JP2006058821A - Colored resin composition, color filter and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored resin composition which ensures less remaining of undissolved matter of the colored resin composition in a non-image portion on a substrate, can uniformly form high density color pixels excellent in adhesion to the substrate, and ensures few defects due to a foreign substance even in die coating. <P>SOLUTION: The colored resin composition comprises a color material, a solvent, a dispersant and a binder resin, wherein the binder resin is a resin including a copolymer of at least one selected from the group consisting of a macromonomer, a monomer having an alcoholic hydroxyl group, a monomer having a carboxyl group, a monomer having N-substituted maleimide and a mono(2-(meth)acryloyloxyethyl) dicarboxylate with another copolymerizable monomer, and wherein the colored resin composition characterized by dispersant containing urethane-based dispersant. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a colored resin composition, a method for producing the same, a color filter, and a liquid crystal display device. More specifically, there is little remaining in the non-image area after development, high pattern adhesion during development, high density color pixels can be uniformly formed, and dry aggregation at the tip of the die lip during application by die coating The present invention relates to a colored resin composition in which generation of lumps is suppressed, a color filter in which pixels are formed using the colored resin composition, and a liquid crystal display device including the color filter.

Conventionally, a pigment dispersion method, a dyeing method, an electrodeposition method, and a printing method are known as methods for producing a color filter used in a liquid crystal display device or the like. Among these, from the viewpoint of spectral characteristics, durability, pattern shape, accuracy, etc., a pigment dispersion method having excellent characteristics on average is most widely adopted.
In recent years, the trend of technological innovation has been rapid, and higher transmission and higher density have been required for color filters. In order to form a high-density color filter, it was necessary to increase the colorant concentration in the colored resin composition to be used. On the other hand, components that contribute to image forming properties such as photosensitivity and solubility are relatively As a result, the original image forming performance was lost, and the undissolved product of the colored resin composition in the non-image area after development was likely to remain. If undissolved colored resin composition remains on the non-pixel area on the substrate, the resulting color filter will cause a decrease in transmittance and contrast, and if it remains on the pattern edge area, the ITO film will peel off. In addition, there has been a situation that affects the subsequent process such as deterioration of the sealing performance in the liquid crystal cell forming process.

  In order to solve such a problem, a method of reducing residue and background contamination by using a specific binder resin has been proposed (see Patent Documents 1 to 4). In addition, a method of adding an organic carboxylic acid compound having a molecular weight of 1000 or less to a colored resin composition has been proposed (see Patent Document 5). When this method was used, an effect of reducing the remaining undissolved matter in the non-pixel portion after development was observed for some of the colored resin compositions obtained by dispersing the pigment with the binder polymer.

On the other hand, various new technologies have also been developed for color filter manufacturing methods. Among the pixel forming processes, for example, with respect to the resist coating process, it has been the mainstream so far to drop the resist on the center of the substrate and make it uniform by spin coating. However, as the size of the substrate has increased, the amount of resist used has increased, and restrictions on the spin coater equipment (motor capabilities, etc.) have increased, and recently, coating technology using the die coating method has been developed. Some have been put to practical use.
JP-A-10-300922 JP-A-11-174224 JP 2000-056118 A JP2003-233179A Japanese Patent Publication No. 3293171

However, depending on Patent Documents 1 to 4, when a phosphate ester type dispersant or some amine-modified polyurethane is used as a dispersant, there are cases where the remaining amount of undissolved material cannot be completely suppressed. It was. In addition, when an organic carboxylic acid compound is added as described in Patent Document 4, not only the non-image area but also the image area adhesion decreases, resulting in a narrow development margin, pixel peeling, and white-out defects. It has been found that it tends to occur. That is, it has become very difficult to satisfy both the reduction in the remaining amount of undissolved material and the adhesion of images, and the yield has to be reduced if high quality is to be maintained.

In addition, the technique of applying a resist by a die coating method is conventionally used in the manufacture of, for example, a floppy (registered trademark) disk. Usually, a coating solution such as a resist is continuously applied to a medium such as a polymer film. It is suitably employed when applying.
On the other hand, 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 the color resist or black resist in which a high concentration of pigment is dispersed is dried at the tip of the die lip, the pigment concentration increases abruptly, which may cause agglomeration of the pigment. 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, and are not easily removed in the subsequent steps, and remain on the substrate until the end. Such agglomerates become pixel defects in the color filter and cause quality defects. If this defective phenomenon occurs frequently, the product yield will be lowered, and this is one of the phenomena that must be avoided. However, in Patent Documents 1 to 5, there are cases in which the generation of foreign matter due to dry aggregation at the tip of the die lip cannot be sufficiently suppressed during application by the die coating method.

The present invention has been made in view of the above-described problems, and its object is as follows.
(1) When applied on the substrate, the undissolved matter of the colored resin composition hardly remains in the non-image area on the substrate, and the adhesion to the substrate is excellent, and high-density color pixels are uniformly formed. To provide a colored resin composition that can be formed.
(2) To provide a colored resin composition capable of producing a color filter with a high yield by suppressing dry aggregation at the tip of the die lip during application by die coating.
(3) To provide a high-quality color filter in which an undissolved colored resin composition does not remain in a non-pixel portion on a substrate.
(4) To provide a high-quality liquid crystal display device using the color filter substrate.

As a result of intensive studies to solve the above problems, the present inventors have used a combination of a binder resin having a specific structure and a dispersant having a specific structure, so that the non-image area on the substrate is not exposed. A colored resin composition that has excellent adhesion to the substrate without residual melt, can uniformly form high-density color pixels, and suppresses the formation of dry agglomerates at the tip of the die lip during coating by die coating. It has been found that it can be obtained, and the present invention has been completed. The present invention comprises a plurality of related inventions, and the gist of each invention is as follows.
(1) A colored resin composition containing a colorant, a solvent, a dispersant, and a binder resin, wherein the binder resin has a macromonomer, a monomer having an alcoholic hydroxyl group, a monomer having a carboxyl group, and an N-position substituted maleimide A resin comprising a copolymer of at least one monomer and another copolymerizable monomer in the group consisting of a monomer and a dicarboxylic acid mono (2- (meth) acryloyloxyethyl), and the dispersant is a urethane type A colored resin composition comprising a dispersant.
(2) A color filter formed using the colored resin composition of (1). (3) A liquid crystal display device formed using the color filter according to (2).

The present invention has the following effects.
(1) When the colored resin composition according to the present invention is applied on a substrate, the undissolved material does not remain in the non-pixel portion on the substrate and is excellent in adhesion to the substrate. High density color pixels can be formed uniformly.
(2) When the colored resin composition according to the present invention is applied onto a substrate by a die coating method, dry aggregation at the tip of the die lip is suppressed, so that there is little generation of foreign matter and a color filter is produced with a high yield. be able to.
(3) In the color filter according to the present invention, the undissolved material of the colored resin composition does not remain in the non-pixel portion on the substrate. In addition, since high-density color pixels having excellent adhesion to the substrate are uniformly formed, the quality is extremely high.
(4) The liquid crystal display device according to the present invention is a high-concentration color that does not leave undissolved colored resin composition in the non-pixel portion on the substrate and has excellent adhesion to the substrate. Since an extremely high quality color filter in which pixels are uniformly formed is used, the quality is extremely high.

The constituent requirements and the like of the present invention will be described in detail below, but these are examples of embodiments of the present invention and are not limited to these contents.
[1] Constituent Components of Color Filter Coloring Composition (Resist) Each constituent component of the color filter coloring composition of the present invention will be described below. The colored resin composition (resist) according to the present invention contains a coloring material, a solvent, a dispersant, and a binder resin as essential components, and if necessary, may contain other additives other than the above components. .

Hereinafter, each component will be described.
In the following, “total solid content” refers to all components in the colored composition for a color filter of the present invention other than the solvent components described later. In addition, “(meth) acryl”, “(meth) acryloyloxy˜”, “(meth) acrylate” and the like are “acrylic and / or methacrylic”, “acryloyloxy˜ and / or methacryloyloxy˜”, “acrylate and / or”. Or (meth) acrylic acid, for example, means “acrylic acid and / or methacrylic acid”.
[1-1] Color material:
A coloring material means what colors the coloring resin composition which concerns on this invention. As the color material, a pigment or a dye can be used, but a pigment is preferable from the viewpoint of heat resistance, light resistance, and the like.

  As the pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment can be used. The structure includes organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. In addition, various inorganic pigments can also be used. Hereinafter, specific examples of usable pigments are indicated by pigment numbers. The following “CI” means a color index (CI).

  Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, and more preferably C.I. I. Pigment Blue 15: 6.

Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. Pigment Green 7 and 36.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208. Of these, C.I. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Of these, C.I. I. Pigment oranges 38 and 71.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Of these, C.I. I. Pigment violet 19 and 23, and more preferably C.I. I. Pigment Violet 23.

Examples of other pigments include barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, and chromium oxide.
A plurality of the above-mentioned various pigments can be used in combination. For example, to adjust chromaticity,
As the pigment, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a purple pigment can be used in combination. The average particle size of these pigments is usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less.

Examples of dyes that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.
Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.
In addition to the above, examples of phthalocyanine dyes include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

  Moreover, when forming the resin black matrix of a color filter using a colored resin composition, a black color material can be used. The black color material may be a single black color material or a mixture of red, green, blue, and the like. Moreover, these color materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, the average particle size is preferably 1 μm or less, preferably 0.5 μm or less.

Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black. Among these, carbon black and titanium black are preferable from the viewpoints of light shielding rate and image characteristics.
Examples of carbon black include the following carbon black.

  As products manufactured by Mitsubishi Chemical Corporation, MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B, etc. are mentioned.

Degussa's products include Printex3, Printex3OP, Printe
x30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, Special Black5, Special Black4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color lack FW18, Color Black FW200, Color Black S160, Color Black
S170 etc. are mentioned.

