. Typical examples are condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol and glycerin. Examples thereof include a condensate of.

【0052】

Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate, and fats such as cyclohexane diisocyanate and isophorone diisocyanate. Aromatic diisocyanates such as cyclic diisocyanates, tolylene diisocyanates, diphenylmethane diisocyanates, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3- Examples thereof include a reaction product with a (meth) acryloyl group-containing hydroxy compound such as hydroxy (1,1,1-trimethacryloyloxymethyl) propane.

【0053】

Examples of ethylenic compounds other than those described above include acrylamides such as ethylenebisacrylamide, allyl esters such as diallyl phthalate, and vinyl group-containing compounds such as divinylphthalate.

【0054】

The ratio of the component (c2) is preferably selected in the range of 10 to 80% by weight with respect to the total solid content in the curable resin composition according to the present invention. Above all, the range of 20 to 70% by weight is particularly preferable.

【0055】

When the curable resin composition according to the present invention contains the ethylenic compound of the component (c2), it directly absorbs light or is photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate polymerization active radicals. It is necessary to add the component (d) (photopolymerization initiator system) having a function to be generated to the curable resin composition. In the present invention, the term "(d) component photopolymerization initiator system" refers to a photopolymerization initiator {hereinafter abbreviated as (d1) component} and an accelerator {hereinafter abbreviated as (d2) component}. It means a mixture in which an additive such as a sensitive dye {hereinafter abbreviated as (d3) component} is used in combination.

【0056】

When the black photopolymerizable layer is formed by the curable resin composition, the component (d) is exposed to an image from the photopolymerizable layer via a pattern mask, so that the component (d) is sensitive to ultraviolet rays to visible rays. It means a compound that exerts its effect, and it is preferable to use an exposure light source corresponding thereto when exposing an image. Further, also in each of the red, green, and blue photopolymerizable layers, in order to form red, green, and blue pixel image patterns between the black matrix patterns by exposure through a pattern mask of each color or other methods. As in the case of the black matrix pattern, as the component (d), a compound exhibiting sensitivity to ultraviolet light to visible light, particularly a compound exhibiting spectral sensitivity at a wavelength of 450 nm or less, particularly 400 nm or less is preferable.

【0057】

Examples of the component (d1) constituting the component (d) include metallocene compounds containing titanosen compounds described in JP-A-59-152396 and JP-A-61-151197, and JP-A-P. hexaarylbiimidazole derivatives as described in 10-39503, JP-halomethyl -s- triazine derivatives, N- aryl -α- amino acids such as N- phenylglycine, N- aryl Le -α- amino salts, N- Examples thereof include radical activators such as aryl-α-amino acid esters.

【0058】

Examples of the component (d2) (accelerator) constituting the component (d) include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, and 2 -Mercapto compounds having a heterocycle such as mercaptobenzoxazole and 2-mercaptobenzimidazole, and aliphatic polyfunctional mercapto compounds can be mentioned. The component (d1) and the component (d2) may each be a mixture of two or more kinds.

【0059】

Specific examples of the component (d) (photopolymerization initiator system) are described on pages 16 to 26 of "Fine Chemicals" (March 1, 1991, vol.20, No.4). In addition to dialkylacetophenone-based, benzoin, thioxanthone derivatives, etc., hexaarylbiimidazole-based, S-trihalomethyltriazine-based, which are described in JP-A-58-403023, JP-A-45-37377, etc. A system in which titanosen and a xanthene dye, an addition-polymerizable ethylenically saturated double bond-containing compound having an amino group or a urethane group, which are described in JP-A-4-221958 and JP-A-4-219756, are combined. , And so on.

【0060】

If the ratio of the component (d) is extremely low, it may cause a decrease in sensitivity to exposed light rays, and conversely, if it is extremely high, the solubility of an unexposed portion in a developer decreases, which causes development failure. Therefore, it is preferable to select it in the range of 0.1 to 30% by weight based on the total solid content in the curable resin composition according to the present invention. Of these, 0.5 to 20% by weight is preferable, and 0.7 to 10% by weight is more preferable.