  Products manufactured by Cabot Corporation include: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL99R, REGA15R BLACK PEARLS 480, PEARLS 130, VULCAN XC72R, ELFTEX-8, and the like.

  The products manufactured by Colombian Carbon are: Raven11, Raven14, Raven15, Raven16, Raven22Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven10, Raven10, Raven10, V , RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000 and the like.

It is particularly preferable to use resin-coated carbon black for the production of a resin black matrix having a high optical density and a high surface resistivity.
Examples of titanium black include the following.
As a method for producing titanium black, a method of heating and reducing a mixture of titanium dioxide and metallic titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium dioxide in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, No. 61-201610), and a method of attaching a vanadium compound to titanium dioxide or titanium hydroxide and reducing it at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610). It is not a thing.

Examples of commercially available titanium black products include Mitsubishi Materials Titanium Black 10S, 12S, 13R, 13M, and 13M-C.
As an example of another black pigment, three color materials of red, green, and blue can be mixed and used as a black pigment.
Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. Is mentioned. The numbers in parentheses above indicate the color index (CI).

  Furthermore, other pigments that can be used in combination are described in C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

The ratio of the coloring material to the total solid content in the colored resin composition is usually 1% by weight or more, preferably 10% by weight or more, and usually 70% by weight or less, preferably 60% by weight or less. When the ratio of the color material is too small, the film thickness with respect to the color density becomes too large, which adversely affects the gap control when the liquid crystal cell is formed. On the other hand, if the proportion of the color material is too large, sufficient image formability may not be obtained.
[1-2] Solvent:
In the colored resin composition of the present invention, the solvent has a function of adjusting the viscosity by dissolving or dispersing the colorant, the dispersant, the binder resin, and other components other than those blended in some cases.

  Examples of the solvent include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2, and apco #. 18 solvent, diisobutylene, amyl acetate, butyl acetate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, soak solvent no. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, (n, sec, t-) butyl acetate, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methyl Ketone, 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, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3-ethoxypropionic acid, 3-ethoxy Methyl propionate, 3-ethoxypropyl Ethyl lopionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, ethylene glycol acetate, ethyl carbitol, butyl carbitol, ethylene glycol monobutyl ether , Propylene glycol-t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate and the like. These solvents may be used alone or in combination of two or more.

The content of the solvent in the entire colored resin composition of the present invention is not particularly limited, but the upper limit is usually 99% by weight or less. When the solvent exceeds 99% by weight, the coloring material, the dispersing agent, etc. are too small to be suitable for forming a coating film. On the other hand, the lower limit of the solvent content is usually 75% by weight or more, preferably 80% by weight or more, and more preferably 82% by weight or more in consideration of viscosity suitable for coating.
[1-3] Dispersant:
It is essential that the colored resin composition of the present invention contains a urethane-based dispersant as a dispersant. In the present invention, by using a combination of this specific dispersant and a specific binder resin described later, high developability of the coating film and the substrate formed from the colored composition while maintaining dispersion stability. It is possible to achieve adhesion, suppression of undissolved residue, and suppression of dry aggregation at the tip of the die lip in die coating.

Urethane dispersants include (1) a polyisocyanate compound, (2) a compound having one or two hydroxyl groups in the same molecule, and (3) a compound having active hydrogen and a tertiary amino group in the same molecule. A dispersion resin obtained by reacting is preferable.
[1-3-1] (1) Polyisocyanate compound,
Examples of the polyisocyanate compound include aromatics such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aliphatic diisocyanates such as diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω'- Alicyclic diisocyanates such as diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α ', α'-tetramethyl Aliphatic diisocyanate having an aromatic ring such as silylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, Examples thereof include triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, trimers thereof, water adducts, and polyol adducts thereof. Preferred as the polyisocyanate is a trimer of an organic diisocyanate, and most preferred is a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate, which may be used alone or in combination.

As a method for producing an isocyanate trimer, the polyisocyanate may be formed by using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.
[1-3-2] (2) Compound having one or two hydroxyl groups in the same molecule As the compound having one or two hydroxyl groups in the same molecule, polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol And those having one terminal hydroxyl group of these compounds alkoxylated with an alkyl group having 1 to 25 carbon atoms, and mixtures of two or more of these.

  Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of polyether diols are those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and the like. The mixture of 2 or more types of these is mentioned. Polyether ester diols include those obtained by reacting mixtures of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diethylene glycol) Propylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1 , 6-hexanediol, 2-methyl-2,4- Nanthanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N -N-alkyl dialkanolamines such as methyldiethanolamine) obtained by polycondensation, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the diols or carbon number 1-25 Polylactone diol or polylactone monool obtained by using polyhydric alcohol as an initiator, for example, polycaprolactone glycol, poly methyl valerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator, and more specifically, a compound obtained by ring-opening addition polymerization of ε-caprolactone to a monool. .

Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate.
Examples of the polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol.
Of the compounds having one or two hydroxyl groups in the same molecule, polyether glycol and polyester glycol are particularly preferable.

The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.
[1-3-3] (3) Compound having active hydrogen and tertiary amino group in the same molecule Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, nitrogen atom or sulfur atom includes a hydroxyl group, The hydrogen atom in functional groups, such as an amino group and a thiol group, is mentioned, Especially, the hydrogen atom of an amino group, especially a primary amino group is preferable.

  The tertiary amino group is, for example, a dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, isopropyl, n-butyl, or the like, and the dialkylamino group is linked to form a heterocyclic structure. Group, more specifically, an imidazole ring or a triazole ring, among which a dimethylamino group and an imidazole ring are preferable because of excellent dispersion stability.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  In addition, the tertiary amino group is a nitrogen-containing heterocycle, such as pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include N-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring, nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring and isoquinoline ring.

  Specific examples of these compounds having an imidazole ring and a primary amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. . Specific examples of the compound having a triazole ring and a primary amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H- 1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino- Examples include 1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole Etc.

  A preferable blending ratio of the dispersion resin raw material is usually 10 to 200 parts by weight, preferably 20 to 190 parts by weight, more preferably 20 to 190 parts by weight of the compound having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. 30 to 180 parts by weight of the compound having an active hydrogen and a tertiary amino group in the same molecule is usually 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight.

  The polystyrene-reduced weight average molecular weight measured by GPC of the urethane-based dispersion resin of the present invention is usually 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. It is a range. When the molecular weight is 1,000 or less, the dispersibility and dispersion stability are poor, and when it is 200,000 or more, the solubility is lowered and the dispersibility is poor, and at the same time, the reaction is difficult to control.

  Manufacture of the urethane type dispersion resin of this invention is performed in accordance with the well-known method of polyurethane resin manufacture. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used.

A normal urethanization reaction catalyst is used as a catalyst for production. Examples include tin series such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stanas octoate, iron series such as iron acetylacetonate and ferric chloride, and tertiary amine series such as triethylamine and triethylenediamine. It is done.
The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g by the amine value of the dispersion resin after the reaction. More preferably, it is the range of 5-80 mgKOH / g, More preferably, it is the range of 10-60 mgKOH / g. When the amine value is less than the above range, the dispersing ability tends to decrease, and when it exceeds the above range, the developability tends to decrease. In addition, when an isocyanate group remains in the dispersion resin by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the dispersion resin has high temporal stability.

As content of the said dispersing agent with respect to the color material component in a coloring composition, it is 10 to 300 weight% normally, Preferably it is 20 to 100 weight%, Especially preferably, it is 30 to 80 weight%. If the amount of the dispersant component is too small, adsorption to the coloring material is insufficient, aggregation cannot be prevented, and viscosity or gelation may occur. After the color filter is formed, cell gap control failure may occur in the liquid crystal cell forming process.
[1-4] Binder Resin The binder resin used in the colored resin composition according to the present invention includes a macromonomer, a monomer having an alcoholic hydroxyl group, a monomer having a carboxyl group, a monomer having an N-substituted maleimide, a monocarboxylic acid mono ( It is essential to include a resin containing a copolymer of at least one of the group consisting of 2- (meth) acryloyloxyethyl) and another copolymerizable monomer. Hereinafter, the monomer and binder resin constituting the binder resin will be described in detail.

The resin does not necessarily have to be produced by actually copolymerizing the monomers, and as a result, the resin may have a structure obtained by copolymerizing the monomers.
[1-4-1] Copolymer of a monomer having a carboxyl group, a macromonomer, a monomer having an alcoholic hydroxyl group and another copolymerizable monomer (hereinafter collectively referred to as “macromonomer-based copolymer”) There is.)
[1-4-1-1] Monomer Having Carboxyl Group Preferred examples of the monomer having a carboxyl group include unsaturated compounds having at least one carboxyl group in the molecule. Specific examples of such monomers include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (Meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl hydrogen phthalate, 2- (meth) acryloyloxypropyl phthalic acid, 2- (meth) acryloyloxypropyl hexahydrophthalic acid, 2 -(Meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropyl hydrogen phthalate, 4- (meth) acryloyloxyethyl trimellitic acid and the like. Of these, methacrylic acid and 2-acryloyloxyethylphthalic acid are preferable.
[1-4-1-2] Macromonomer As the macromonomer, a polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) 1,000 to preferably have one polymerizable carbon-carbon double bond in the molecule. 10,000, especially 2,000 to 8,000 compounds are preferably used. The macromonomer is, for example, at least one monomer homopolymer or copolymer selected from the group consisting of styrene, alkyl (meth) acrylate, acrylonitrile, vinyl acetate, butadiene and isoprene. And those having a (meth) acryloyl group at the molecular ends.

As a specific example of such a macromonomer, a macromonomer having a (meth) acryloyl group at one molecular end of a polystyrene oligomer, polymethyl (meth) acrylate oligomer, or polybutyl (meth) acrylate oligomer is preferable. It is mentioned as a thing. As commercial products, AS-6 (manufactured by Toa Gosei Chemical Co., Ltd., one-end methacryloylated polystyrene oligomer, Mn = 6,000), AA-6 (manufactured by Toa Gosei Chemical Co., Ltd., one-end) Methacryloylated polymethylmethacrylate oligomer, Mn = 6,000) and AB-6 (manufactured by Toa Gosei Chemical Co., Ltd., one-end methacryloylated polybutylacrylate oligomer, Mn = 6,000) Easy to obtain. In addition, as the macromonomer, for example, a polysiloxane oligomer having a (meth) acryloyl group at one molecular end is also preferably used.
[1-4-1-3] Monomer having an alcoholic hydroxyl group having an alcoholic hydroxyl group is preferably an unsaturated compound having at least one alcoholic hydroxyl group in the molecule. It is done. Specific examples of such monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-hydroxymethylacrylamide, 2-hydroxy-3-phenoxypropyl (meth) acrylate. And polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and glycerol (meth) acrylate. Of these, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, and glycerol (meth) acrylate are preferable. In the case of glycerol (meth) acrylate, a compound of the following structural formula (VI) is preferable.

(In the above formula (VI), R ¹ represents a hydrogen atom or a methyl group, preferably a methyl group.)
[1-4-1-4] Other copolymerizable monomer The other copolymerizable monomer is not particularly limited as long as it is a monomer that can be copolymerized with any of the above monomers. Saturated carboxylic acid alkyl ester, unsaturated carboxylic acid aryl alkyl ester, unsaturated carboxylic acid aryl ester, unsaturated carboxylic acid alicyclic hydrocarbon ester, unsaturated carboxylic acid aminoalkyl ester, unsaturated carboxylic acid glycidyl ester, Carboxylic acid vinyl esters, vinyl cyanide and aliphatic conjugated dienes can be mentioned as preferred.

Specific examples of such monomers include the following compounds.
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, indene, o-vinylbenzylmethyl ether Aromatic vinyl compounds such as m-vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether;
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) a Relate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meta ) Acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, etc. Saturated carboxylic acid esters;
2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate Unsaturated carboxylic acid aminoalkyl esters such as 3-dimethylaminopropyl (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, methallyl glycidyl ether;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples thereof include macromonomers having a monoacryloyl group or a monomethacryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.

Among these, (meth) acrylic acid alkyl ester, (meth) acrylic acid aryl alkyl ester, (meth) acrylic acid aryl ester, (meth) acrylic acid alicyclic hydrocarbon ester and carboxylic acid vinyl ester are preferable.
The macromonomer, the monomer having an alcoholic hydroxyl group, the monomer having a carboxyl group, and other copolymerizable monomers may be used alone or in combination of two or more.

  In the macromonomer copolymer, the copolymerization ratio of (macromonomer) / (monomer having an alcoholic hydroxyl group) / (monomer having a carboxyl group) / (other copolymerizable monomer) is 100 parts by weight of the total monomer. The weight ratio is usually (1-50) / (1-30) / (1-30) / (1-80), preferably (5-20) / (5-20) / (5-20). / (10-70). Specific examples of the macromonomer copolymer include polystyrene macromonomer / 2-hydroxypropyl methacrylate / methacrylic acid / benzyl methacrylate copolymer, polymethyl methacrylate macromonomer / 2-hydroxy-3-phenoxypropyl. Acrylate / methacrylic acid / benzyl methacrylate copolymer, polystyrene macromonomer / 2-hydroxyethyl methacrylate / 2-acryloyloxyethylphthalic acid / methyl methacrylate copolymer, polystyrene macromonomer / 2-hydroxyethyl Methacrylate / methacrylic acid / benzyl methacrylate copolymer, polymethyl methacrylate macromonomer / 2-hydroxyethyl methacrylate / methacrylic acid / benzyl methacrylate Rate, polystyrene macromonomer / 2-hydroxyethyl methacrylate / methacrylic acid / dicyclopentenyl methacrylate, and the like.

  Of the copolymers of a monomer having an alcoholic hydroxyl group and another copolymerizable monomer, when the monomer having an alcoholic hydroxyl group is glycerol (meth) acrylate, in particular, glycerol (meth) acrylate and acrylic acid And / or a carboxylic acid-containing unsaturated monomer containing methacrylic acid as an essential component and, optionally, mono (2- (meth) acryloyloxyethyl) succinate, styrene, methyl acrylate, methyl methacrylate, 2- Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate macromonomer Copolymer preferably with at least one member selected from the group consisting of, and specific examples thereof include compounds described in Patent Document 2 (Japanese Patent Laid-Open No. 11-174224).

The macromonomer copolymer used in the present invention has a polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) measured by GPC (carrier: tetrahydrofuran) of 5,000.
It is 00-200,000, Preferably it is 10,000-80,000.
Such a polymer having Mw is usually obtained by radical polymerization of a macromonomer, a monomer having an alcoholic hydroxyl group, a monomer having a carboxyl group, and other copolymerizable monomers in the presence of a solvent, whereby a polymerization conversion rate of 90% by weight is obtained. More preferably, it can be obtained at 95% by weight or more.

At that time, a chain transfer agent may be used to control Mw. As such a chain transfer agent, α-methylstyrene dimer is preferable. The α-methylstyrene dimer is used in an amount of 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total monomer.
In addition, α-methylstyrene dimer has (i) 2,4-diphenyl-4 as an isomer.
-Methyl-1-pentene (b) 2,4-diphenyl-4-methyl-2-pentene (c) 1,1,3-trimethyl-3-phenylindane. A preferable composition as the α-methylstyrene dimer as the chain transfer agent is that when the total amount is 100 parts by weight, the component (a) is 40 parts by weight or more, and the component (b) and / or the component (c) is 60 parts by weight. More preferably, the component (a) is 50 parts by weight or more, and the component (b) and / or the component (c) is 50 parts by weight or less.

The amount of the macromonomer copolymer used in the present invention is 2 to 100 parts by weight, preferably 5 to 60 parts by weight, based on 100 parts by weight of the color material, in terms of solid content. When the amount of the macromonomer copolymer used is too small, the finely divided pigment is re-aggregated after the pigment dispersion treatment, and the contrast of the color filter and the uniformity of the coating film are lowered. On the other hand, when the amount of the macromonomer copolymer used is too large, the viscosity increases during the pigment treatment and handling becomes difficult.
[1-4-2] Copolymer of monomer having N-substituted maleimide and other copolymerizable monomer (hereinafter, sometimes referred to as “N-substituted maleimide copolymer”)
In the N-position substituted maleimide copolymer used in the present invention, examples of the N-position substituent in the N-position substituted maleimide monomer include (cyclo) alkyl group, aryl group, aralkyl group, and substituted derivatives thereof. Among these N-position substituents, an aryl group and a substituted aryl group are particularly preferable. Specific examples of N-substituted maleimide monomers include N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N- In addition to N- (substituted) arylmaleimide such as m-methylphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, N -Cyclohexylmaleimide etc. can be mentioned. These N-substituted maleimide monomers can be used alone or in admixture of two or more. The other copolymerizable monomer is not limited as long as it can be copolymerized with the N-substituted maleimide monomer, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups. (Hereinafter simply referred to as “carboxyl group-containing unsaturated monomer”) and other copolymerizable ethylenically unsaturated monomers (hereinafter simply referred to as “other unsaturated monomers”). Monomer mixtures are preferred. Examples of the carboxyl group-containing unsaturated monomer include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethacrylic acid, cinnamic acid, ω-carboxy-polycaprolactone monoacrylate, and ω-carboxy-poly. Unsaturated monocarboxylic acids such as caprolactone monomethacrylate, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, anhydrous Examples thereof include unsaturated dicarboxylic acids (anhydrides) such as citraconic acid and mesaconic acid; trivalent or higher unsaturated polycarboxylic acids (anhydrides). These carboxyl group-containing unsaturated monomers can be used alone or in admixture of two or more.

Examples of the other unsaturated monomer include the same compounds as the “other copolymerizable monomers” of [1-4-1-4]. These other unsaturated monomers can be used alone or in admixture of two or more.
The N-substituted maleimide copolymer is preferably a copolymer of N-phenylmaleimide, more preferably a copolymer of N-phenylmaleimide, a carboxyl group-containing unsaturated monomer, and another unsaturated monomer. Particularly preferably, N-phenylmaleimide, (meth) acrylic acid, styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, polystyrene It is a copolymer (hereinafter referred to as “alkali-soluble resin (I)”) with at least one selected from the group of macromonomers and polymethylmethacrylate macromonomers.

Specific examples of the alkali-soluble resin (I) include N-phenylmaleimide / methacrylic acid / styrene / benzyl methacrylate copolymer, N-phenylmaleimide / methacrylic acid / styrene / phenyl methacrylate copolymer, N-phenylmaleimide / methacrylic acid. Acid / styrene / benzyl methacrylate / polystyrene macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / phenyl methacrylate / polystyrene Macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / phenylmethacrylate / polymethylmethacrylate macromonomer copolymer, N-Fe Rumaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer N-phenylmaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / phenyl methacrylate / polystyrene macromonomer copolymer, N-phenylmaleimide / methacrylic acid / styrene / 2-hydroxyethyl methacrylate / phenyl methacrylate / polymethyl methacrylate macro A monomer copolymer etc. can be mentioned.