【0061】

The component (d) can be blended with the component (d3) (sensitizing dye) according to the wavelength of the image exposure light source, if necessary, for the purpose of improving the sensitivity. Examples of these (d3) components include xanthene dyes described in JP-A-4-221958, JP-A-4-219756, etc., JP-A-3-239703, JP-A-5-289335, and the like. A coumarin dye having a heterocycle, a 3-ketocoumarin compound described in JP-A-3-239703, JP-A-5-289335, etc., and a pyrromethene dye described in JP-A-6-19240. , Others, Japanese Patent Application Laid-Open No. 47-2528, Japanese Patent Application Laid-Open No. 54-155292, Japanese Patent Application Laid-Open No. 45-37377, Japanese Patent Application Laid-Open No. 48-84183, Japanese Patent Application Laid-Open No. 52-112681, Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-Open No. 60-88005, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2-69, Japanese Patent Application Laid-Open No. 57-168088, Japanese Patent Application Laid-Open No. 5-107761, Examples thereof include dyes having a dialkylaminobenzene skeleton described in Kaihei 5-210240 and JP-A-4-288818.

【0062】

Of these (d3) components, an amino group-containing sensitizing dye is preferable, and a compound having both an amino group and a biphenyl group in the same molecule is more preferable. Particularly preferred are, for example, 4,4'-bis (dimethylamino) benzophenone (Michler's ketone), 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3, Benzophenone compounds such as 3'-diaminobenzophenone, 3,4-diaminobenzophenone, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) ) Benzophenone [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzophenone, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2-( p-Dimethylaminophenyl) benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p) -Diethylaminophenyl) 1,3,4-thiazazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethyl) P-dialkylaminophenyl group-containing compounds such as aminophenyl) pyrimidine and (p-diethylaminophenyl) pyrimidine. The most preferred of these is 4,4'-dialkylaminobenzophenone.

【0063】

The ratio of the component (d3) is preferably selected in the range of 0 to 20% by weight with respect to the total solid content in the curable resin composition according to the present invention. It is more preferably 0.2 to 15% by weight, still more preferably 0.5 to 10% by weight.

【0064】

As described above, the curable resin composition according to the present invention may further contain the component (e) {components other than the component (a) or the component (d)} as necessary, but the component (e) may be a component. , Thermopolymerization inhibitor {hereinafter abbreviated as (e1) component}, Plasticizer {hereinafter abbreviated as (e2) component}, dispersant, dispersion aid, storage stabilizer, surface protectant, smoothing agent, coating Auxiliary agents, adhesion improvers, coatability improvers, development improvers, silane coupling agents and the like can be added. Examples of the component (e1) include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like. The blending amount of these (e1) components is preferably selected in the range of 0 to 3% by weight with respect to the total solid content in the curable resin composition.

【0065】

Examples of the component (e2) include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. The blending amount of these (e2) components is preferably selected in the range of 10% by weight or less with respect to the total solid content in the curable colored resin composition.

【0066】

Next, a method for preparing a curable resin composition for a color filter according to the present invention will be described. First, the components (a) and (b) are weighed in predetermined amounts, and in the dispersion treatment step, the component (a) is dispersed in the component (b) to obtain a liquid curable resin composition (ink-like substance). .. In this dispersion treatment step, a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer and the like can be used. Since the component (a) is made into fine particles by this dispersion treatment, the coating characteristics of the curable resin composition are improved, and a color filter having an improved transmittance of transmitted light can be obtained.

【0067】

When the component (a) is dispersed in the component (b), it is preferable to disperse the component (c1) and / or the component (c2), a dispersant such as a surfactant, a dispersion aid, etc. in combination as appropriate. .. In particular, it is preferable to use a polymer dispersant because it is excellent in dispersion stability over time. For example, in the case of dispersion treatment using a sand grinder, it is preferable to use glass beads having a diameter of 0.1 to several millimeters or zirconia beads. The temperature during the dispersion treatment is usually set in the range of 0 ° C to 100 ° C, preferably room temperature to 80 ° C. The dispersion time varies depending on the composition of the ink-like substance {(a) component, (b) component, dispersant}, the size of the sand grinder device, and the like, and therefore needs to be appropriately adjusted.

【0068】

The ink-like substance obtained by the above dispersion treatment step is mixed with the component (c1) and / or the component (c2), and if necessary, a predetermined amount of the component (d), the component (e), etc. to be uniform. Use as a dispersion solution. Since fine dust may be mixed in each of the dispersion treatment step and the mixing step, it is preferable to filter the obtained ink-like substance with a filter or the like.

【0069】

Next, the color filter according to the second invention of the present invention and the manufacturing method according to the third invention will be described. The material of the transparent substrate of the color filter is not particularly limited as long as it is transparent and has appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethylmethacrylate, and polysulfone thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, and poly (meth) acrylics. Examples thereof include a thermoplastic resin sheet such as a based resin, and various types of glass. Among these, glass and heat-resistant resin are preferable from the viewpoint of heat resistance.