  The copolymerization ratio of the N-substituted maleimide monomer in the N-substituted maleimide copolymer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, if the copolymerization ratio of the N-substituted maleimide monomer is too small, the heat resistance of the resulting pixel tends to decrease, and if it is too large, the alkali solubility of the resulting copolymer decreases, resulting in an unexposed area. There is a risk that residues and soiling may occur on the substrate or the light shielding layer. In addition, when the N-substituted maleimide copolymer is a copolymer of an N-substituted maleimide monomer, a carboxyl group-containing unsaturated monomer, and another unsaturated monomer, the carboxyl group-containing unsaturated monomer The copolymerization ratio is usually 5 to 50% by weight, preferably 10 to 40% by weight, and the copolymerization ratio of other unsaturated monomers is usually 10 to 90% by weight, preferably 20 to 80% by weight. is there. In this case, if the copolymerization ratio of the carboxyl group-containing unsaturated monomer is too small, the solubility of the resulting radiation-sensitive composition in an alkali developer tends to decrease, and if too large, development with an alkali developer is performed. Occasionally, the formed pixel tends to drop off from the substrate and the film surface of the pixel becomes rough. In particular, the N-substituted maleimide copolymer containing a carboxyl group-containing unsaturated monomer at the specific copolymerization ratio has excellent solubility in an alkaline developer, and the copolymer is used as a binder. The radiation-sensitive composition used as is very rarely left undissolved material after development with an alkaline developer, and hardly causes scumming, film residue, etc. in areas other than the part forming pixels on the substrate. Moreover, the pixel obtained from the composition does not excessively dissolve in the alkaline developer, has excellent adhesion to the substrate, and does not have a possibility of falling off the substrate. The N-position substituted maleimide copolymers can be used alone or in admixture of two or more.

  In the present invention, other alkali-soluble resins may be used in combination with the N-substituted maleimide copolymer as the case may be. Examples of such other alkali-soluble resins include resins containing acidic functional groups such as carboxyl groups and phenolic hydroxyl groups. Among the other alkali-soluble resins, the carboxyl group-containing resin is preferably a copolymer of the carboxyl group-containing unsaturated monomer and the other unsaturated monomer, more preferably acrylic acid and Copolymers of methacrylic acid and at least one selected from the group of methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, styrene, polystyrene macromonomer and polymethyl methacrylate macromonomer (Hereinafter referred to as “alkali-soluble resin (II)”). Specific examples of the alkali-soluble resin (II) include acrylic acid / benzyl acrylate copolymer, methacrylic acid / benzyl acrylate copolymer, acrylic acid / benzyl acrylate / styrene copolymer, methacrylic acid / benzyl acrylate / styrene copolymer. Polymer, acrylic acid / methyl acrylate / styrene copolymer, methacrylic acid / methyl acrylate / styrene copolymer, acrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, methacrylic acid / benzyl acrylate / polystyrene macromonomer copolymer, Acrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl acrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / methyl acetate Rate / polystyrene macromonomer copolymer, methacrylic acid / methyl acrylate / polystyrene macromonomer copolymer, acrylic acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / methyl acrylate / polymethyl methacrylate macromonomer copolymer Polymer, acrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate copolymer, acrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, acrylic acid / methyl methacrylate / styrene copolymer Polymer, Methacrylic acid / Methyl methacrylate / Styrene copolymer, Acrylic acid / Benzyl methacrylate / Polystyrene macromonomer copolymer, Methacrylic acid / Benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / methyl methacrylate / polystyrene macromonomer Copolymer, methacrylic acid / methyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / methyl methacrylate / polymethyl methacrylate macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, methacrylic acid / 2- Droxyethyl methacrylate / benzyl methacrylate / polystyrene macromonomer copolymer, acrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate / polymethyl An acrylic acid copolymer of a methacrylate macromonomer copolymer can be exemplified.

  These alkali-soluble resins (II) can be used alone or in admixture of two or more. The amount of the resin used when the other alkali-soluble resin is used is usually 50% by weight or less, preferably 30% by weight or less based on the total amount of the alkali-soluble resin. In this case, when the usage-amount of other alkali-soluble resin exceeds 50 weight%, there exists a tendency for the heat resistance of the pixel obtained to fall.

The polystyrene-reduced weight average molecular weight (hereinafter simply referred to as “weight average molecular weight”) measured by gel permeation chromatography (GPC; elution solvent tetrahydrofuran) of each component constituting the binder resin containing the N-position substituted maleimide copolymer. , Preferably 3,000 to 300,000, particularly preferably 5,000 to 100,000. By using such an alkali-soluble resin having a specific weight average molecular weight, a radiation-sensitive composition excellent in developability can be obtained, thereby forming a pixel having a sharp pattern edge, At the time of development, background stains, film residue, and the like in regions other than the portion where the pixels are formed on the substrate are less likely to occur.
[1-4-3] Copolymer of dicarboxylic acid mono (2- (meth) acryloyloxyethyl) and other copolymerizable monomer Dicarboxylic acid mono (2- (meth) acryloyl) used in the present invention At least one monomer selected from (Roxyethyl) (hereinafter referred to as “monofunctional monomer (a1)”) and another copolymerizable monofunctional monomer. The copolymer (hereinafter referred to as “copolymer (A1)”) will be described.

Examples of the dicarboxylic acid in the monofunctional monomer (a1) include the following compounds.
Aliphatic dicarboxylic acids having 4 to 20 carbon atoms, preferably 4 to 10 carbon atoms, such as oxalic acid, malonic acid, succinic acid, glutaric acid and adipic acid;
Alicyclic dicarboxylic acids having 7 to 24 carbon atoms, preferably 8 to 14 carbon atoms, such as hexahydrophthalic acid, hexahydroisophthalic acid and hexahydroterephthalic acid;
Aromatic dicarboxylic acids having 8 to 24 carbon atoms, preferably 8 to 14 carbon atoms, such as phthalic acid, isophthalic acid and terephthalic acid.

Among these dicarboxylic acids, aliphatic dicarboxylic acids having 4 to 8 carbon atoms are preferable, and succinic acid is particularly preferable. In this invention, a monofunctional monomer (a1) can be used individually or in mixture of 2 or more types.
The other copolymerizable monofunctional monomer means a monomer having one copolymerizable unsaturated bond and can be copolymerized with the monofunctional monomer (a1). And the copolymer (A1) to be obtained is not limited as long as it becomes alkali-soluble. Body (hereinafter referred to as “monofunctional monomer (a2)”) and other copolymerizable monofunctional monomers (hereinafter simply referred to as “other monofunctional monomers”). A monomer mixture consisting of Examples of the monofunctional monomer (a2) include the following compounds.

Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or the like;
Trivalent or higher unsaturated polycarboxylic acids or anhydrides thereof, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, and the like.

These monofunctional monomers (a2) can be used alone or in admixture of two or more.
Moreover, as another monofunctional monomer, the same compound as the “other copolymerizable monomer” in [1-4-1-4] can be exemplified. These other monofunctional monomers can be used alone or in admixture of two or more.

As the copolymer (A1), in particular, a monofunctional monomer (a1) and a monofunctional monomer containing (meth) acrylic acid as essential components and optionally containing ω-carboxypolycaprolactone mono (meth) acrylate. Monomer (a2), styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, N-phenylmaleimide, polystyrene A copolymer (hereinafter referred to as “alkali-soluble resin (III)”) with at least one selected from the group of macromonomers and polymethylmethacrylate macromonomers is preferred.

Specific examples of the alkali-soluble resin (III) include the following compounds.
(Meth) acrylic acid / monofunctional monomer (a1) / styrene copolymer, (meth) acrylic acid / monofunctional monomer (a1) / methyl (meth) acrylate copolymer, (meth) acrylic Acid / monofunctional monomer (a1) / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / benzyl (meth) acrylate copolymer, ( (Meth) acrylic acid / monofunctional monomer (a1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / glycerol mono (meth) acrylate copolymer, (Meth) acrylic acid / monofunctional monomer (a1) / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (a1) / polystyrene macromonomer copolymer, or (meta Acu Le acid / monofunctional monomer (a1) / polymethyl methacrylate consisting macromonomer copolymer terpolymer (hereinafter, referred to as "alkali-soluble resin (IIIa)".);
(Meth) acrylic acid / monofunctional monomer (a1) / styrene / methyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / 2-hydroxyethyl ( (Meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / Styrene / phenyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (A1) / styrene / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / polystyrene macromonomer copolymer, (meth) acrylic Luric acid / monofunctional monomer (a1) / styrene / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / methyl (meth) acrylate / 2-hydroxyethyl (Meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / methyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer Body (a1) / methyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / methyl (meta ) Acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / methyl (meth) acrylate / glycerol mono (meth) a Chryrate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / methyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (a1) / Methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / Monofunctional monomer (a1) / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / 2-hydroxyethyl ( (Meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) a Relate / monofunctional monomer (a1) / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / 2-hydroxyethyl (meth) acrylate / glycerol Mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional Monomer (a1) / 2-hydroxyethyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / 2-hydroxyethyl (meth) acrylate / poly Methyl methacrylate macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / benzyl (meth) acrylate / polymer Enenyl (meth) acrylate copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / benzyl (meth) acrylate copolymer, (meth) acrylic acid / Monofunctional monomer (a1) / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / benzyl (meth) acrylate / N -Phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (a1) / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1 ) / Benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / ω-carboxy Polycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / phenyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / phenyl (meth) acrylate / glycerol Mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / phenyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (A1) / phenyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / phenyl (meth) acrylate / polymethylmethacrylate macromonomer copolymer, (Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (b1) / Lyserol mono (meth) acrylate copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / N-phenylmaleimide copolymer, (meth) acrylic acid / Ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / polystyrene macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional mono Monomer (a1) / polymethylmethacrylate macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / N-phenylmaleimide / glycerol mono (meth) acrylate copolymer, (meth) acrylic Acid / monofunctional monomer (a1) / N-phenylmaleimide / polystyrene macromoly Nomer copolymer or quaternary copolymer consisting of (meth) acrylic acid / monofunctional monomer (a1) / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer (hereinafter referred to as “alkali-soluble resin”). IIIb) ".
);
(Meth) acrylic acid / monofunctional monomer (a1) / styrene / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1 ) / Styrene / methyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / methyl (meth) acrylate / phenyl (meth) acrylate copolymer Copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / styrene / methyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional mono Monomer (a1) / styrene / methyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid Monofunctional monomer (a1) / styrene / methyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / methyl (meth) acrylate / Polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / monofunctional mono Monomer (a1) / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / 2-hydroxyethyl (meth) ) Acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (Meth) acrylate / monofunctional monomer (a1) / styrene / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / 2-hydroxyethyl (Meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide copolymer, (Meth) acrylic acid / monofunctional monomer (a1) / styrene / 2-hydroxyethyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / Styrene / 2-hydroxyethyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic Acid / monofunctional monomer (a1) / styrene / benzyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional mono Monomer (a1) / styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer , (Meth) acrylic acid / monofunctional monomer (a1) / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / Benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / Tylene / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / styrene / phenyl (meth) Acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / phenyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer Body (a1) / styrene / phenyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / phenyl (meth) acrylate / polystyrene macromonomer copolymer Coalescence, (meth) acrylic acid / monofunctional monomer (a1) / styrene / phenyl ( (Meth) acrylate / polymethylmethacrylate macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / styrene / glycerol mono (meth) acrylate copolymer Polymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / styrene / N-phenylmaleimide copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone Mono (meth) acrylate / monofunctional monomer (a1) / styrene / polystyrene macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1 ) / Styrene / Polymethylmethacrylate macromonomer Polymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / N-phenylmaleimide / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) ) / Styrene / N-phenylmaleimide / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / N-phenylmaleimide / polymethylmethacrylate macromonomer copolymer, (meta ) Acrylic acid / monofunctional monomer (a1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (A1) / Methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate Copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer, (Meth) acrylic acid / monofunctional monomer (a1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional mono Monomer (a1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (a1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / Functional monomer (a1) / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / methyl (Meth) acrylate / benzyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / methyl (meta ) Acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / methyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (Meth) acrylic acid / monofunctional monomer (a1) / methyl (meth) acrylate Benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (a1) / methyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (Meth) acrylic acid / monofunctional monomer (a1) / methyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meta) ) Acrylate / monofunctional monomer (a1) / methyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / methyl (meth) acrylate / Phenyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (Meth) acrylic acid / monofunctional monomer (a1) / methyl (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (a1 ) / Methyl (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / methyl (meth) acrylate / phenyl (meth) acrylate / poly Methyl methacrylate macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / methyl (meth) acrylate / glycerol mono (meth) acrylate copolymer , (Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylic Rate / monofunctional monomer (a1) / methyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer ( a1) / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / methyl (meth) acrylate / poly Methyl methacrylate macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / methyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / Monofunctional monomer (a1) / Methyl (meth) acrylate / N-phenylmale Mido / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / methyl (meth) acrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / Monofunctional monomer (a1) / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) Acrylate / monofunctional monomer (a1) / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / 2-hydroxyethyl (Meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate Rate copolymer, (meth) acrylic acid / monofunctional monomer (a1) / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / Monofunctional monomer (a1) / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / 2- Hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / 2 -Hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer, ) Acrylic acid / monofunctional monomer (a1) / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer Body (a1) / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (a1) / 2-hydroxyethyl (meta ) Acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polymethyl methacrylate Macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprola Kuton mono (meth) acrylate / monofunctional monomer (a1) / 2-hydroxyethyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid ω-carboxypolycaprolactone mono (meth) acrylate / Monofunctionality





Monomer (a1) / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / 2-hydroxyethyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / 2-hydroxyethyl (meta ) Acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / 2-hydroxyethyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer Coalescence, (meth) acrylic acid / monofunctional monomer (a1) / 2- Droxyethyl (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide / polymethyl Methacrylate macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / benzyl (meth) acrylate / phenyl (meth) acrylate copolymer, ( (Meth) acrylic acid / monofunctional monomer (a1) / benzyl (meth) acrylate / phenyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional monomer ( a1) / benzyl (meth) acrylate / phenyl (meth) a Relate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (a1) / benzyl (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / Monofunctional monomer (a1) / benzyl (meth) acrylate / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / mono Functional monomer (a1) / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1 ) / Benzyl (meth) acrylate / N-phenylmaleimide Polymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / ω -Carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / Benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (a1) / benzyl (meth) acrylate / N-phenylmaleimide / polystyrene Macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (A1) / benzyl (meth) acrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / Phenyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / phenyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / phenyl (meth) acrylate / polystyrene macromonomer copolymer, (meta Acrylic acid / ω-carboxypolycaprola Ton mono (meth) acrylate / monofunctional monomer (a1) / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / phenyl (meta ) Acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (a1) / phenyl (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer Copolymer, (meth) acrylic acid / monofunctional monomer (a1) / phenyl (meth) acrylate / N-phenylmaleimide / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (Meth) acrylate / monofunctional monomer (a1) / glycero Mono (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / N-phenylmaleimide / polystyrene macromonomer Polymer or five-component copolymer consisting of (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / monofunctional monomer (a1) / N-phenylmaleimide / polymethylmethacrylate macromonomer copolymer (Hereinafter referred to as “alkali-soluble resin (IIIc)”.
);
(Meth) acrylic acid / monofunctional monomer (a1) / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / mono Functional monomer (a1) / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (a1) / Styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / 2-hydroxyethyl (meth) acrylate / Benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (Meth) acrylic acid / monofunctional monomer (a1) / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / monofunctional Monomer (a1) / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / 2-hydroxyethyl (meth) acrylate / Phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (Meth) acrylic acid / monofunctional monomer (a1) / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / monofunctional monomer (A1) / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / benzyl (meth) acrylate / Glycerol mono (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / monofunctional monomer (a1) / styrene / phenyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenyl Maleimide copolymer, (meth) acrylic acid / monofunctional monomer Body (a1) / styrene / phenyl (meth) acrylate / glycerol mono (meth) acrylate / polystyrene macromonomer copolymer or (meth) acrylic acid / monofunctional monomer (a1) / styrene / phenyl (meth) acrylate / Hexane copolymer consisting of glycerol mono (meth) acrylate / polymethyl methacrylate macromonomer copolymer (hereinafter referred to as “alkali-soluble resin (IIId)”). )etc.

  In the present invention, among the alkali-soluble resin (IIIa), alkali-soluble resin (IIIb), alkali-soluble resin (IIIc) and alkali-soluble resin (IIId), those monofunctional monomers (a1) are succinic acid. A resin that is mono (2- (meth) acryloyloxyethyl) is particularly preferred. The copolymerization ratio of the monofunctional monomer (a1) in the copolymer (A1) is usually 5 to 35% by weight, preferably 10 to 25% by weight. In this case, if the copolymerization ratio of the monofunctional monomer (a1) is too small, there is a possibility that a residue, a ground stain or the like may be generated on the unexposed substrate or the light shielding layer. At the time of development by, the formed pixels tend to drop off from the substrate. When the copolymer (A1) is a copolymer of a monofunctional monomer (a1), a monofunctional monomer (a2), and another unsaturated monomer, a monofunctional monomer The copolymerization ratio of the body (a2) is usually 5 to 50% by weight, preferably 10 to 40% by weight, and the copolymerization ratio of other unsaturated monomers is usually 15 to 90% by weight, preferably 35 ~ 80% by weight. In this case, if the copolymerization ratio of the monofunctional monomer (a2) is too small, the solubility of the resulting radiation-sensitive composition in an alkali developer tends to decrease, and if it is too large, it depends on the alkali developer. At the time of development, the formed pixel tends to drop off from the substrate and the film surface of the pixel is likely to be rough. The copolymer (A1) containing the monofunctional monomer (a2) at the specific copolymerization ratio together with the monofunctional monomer (a1) has excellent solubility in an alkali developer. The radiation-sensitive composition using the copolymer as a binder has very little undissolved material remaining after development with an alkaline developer, and the residue on the unexposed portion of the substrate or the light shielding layer, Background stains and the like hardly occur, and the pixel obtained from the composition does not excessively dissolve in an alkaline developer, has excellent adhesion to the substrate, and does not fall off the substrate. It will be a thing. The said copolymer (A1) can be used individually or in mixture of 2 or more types.

  In the present invention, in some cases, other alkali-soluble resins can be used in combination with the copolymer (A1). As said other alkali-soluble resin, resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group, can be mentioned, for example. As such another alkali-soluble resin, a resin having a carboxyl group is preferable, more preferably the monofunctional monomer (a2) exemplified for the copolymer (A1) and the other monofunctional monomer. In particular, a monofunctional monomer (a2) containing (meth) acrylic acid as an essential component and optionally containing ω-carboxypolycaprolactone mono (meth) acrylate, styrene, methyl ( Selected from the group of (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate macromonomer At least one copolymer (hereinafter referred to as "alkali Soluble resin (IV) "hereinafter.) Are preferred.

  Specific examples of the alkali-soluble resin (IV) include (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl ( (Meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer , (Meth) acrylic acid / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic Acid / 2-hydroxyethyl (meta Acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, methacrylic acid / styrene / Benzyl methacrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / styrene / benzyl methacrylate / glycerol ( It can be mentioned data) acrylate / N- phenylmaleimide copolymer. These alkali-soluble resins (IV) can be used alone or in admixture of two or more. The amount of the resin used when the other alkali-soluble resin is used is usually 50% by weight or less, preferably 30% by weight or less based on the total amount of the alkali-soluble resin. In this case, if the amount of other alkali-soluble resin used is too large, there is a tendency that residues, background stains, and the like are likely to occur on the unexposed portion of the substrate or the light shielding layer.