【0070】

For the transparent substrate and the black matrix-forming substrate, in order to improve the surface physical properties such as adhesiveness, if necessary, corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc. May be done. The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. When thin film formation treatment of various resins is performed, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

【0071】

The color filter according to the second invention of the present invention can be manufactured by providing a black matrix on a transparent substrate and usually forming red, green, and blue pixel images. The curable resin composition is used as at least one kind of resist-forming coating liquid among black, red, green and blue. For black resist, it is on the plain glass surface on the transparent substrate, for red, green, and blue, it is on the resin black matrix forming surface formed on the transparent substrate, or metal black formed by using a chromium compound or other light-shielding metal material. On the matrix-forming surface, each process of coating, heat-drying, image exposure, development, and thermosetting is performed to form a pixel image of each color.

【0072】

The black matrix is formed on a transparent substrate by utilizing a light-shielding metal thin film or a pigment dispersion liquid for a black matrix. As the light-shielding metal material, a chromium compound such as metallic chromium, chromium oxide, or chromium nitride, a nickel-tungsten alloy, or the like is used, and these may be laminated in a plurality of layers.

【0073】

These metal light-shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape by a positive photoresist, etching by mixing dicerium ammonium nitrate and perchloric acid with respect to chromium. A black matrix can be formed by using a liquid and engraving other materials with an etching solution suitable for the material, and finally peeling the positive photoresist with a special release agent.

【0074】

In this case, first, a thin film of these metals or metal / metal oxides is formed on the transparent substrate by a vapor deposition or sputtering method. Next, after forming a coating film of the curable resin composition on this thin film, the coating film is exposed and developed using a photomask having a repeating pattern such as stripes, mosaics, and triangles to form a resist image. After that, the coating film can be etched to form a black matrix.

【0075】

When a pigment dispersion liquid for a black matrix is used, a curable resin composition containing a black coloring material is used to form a black matrix. For example, black color materials such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, etc., or red, green, blue, etc. appropriately selected from inorganic or organic pigments and dyes. A black matrix can be formed by using a curable resin composition containing a black color material by mixing in the same manner as the method for forming red, green, and blue pixel images described below.

【0076】

A curable resin composition for a color filter containing a coloring material of one of red, green, and blue is applied onto a transparent substrate provided with a black matrix, dried, and then a photomask is placed on the coating film. A pixel image is formed through this photomask by image exposure, development, and if necessary, thermosetting or photocuring to create a colored layer. A color filter image can be formed by performing this operation on each of the three color filter curable resin compositions of red, green, and blue.

【0077】

The curable resin composition for a color filter can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method or the like. Above all, according to the die coating method, the amount of coating liquid used is significantly reduced, there is no influence of mist adhering when the spin coating method is used, and the generation of foreign substances is suppressed. Is preferable.

【0078】

The coating conditions by the die coating method may be appropriately selected depending on the composition of the curable resin composition for a color filter, the type of the color filter to be produced, and the like. For example, the lip width of the nozzle tip is preferably 50 to 500 μm, and the distance between the nozzle tip and the substrate surface is preferably 30 to 300 μm. In order to adjust the thickness of the coating film, the traveling speed of the lip and the discharge amount of the liquid curable resin composition from the lip may be adjusted.

【0079】

After applying the curable resin composition to the substrate, the coating film is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after pre-drying, it is heated again to dry. The conditions for pre-drying can be appropriately selected according to the type of the component (b), the performance of the dryer used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 80 ° C, preferably 50 to 70 °, depending on the type of component (b) and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes at the temperature of C.

【0080】

The temperature condition for reheating and drying is preferably 50 to 200 ° C, which is higher than the pre-drying temperature, particularly 70 to 160 ° C, and particularly preferably 70 to 130 ° C. The drying time is preferably in the range of 10 seconds to 10 minutes, particularly 15 seconds to 5 minutes, although it depends on the heating temperature. The higher the drying temperature, the better the adhesiveness to the transparent substrate, but if it is too high, the compound constituting the component (d) may be decomposed to induce thermal polymerization, resulting in poor development. The thickness of the curable resin composition coating film for a color filter after drying is in the range of 0.5 to 3 μm, preferably 1 to 2 μm. In the drying step of the coating film, a vacuum drying method may be used in which the coating film is dried in the vacuum chamber without increasing the temperature.