  The copolymer of the dicarboxylic acid mono (2- (meth) acryloyloxyethyl) used in the present invention and other copolymerizable monomers contains the copolymer (A1) as an essential component, and the alkali-soluble resin. The weight average molecular weight in terms of polystyrene (hereinafter simply referred to as “weight average molecular weight”) measured by gel permeation chromatography (GPC; elution solvent tetrahydrofuran) of each of the components is preferably 3,000 to 300,000, particularly Preferably it is 5,000-100,000. By using such an alkali-soluble resin having a specific weight average molecular weight, a radiation-sensitive composition excellent in developability can be obtained, thereby forming a pixel having a sharp pattern edge, Residues, background stains, film residues, and the like are less likely to occur on the unexposed substrate or the light shielding layer during development.

The binder resin described above is a compound known per se, and is the same as those described in Patent Documents 1 to 3 and JP-A-8-259876.
[1-4-4] A structure obtained by adding an epoxy moiety of a compound having an ethylenically unsaturated group and an epoxy group to the carboxyl group of the binder resin, and having the ethylenically unsaturated group and the epoxy group Resin having a specific structure of the compound When the binder resin used in the present invention has a carboxyl group, the epoxy moiety of the compound having an ethylenically unsaturated group and an epoxy group in the carboxyl group is further added. You may have the structure added.

The above resin does not necessarily have to be produced by actually reacting a resin having a carboxylic acid with a compound having an ethylenically unsaturated group and an epoxy group. As a result, the resin having a carboxylic acid has a carboxylic acid moiety. And a structure obtained by adding an epoxy portion of a compound having an ethylenically unsaturated group and an epoxy group.
Specifically, the compound having an ethylenically unsaturated group and an epoxy group can be represented by the following structural formula (1).

Here, in the structural formula (1), R ₁ represents a divalent linking group, and R ₂ represents hydrogen or a methyl group.
In the structural formula (1), R ₁ is not particularly limited as long as it is a divalent linking group, and various organic groups having about 1 to 30 carbon atoms can be used. It is an alkyl group containing 3 or more linear structures, branched structures or cyclic structures, and is preferably an alkyl group containing a linear structure, branched structure or cyclic structure having 20 or less carbon atoms, particularly 10 or less. If the number of carbon atoms is too small, in other words, if the distance between the epoxy group and the ethylenically unsaturated group is too short, the developability and solubility may be insufficient. However, when there are too many carbon atoms, the amount of ethylenically unsaturated double bonds in the binder resin tends to decrease, and it is difficult to obtain in practice. In a preferred embodiment, in the above structural formula I, R ₁ is an alkyl chain having a straight chain structure, a branched structure or a cyclic structure having 1 to 20 carbon atoms, particularly an alkyl group having 3 to 10 carbon atoms, Represents a linear alkyl group having 3 to 10 carbon atoms.

Specific examples of the compound represented by the structural formula (1) include various 4-hydroxyalkyl acrylate glycidyl ethers and 4-hydroxyalkyl methacrylate glycidyl ethers, and more specifically, 4-hydroxybutyl. Mention may be made of acrylate glycidyl ether.
The compound having an ethylenically unsaturated group and an epoxy group represented by the structural formula (1) may be used alone or in combination of two or more, or a compound having an ethylenically unsaturated group and an epoxy group other than the above (1). Can be used.

  By using the above compound, a photosensitive composition excellent in developability and solubility can be obtained. The reason for this is not clear, but in the above compound having a linear structure, the number of atoms from the ethylenically unsaturated group to the epoxy group (the atoms adjacent to the ethylenically unsaturated group and the carbon atoms constituting the epoxy group) This is presumed to be because the number of atoms in one continuous atomic sequence connecting the two is relatively long (for example, 8 or more).

  For example, 4-hydroxybutyl acrylate glycidyl ether is used as a compound having an ethylenically unsaturated group and an epoxy group as a structure obtained by adding a “compound having an ethylenically unsaturated group and an epoxy group” to a resin having a carboxylic acid. In the case of the resin, a resin having either or both of the following structures in the molecule can be mentioned.

The acid value of the binder resin in the present invention is usually 10 to 200 KOHmg / g, preferably 20 to 150 KOHmg / g.
The acid value of the “resin having a carboxylic acid” in the present invention is usually 80 to 500 KOH mg / g, preferably 100 to 350 KOH mg / g, and more preferably 150 to 300 KOH mg / g. In addition, when the compound having an ethylenically unsaturated group and an epoxy group is added, the introduction rate of the “resin having a carboxylic acid” into the carboxylic acid is usually 10 to 90 mol%, preferably 30 to 80 mol%. . If the introduction rate is too small, the side chain having an ethylenically unsaturated double bond cannot be sufficiently introduced, so the sensitivity tends to decrease. On the other hand, if the introduction rate is too large, the developability of the photosensitive composition is low. There is a tendency to get worse.

For the synthesis of the binder resin in the present invention, a method of reacting a carboxylic acid of a resin having a carboxylic acid with a compound having an ethylenically unsaturated group and an epoxy group is preferably used. As a method of reacting a compound having an ethylenically unsaturated group and an epoxy group with a carboxyl group of a resin having a carboxylic acid, a known method can be used.
For example, a resin body having the above carboxylic acid and a compound having an unsaturated group and an epoxy group are converted into tertiary amines such as triethylamine and benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, benzyltriethylammonium. An epoxy compound can be introduced into the carboxyl group of the polymer by reacting in a quaternary ammonium salt such as chloride, pyridine, triphenylphosphine and the like at a reaction temperature of 50 to 150 ° C. for several to several tens of hours in an organic solvent. .

The usage-amount of the binder resin in this invention is 10-1000 weight part normally with respect to 100 weight part of coloring materials, Preferably it is 20-500 weight part. In this case, if the amount of the binder resin resin used is too small, for example, the alkali developability may be reduced, or a residue, background stains, etc. may be generated on the unexposed substrate or the light shielding layer. However, since the colorant concentration is relatively lowered, it may be difficult to achieve the target color density as a thin film.
[1-5] Other solid content The colored composition for a color filter of the present invention may further contain a solid content other than the above components as necessary. Examples of such components include photopolymerizable monomers, photopolymerization initiation systems, organic carboxylic acids, organic carboxylic anhydrides, dispersion aids, surfactants, thermal polymerization inhibitors, plasticizers, storage stabilizers, and surface protection agents. , Adhesion improvers, development improvers and the like.
[1-5-1] Photopolymerizable monomer The photopolymerizable monomer is not particularly limited as long as it is a low molecular weight compound that can be polymerized. However, an addition polymerizable compound having at least one ethylenic double bond (hereinafter, referred to as “polymerizable monomer”). (Referred to as “ethylenic compound”). The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiation system described later when the colored resin composition of the present invention is irradiated with actinic rays. . In addition, the monomer in this invention means the concept which opposes what is called a polymeric substance, and means the concept also containing a dimer, a trimer, and an oligomer other than the monomer of a narrow sense.

  Examples of the ethylenic compound include an unsaturated carboxylic acid, an ester thereof with a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, An ester, a polyisocyanate compound and a (meth) acryloyl-containing hydroxy compound obtained by an esterification reaction with a saturated carboxylic acid and a polyvalent carboxylic acid and the polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound or aromatic polyhydroxy compound; And an ethylenic compound having a urethane skeleton obtained by reacting.

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, penta Acrylic esters such as erythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate and the like can be mentioned. In addition, the acrylic acid part of these acrylates is a methacrylic acid ester replaced with a methacrylic acid part, an itaconic acid ester replaced with an itaconic acid part, a crotonic acid ester replaced with a crotonic acid part, or a maleic acid replaced with a maleic acid part Examples include esters.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate, and the like.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Representative examples include 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. And the like.

  Examples of ethylenic compounds 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; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanate; aromatic diisocyanate such as tolylene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3-hydroxy ( Reaction products with (meth) acryloyl group-containing hydroxy compounds such as 1,1,1-trimethacryloyloxymethyl) propane And the like.

  Other examples of the ethylenic compound used in the present invention include acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate; Polyacrylates or polymethacrylates of trihydric or higher polyhydric alcohols described in Patent Documents 1 to 3 described above and dicarboxylic acid-modified products thereof are also known compounds.

  The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. The polyfunctional monomer provided is preferred, and particularly preferably in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mg-KOH / g, and particularly preferably 5 to 30 mg-KOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution characteristics are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel is deteriorated. Therefore, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted to fall within the above range. Is essential.

  In the present invention, more preferred polyfunctional monomers having acid groups are dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and succinic acid ester of dipentaerythritol pentaacrylate, which are commercially available as TO1382 manufactured by Toagosei Co., Ltd. It is a mixture as a component. Other polyfunctional monomers can be used in combination with this polyfunctional monomer.

The blending ratio of these ethylenic compounds is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and usually 80% by weight, based on the total solid content of the colored resin composition of the present invention. Hereinafter, it is preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less. The ratio to the colorant is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, particularly preferably 20% by weight or more, and usually 200% by weight or less, preferably 100% by weight. Hereinafter, it is more preferably 80% by weight or less.
[1-5-2] Photopolymerization initiator system The photopolymerization initiator is usually used as a mixture (photopolymerization initiator system) with an accelerator and an additive such as a sensitizing dye added as necessary. . The photopolymerization initiator system is a component having a function of generating a polymerization active radical by directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of the photopolymerization initiator constituting the photopolymerization initiator system component include metallocene compounds including titanocene compounds described in JP-A Nos. 59-152396 and 61-151197, and the above-mentioned patent documents. 1-3, N-aryl-α-amino acids such as hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives and N-phenylglycine described in JP-A-10-39503, N Radical activators such as -aryl-α-amino acid salts and N-aryl-α-amino acid esters, α-aminoalkylphenone compounds, and oxime ester initiators described in JP-A-2000-80068. Can be mentioned.

Specific examples of the polymerization initiator that can be used in the present invention are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-
(4-Methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4
Halomethylated triazine derivatives such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine;
2-trichloromethyl-5- (2'-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2'-benzofuryl) vinyl] -1,3,4-oxa Diazole, 2-trichloromethyl-5- [β- (2 '-(6 "-benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5 monofuryl-1,3, Halomethylated oxadiazole derivatives such as 4-oxadiazole;
2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2- ( 2'-Fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl)
Imidazole derivatives such as -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5-diphenylimidazole dimer;
Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1
-Anthraquinone derivatives such as chloroanthraquinone;
Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 '-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl -Acetophenone derivatives such as (p-butylphenyl) ketone;
Thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2
Thioxanthone derivatives such as 1,4-diisopropylthioxanthone;
Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl P-diethylaminobenzoate; Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine; Phenazines such as 9,10-dimethylbenzphenazine Derivatives;
Anthrone derivatives such as benzanthrone;
Di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentagenyl-Ti-bis-2,3,4,5,6-pentafluorophenyl -1 monoyl, di-cyclopentagenyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentagenyl-Ti-bis-2,4,6-tri Fluorophen-1-yl, di-cyclopentagenyl-Ti-2,6-dipuruolophen-1-yl, di-cyclopentagenyl-Ti-2,4-difluorophenyl-1-yl, Di-methylcyclopentaenyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentagenyl-Ti-bis-2,6-di-fluoropheny -1-yl, di-cyclopentagenyl-Ti-2,6-di-fluoro-3- (pi 1-yl) - titanocene derivatives such as 1-yl;
2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-
Dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, Α-aminoalkylphenone compounds such as 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone;
1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- Oxime ester compounds such as 3-yl]-, 1- (O-acetyloxime).

  Examples of the accelerator constituting the photopolymerization initiator system component include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, and 2-mercaptobenzoxazole. A mercapto compound having a heterocyclic ring such as 2-mercaptobenzimidazole or an aliphatic polyfunctional mercapto compound is used.

These photopolymerization initiators and accelerators may be used alone or in combination of two or more.
As a specific photopolymerization initiator system component, for example, dialkyl acetophenone system described in pages 16 to 26 of “Fine Chemical” (March 1, 1991, vol. 20, No. 4). Benzoin, thioxanthone derivatives, and the like, as well as hexaarylbiimidazole series, S-trihalomethyltriazine series, and JP-A-4-221958 described in JP-A-58-403023 and JP-B-45-37377. Japanese Patent Publication No. JP-A-4-219756, etc., a combination of a titanocene and a xanthene dye, an addition-polymerizable ethylenic saturated double bond-containing compound having an amino group or a urethane group, the aforementioned patent document 1 to 3 are combined with a biimidazole compound and an acetophenone compound and / or a benzophenone compound. The combined system etc. are mentioned.

The blending ratio of the photopolymerization initiator component is generally 0.1 to 40% by weight, preferably 0.5 to 30% by weight, based on the total solid content of the color filter coloring composition of the present invention. If the blending ratio is extremely low, the sensitivity to exposure light may be reduced. On the other hand, if the blending ratio is extremely high, the solubility of the unexposed part in the developer may be reduced, leading to poor development.
If necessary, a sensitizing dye corresponding to the wavelength of the image exposure light source can be added to the photopolymerization initiator system component for the purpose of increasing the sensitivity. These sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, and 3-ketocoumarin compounds described in Kaihei 3-239703 and 5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP 47-2528, JP 54-155292, JP 45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-6988, JP-A-57-168088. No. 5, JP-A-5-107761, JP-A-5-210240, and JP-A-4-288818. Mention may be made of a dye or the like having a skeleton.

  Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Benzothiazole, 2- (p-diethyl Aminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, (p -Dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. and p-dialkylaminophenyl group-containing compounds. Of these, 4,4'-dialkylaminobenzophenone is most preferred. A sensitizing dye may also be used individually by 1 type, and 2 or more types may be mixed and used for it.

The blending ratio of the sensitizing dye in the colored resin composition according to the present invention is usually 0% by weight or more, preferably 0.2% by weight or more, more preferably 0.5% in the total solid content of the colored resin composition. It is in the range of not less than wt%, usually not more than 20 wt%, preferably not more than 15 wt%, more preferably not more than 10 wt%.
[1-5-3] Organic carboxylic acid, organic carboxylic acid anhydride The colored composition of the present invention may contain an organic carboxylic acid having a molecular weight of 1000 or less and / or an organic carboxylic acid anhydride. These are preferably contained when the dispersant is a urethane-based dispersant.

  Specific examples of the organic carboxylic acid compound include aliphatic carboxylic acids and aromatic carboxylic acids. Aliphatic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid, methacrylic acid and other monocarboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid And dicarboxylic acids such as adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid and fumaric acid, and tricarboxylic acids such as tricarbaric acid and aconitic acid. Examples of the aromatic carboxylic acid include carboxylic acids in which a carboxyl group is directly bonded to a phenyl group such as benzoic acid and phthalic acid, and carboxylic acids in which the carboxyl group is bonded to the phenyl group through a carbon bond. Among these, those having a molecular weight of 600 or less, particularly those having a molecular weight of 50 to 500, specifically maleic acid, malonic acid, succinic acid, and itaconic acid are preferred.

Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specifically, acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, Aliphatic carboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, n-octadecyl succinic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride Things. Examples of the aromatic carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among these, those having a molecular weight of 600 or less, particularly those having a molecular weight of 50 to 500, specifically maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferred.

The addition amount of these organic carboxylic acids and / or organic carboxylic anhydrides is usually 0.01 to 10% by weight, preferably 0.03 to 5% by weight, more preferably 0.05 to 3% in the total solid content. It is in the range of wt%.
By adding these organic carboxylic acids and / or organic carboxylic anhydrides having a molecular weight of 1000 or less, it is possible to further reduce the remaining undissolved coloring composition while maintaining high pattern adhesion. Japanese Patent No. 3293171 proposes a method of adding an organic carboxylic acid compound having a molecular weight of 1000 or less to a colored composition. As described above, this method decreases the adhesion of the image area, and as a result, development is performed. The margin is narrowed, and pixel peeling and white defect are likely to occur.
[1-5-4] Dispersion aid Examples of the dispersion aid include pigment derivatives.

  As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine And derivatives such as pigments. Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, preferably a sulfonamide group and a quaternary salt thereof, and a sulfonic acid group, and more preferably a sulfonic acid group. In addition, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions. Specific examples of pigment derivatives include azo pigment sulfonic acid derivatives, phthalocyanine pigment sulfonic acid derivatives, quinophthalone pigment sulfonic acid derivatives, anthraquinone pigment sulfonic acid derivatives, quinacridone pigment sulfonic acid derivatives, and diketopyrrolopyrrole pigment sulfonic acid. And sulfonic acid derivatives of dioxazine pigments.

A pigment derivative or the like may be added as a dispersion aid in order to improve the dispersibility of the pigment and the dispersion stability. Pigment derivatives include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, isoindoline, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolo Derivatives such as pyrrole and dioxazine pigments may be mentioned. As substituents of pigment derivatives, sulfonic acid groups, sulfonamide groups and their quaternary salts, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. can be directly in the pigment skeleton or alkyl groups, aryl groups, complex groups. Examples thereof include those bonded via a ring group and the like, preferably a sulfonamide group and a quaternary salt thereof, and a sulfonic acid group, and more preferably a sulfonic acid group. In addition, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different numbers of substitutions. Specific examples of pigment derivatives include azo pigment sulfonic acid derivatives, phthalocyanine pigment sulfonic acid derivatives, quinophthalone pigment sulfonic acid derivatives, isoindoline pigment sulfonic acid derivatives, anthraquinone pigment sulfonic acid derivatives, quinacridone pigment sulfonic acid derivatives, Examples thereof include sulfonic acid derivatives of diketopyrrolopyrrole pigments and sulfonic acid derivatives of dioxazine pigments. Among them, sulfonic acid derivatives of Pigment Yellow 138, sulfonic acid derivatives of Pigment Yellow 139, sulfonic acid derivatives of Pigment Red 254, sulfonic acid derivatives of Pigment Red 255, sulfonic acid derivatives of Pigment Red 264, and sulfonic acid derivatives of Pigment Red 272 are preferable. Pigment Red 209, Pigment Orange 71 sulfonic acid derivative, Pigment Violet 23 sulfonic acid derivative, more preferably Pigment Yellow 138 sulfonic acid derivative, and Pigment Red 254 sulfonic acid derivative. The addition amount of the pigment derivative is usually 0.1% by weight or more, usually 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, and further preferably 5% by weight or less based on the pigment. is there. This is because if the addition amount is small, the effect is not exhibited, and conversely if the addition amount is too large, dispersibility and dispersion stability are deteriorated.
[1-5-5] Surfactant A variety of surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used as surfactants, which may adversely affect various properties. It is preferable to use a nonionic surfactant from the viewpoint of low. The concentration range of the surfactant is usually 0.001% by weight or more, preferably 0.005% by weight or more, more preferably 0.01% by weight or more, and most preferably 0.03% by weight based on the total amount of the composition. In addition, the range of usually 10% by weight or less, preferably 1% by weight or less, more preferably 0.5% by weight or less, and most preferably 0.3% by weight or less is used.
[1-5-6] Thermal polymerization inhibitor Examples of the thermal polymerization inhibitor include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol, and the like. . The blending amount of the thermal polymerization inhibitor is preferably in the range of 0% by weight to 3% by weight with respect to the total solid content of the composition.
[1-5-7] Plasticizer Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetyl glycerin and the like. Is used. The blending amount of these plasticizers is preferably in the range of usually 10% by weight or less with respect to the total solid content of the composition.
[2] Preparation of colored resin composition (coating solution for color filter) Next, a method for preparing the colored resin composition according to the present invention will be described.