【0081】

Image exposure is performed by superimposing a negative matrix pattern on a coating film of a curable resin composition and irradiating a light source of ultraviolet rays or visible light through this mask pattern. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by oxygen, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer. The light source used for the above image exposure is not particularly limited. Examples of the light source include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arcs, fluorescent lamps, argon ion lasers, YAG lasers, etc. Examples thereof include laser light sources such as an excimer laser, a nitrogen laser, a helium cadmium laser, and a semiconductor laser. An optical filter can also be used when irradiating and using light of a specific wavelength.

【0082】

In the color filter according to the second invention of the present invention, a coating film made of the curable resin composition according to the first invention is image-exposed with the above-mentioned light source, and then an organic solvent or a surfactant and an alkaline compound are used. An image can be formed and prepared on a substrate by development using an aqueous solution containing. The aqueous solution can further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

【0083】

As alkaline compounds, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, natriu hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate , Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-di- or triethanolamine, mono-di- or trimethyl Organics such as ami, mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline Examples include alkaline compounds. These alkaline compounds may be a mixture of two or more kinds.

【0084】

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples thereof include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates and sulfosuccinic acid ester salts, and amphoteric surfactants such as alkyl betaines and amino acids.

【0085】

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent can be used alone or mixed with water.

【0086】

The conditions of the development process are not particularly limited, and the development temperature is usually in the range of 10 to 50 ° C, particularly 15 to 45 ° C, particularly preferably 20 to 40 ° C, and the development methods are immersion development method and spray development. Any method such as a method, a brush development method, or an ultrasonic development method can be used.

【0087】

In addition to the above-mentioned manufacturing method, the color filter according to the second invention of the present invention contains (1) (b) component, (a) phthalocyanine pigment as component, and (c) polyimide resin as component. It can also be produced by a method of applying the curable resin composition containing the mixture to a substrate and forming a pixel image by an etching method. Further, (2) a method of forming a pixel image directly on a transparent substrate by a printing machine using a curable resin composition containing a phthalocyanine pigment as a coloring ink, and (3) a curable resin composition containing a phthalocyanine pigment. Examples thereof include a method in which a material is used as an electrodeposition solution and a substrate is immersed in the electrodeposition solution to deposit a colored film on an ITO electrode having a predetermined pattern. Further, (4) a method in which a film coated with a curable resin composition containing a phthalocyanine pigment is attached to a transparent substrate and peeled off, image exposure and development are performed to form a pixel image, and (5) a method containing a phthalocyanine pigment is included. Examples thereof include a method of forming a pixel image with an inkjet printer using a curable resin composition with colored ink. As the method for producing the color filter, a method suitable for the composition of the curable resin composition for the color filter is adopted.

【0088】

The color filter after development is subjected to a thermosetting treatment. The thermosetting treatment conditions at this time are selected in the temperature range of 100 to 280 ° C, preferably in the range of 150 to 250 ° C, and the time is selected in the range of 5 to 60 minutes. Through these series of steps, the formation of a one-color patterning image is completed. This process is repeated in sequence to pattern black, red, green, and blue to form a color filter. The order of patterning the four colors is not limited to the above-mentioned order.

【0089】

The color filter according to the second invention of the present invention forms a transparent electrode such as ITO on an image as it is and is used as a part of parts such as a color display and a liquid crystal display device, but has surface smoothness. If necessary, a top coat layer such as polyamide or polyimide can be provided on the image in order to improve the durability and durability. In addition, in some applications such as a plane orientation type drive system (IPS mode), a transparent electrode may not be formed.

【0090】

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded. The details of the component (a) used (coloring material) in the following Examples and Comparative Examples are as shown in Table 1, and the details of the component (b) used (solvent component) are shown in Table 1. As shown in -2.

【0091】

[table 1]

<img file="JP2003138223A_D0001.tif" />【0092】

[Table 2]

<img file="JP2003138223A_D0002.tif" />【0093】

[Example 1 to Example 3, Comparative Example 1 to Comparative Example 3] &lt;Preparation of curable resin composition&gt; Each component constituting the liquid curable resin composition is weighed in the amount shown in Table 3, and zirconia beads (0.5 mm in diameter) 3.6 times by weight based on the total amount. ) Was stored in a paint shaker and subjected to a dispersion treatment for 7 hours to prepare.

【0094】

[Table 3]

<img file="JP2003138223A_D0003.tif" />【0095】

[Chemical 1]

<img file="JP2003138223A_D0004.tif" />【0096】

[Chemical 2]

<img file="JP2003138223A_D0005.tif" />【0097】

&lt;Manufacturing of color filter&gt; A liquid black curable resin composition was applied to a glass substrate (manufactured by Asahi Glass Co., Ltd., AN635) having a length of 370 mm, a width of 470 mm, and a thickness of 0.7 mm with a die coater. The die coater used was a stainless steel die coater with a width of 360 mm, the lip spacing was 200 μm, and the gap with the glass substrate surface was 100 μm. At the time of application, the liquid discharge amount was adjusted so that the dry film thickness was 0.7 μm. Then, after drying at 60 ° C for 1 minute, it was dried by heating at 110 ° C for 2 minutes. Then, a polyvinyl alcohol aqueous solution was applied onto the coating film of the curable resin composition so that the dry film thickness was 1.5 μm, and then dried to form an oxygen blocking layer.

【0098】

Next, using a negative photomask for black matrix that repeats at a pitch of 30 μm in width, 330 μm in length, and 110 μm in width, and using a 2 kW high-pressure mercury lamp, 300 mJ / cm.²The exposure process was performed with the exposure amount of. Then, the development process was carried out using a 0.1 wt% sodium carbonate aqueous solution at a developer temperature of 23 ° C. Then, 3kg / cm²A black matrix was formed by spray washing with water pressure for 30 seconds. Then, the thermosetting treatment was carried out at a temperature of 200 ° C. for 7 minutes.

【0099】

Next, using a liquid curable resin composition containing each of the red, green, and blue materials, each treatment of coating, pre-drying, heat-drying, exposure, development, washing with water, and thermosetting is performed in the same procedure as above. Was performed to sequentially form each color pattern, and a color filter was obtained. At this time, the liquid discharge amount was adjusted so that the dry film thickness was 1.3 μm. The exposure amount is 500mJ / cm for each color.²For the development treatment, a 0.1 wt% sodium carbonate aqueous solution was used, and development was performed at a developer temperature of 25 ° C. After development, 10kg / cm²The water pressure was sprayed for 30 seconds. At the end of each color, a thermosetting treatment was performed at 200 ° C for 15 minutes. The developing machine used was the same as that used for forming the black matrix described above. In this way, 100 color filters with a resin black matrix were produced using the curable resin compositions having the solvent compositions of Examples 1 to 3 and Comparative Examples 1 to 3.

【0100】

&lt;Evaluation test of color filter&gt; The presence or absence of foreign matter defects was measured for the obtained color filter, and the occurrence rate of foreign matter defects is shown in Table-4. In Table 4, black, red, green, and blue mean liquid curable resin compositions (resists) of each color. Foreign matter defects are [(major axis)²+ (Short diameter)²] Is defined as a foreign matter with a square root of 60 μm or more, and the value obtained by dividing the number of color filters in which foreign matter defects due to aggregation of each color resist are found by the total number of manufactured sheets (100 sheets) is defined as the foreign matter defect occurrence rate. Defined.

【0101】

[Table 4]

<img file="JP2003138223A_D0006.tif" />【0102】

From Table-1 to Table-4, the following is clear. (1) Since the color filter using the curable resin composition according to the present invention uses the component (b2) as the component (b), the rate of occurrence of foreign matter defects is low (see Examples 1 to 3). ). (2) On the other hand, the one of Comparative Example 1 in which only the component (b3) is used as the component (b) has a high foreign matter defect occurrence rate. (3) Further, those of Comparative Example 2 and Comparative Example 3 which do not contain either the component (b1) or the component (b2) as the component (b) have a high foreign matter defect occurrence rate.

【0103】

[Effect of the invention]

The present invention has been described in detail above, and has the following specially advantageous effects, and its industrial utility value is extremely large. 1. The curable resin composition according to the present invention is less likely to dry and aggregate in the step of being applied to the surface of the substrate even if the coloring material has a high concentration, and the generation of foreign substances is small. 2. When the curable resin composition according to the present invention is applied to the surface of a substrate, according to the die coating method, agglomerates are less likely to occur on the die lip, and a high quality product can be obtained with a high yield. 3. According to the method for manufacturing a color filter according to the present invention, a high-quality product with few pixel defects can be obtained with a high yield. 4. Since the color filter according to the present invention is of high quality, high quality color displays, liquid crystal display devices, etc. using the color filter can be obtained.