  First, a predetermined amount of each of the coloring material, the solvent, and the dispersing agent is weighed, and in the dispersion treatment step, the coloring material is dispersed to obtain a liquid colored resin composition (ink-like liquid). 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, or the like can be used. By performing this dispersion treatment, the color material is made into fine particles, so that the coating characteristics of the colored resin composition are improved and the transmittance of the product color filter substrate is improved.

  When dispersing the color material, it is preferable to use a binder resin or a dispersion aid as appropriate. As the binder resin used for dispersing the colorant, it is particularly preferable to use a resin having a structure in which an epoxy part of an epoxy group-containing unsaturated compound is added to a carboxyl group part of a resin having a carboxyl group. Moreover, when performing a dispersion process using a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set to 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time varies depending on the composition of the ink-like liquid {coloring material, solvent, dispersant having a nitrogen-containing functional group}, the size of the sand grinder apparatus, and the like, and therefore needs to be adjusted as appropriate.

The ink-like liquid obtained by the dispersion treatment is mixed with a solvent, a binder resin, and in some cases, a predetermined amount of a photopolymerizable monomer, a photopolymerization initiator system component, and other components than the above, to obtain a uniform dispersion solution And In addition, in each process of a dispersion | distribution process and mixing, since fine refuse may mix, it is preferable to filter the obtained ink-like liquid with a filter etc.
[3] Production of Color Filter Substrate Next, the color filter according to the present invention will be described. The color filter according to the present invention is characterized in that pixels are formed on a substrate using the above-described colored resin composition.
[3-1] Transparent substrate (support)
The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Materials include, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, polycarbonate, polymethyl methacrylate, polysulfone thermoplastic resin sheets, epoxy resins, unsaturated polyester resins, and poly (meth) acrylic. Examples thereof include thermosetting resin sheets such as a resin, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.

For transparent substrates and black matrix forming substrates, to improve surface properties such as adhesion, corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agents and urethane resins, as necessary May be performed. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01 micrometer or more normally, Preferably it is 0.05 micrometer or more, and is 10 micrometers or less normally, Preferably it is the range of 5 micrometers or less.
[3-2] Black Matrix A color filter according to the present invention can be manufactured by providing a black matrix on the above-described transparent substrate and further forming pixel images of red, green, and blue normally. The colored resin composition is used as a coating solution for forming at least one of these black, red, green, and blue colors. For black resist, metal formed on the transparent glass on the transparent substrate, on the resin black matrix forming surface formed on the transparent substrate for red, green, and blue, or using a chromium compound or other light shielding metal material On the black matrix forming surface, each process of coating, heat drying, image exposure, development and thermosetting is performed to form a pixel image of each color.

The black matrix is formed on a transparent substrate using a light-shielding metal thin film or a photosensitive colored resin composition for black matrix. As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide, and chromium nitride, nickel and tungsten alloys, and the like may be used, and these may be laminated in a plurality of layers.
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, ceric ammonium nitrate, perchloric acid and / or nitric acid are added to chromium. Other materials are etched using an etchant according to the material, and finally the positive photoresist is stripped with a special stripper to form a black matrix. be able to.

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

When using the black resin coloring resin composition, a black matrix is formed using a colored resin composition containing a black color material. For example, black color material such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black, or a plurality of black color materials, or red, green, blue and the like appropriately selected from inorganic or organic pigments and dyes A black matrix can be formed in the same manner as described below for forming a red, green, and blue pixel image using a colored resin composition containing a black color material by mixing.
[3-3] Formation of Pixels On a transparent substrate provided with a black matrix, a colored resin composition containing a coloring material of one color of red, green, and blue is applied, dried, and then photo-coated on the coating film. Overlaid with masks, a pixel image is formed through this photomask by image exposure, development, and if necessary, thermal curing or photocuring to form a colored layer. A color filter image can be formed by performing this operation for each of the three colored resin compositions of red, green, and blue.

  The color resin composition for color filters 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 solution used is greatly reduced, there is no influence of mist adhering when using the spin coating method, and the generation of foreign matter is further suppressed. It is preferable from a viewpoint.

If the thickness of the coating film is too large, pattern development becomes difficult and gap adjustment in the liquid crystal cell forming process may be difficult. On the other hand, if it is too small, it is difficult to increase the pigment concentration. Color expression may be impossible. The thickness of the coating film is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm as the film thickness after drying. The range is as follows.
[3-4] Drying of coating film The coating film after the colored resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after preliminary drying, it is heated again and dried. The conditions for the preliminary drying can be appropriately selected according to the type of the solvent component, the performance of the dryer to be used, and the like. The drying temperature and drying time are selected according to the type of the solvent component, the performance of the dryer used, and the like. Specifically, the drying temperature is usually 40 ° C. or higher, preferably 50 ° C. or higher, and usually 80 The drying time is usually 15 seconds or longer, preferably 30 seconds or longer, and usually 5 minutes or shorter, preferably 3 minutes or shorter.

The temperature condition for reheat drying is preferably higher than the pre-drying temperature. Specifically, it is usually 50 ° C. or higher, preferably 70 ° C. or higher, and usually 200 ° C. or lower, preferably 160 ° C. or lower, particularly preferably 130 ° C. It is the range below ℃. Moreover, although it depends on the heating temperature, the drying time is usually 10 seconds or more, preferably 15 seconds or more, and usually 10 minutes or less, preferably 5 minutes. The higher the drying temperature is, the better the adhesion to the transparent substrate is. However, when the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. In addition, as a drying process of this coating film, you may use the reduced pressure drying method which dries in a reduced pressure chamber, without raising temperature.
[3-5] Exposure Step Image exposure is performed by superimposing a negative matrix pattern on the coating film of the colored resin composition and irradiating an ultraviolet light source or a visible light source through this mask pattern. At this time, if necessary, exposure may be performed after an oxygen blocking layer such as a polyvinyl alcohol layer is formed on the photopolymerizable layer in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. As the light source, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a fluorescent lamp, a lamp light source, an argon ion laser, a YAG laser, Examples include an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.
[3-6] Development Step The color filter according to the present invention is an organic solvent or surfactant after image exposure with the above-mentioned light source to the coating film using the colored resin composition according to the present invention. By carrying out development using an aqueous solution containing an alkaline compound and an alkaline compound, an image can be formed on a substrate for production. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, 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 trimethylamine Mono-di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Machine alkaline compounds. These alkaline compounds may be a mixture of two or more.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkylbenzene sulfonic acids. Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinate esters, and amphoteric surfactants such as alkylbetaines and amino acids.

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 in combination with an aqueous solution.
There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, more preferably 40 ° C. or lower. Is preferred. The development method can be any method such as immersion development, spray development, brush development, and ultrasonic development.

In addition to the manufacturing method described above, the color filter according to the present invention includes (1) a curable coloring resin composition containing a solvent, a phthalocyanine pigment as a color material, and a polyimide resin as a binder resin. It can also be manufactured by a method of applying and forming a pixel image by an etching method. In addition, (2) a method of forming a pixel image directly on a transparent substrate using a colored resin composition containing a phthalocyanine pigment as a color ink, and (3) a colored resin composition containing a phthalocyanine pigment. Examples thereof include a method in which a colored film is deposited on an ITO electrode that is used as an electrodeposition solution and is immersed in the electrodeposition solution to form a predetermined pattern. Further, (4) a method in which a film coated with a colored resin composition containing a phthalocyanine pigment is attached to a transparent substrate and peeled off, image exposure and development to form a pixel image, and (5) a phthalocyanine pigment is contained. Examples thereof include a method of forming a pixel image with an ink jet printer using a colored resin composition as a colored ink. The manufacturing method of a color filter employ | adopts the method suitable for this according to the composition of the colored resin composition for color filters.
[3-7] Thermosetting treatment The color filter after development is subjected to thermosetting treatment. In this case, the temperature is usually 100 ° C. or higher, preferably 150 ° C. or higher, and usually 280 ° C. or lower, preferably 2 ° C.
It is selected in the range of 50 ° C. or less, and the time is selected in the range of 5 minutes or more and 60 minutes or less. Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above.
[3-8] Formation of Transparent Electrode The color filter according to the present invention forms a transparent electrode such as ITO on an image as it is, and is used as a part of components such as a color display and a liquid crystal display device. However, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.
[4] Liquid crystal display device (panel)
Next, a manufacturing method of the liquid crystal display device (panel) according to the present invention will be described. The liquid crystal display device according to the present invention is generally formed by forming an alignment film on the color filter according to the present invention, spraying spacers on the alignment film, and then bonding to the counter substrate to form a liquid crystal cell. The liquid crystal is injected into the liquid crystal cell and connected to the counter electrode to complete. The alignment film is preferably a resin film such as polyimide. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to form a surface state in which the tilt of the liquid crystal can be adjusted.

  As the spacer, a spacer having a size corresponding to a gap (gap) with the counter substrate is used, and a spacer of 2 to 8 μm is usually preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by a photolithography method, and this can be used instead of the spacer. As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable.

The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 μm or more and 8 μm or less. After being bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by UV irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . The degree of vacuum in the liquid crystal cell is usually in the range of 1 × 10 ⁻² Pa or more, preferably 1 × 10 ⁻³ Pa or more, and usually 1 × 10 ⁻⁷ Pa or less, preferably 1 × 10 ⁻⁶ Pa or less. . The liquid crystal cell is preferably heated during decompression, and the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower. The warming holding at the time of depressurization is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal. The liquid crystal cell into which the liquid crystal is injected has a liquid crystal display device (panel) completed by sealing the liquid crystal injection port by curing the UV curable resin.

  The type of liquid crystal is not particularly limited, and may be any of conventionally known liquid crystals such as aromatic, aliphatic, and polycyclic compounds, and may be any of lyotropic liquid crystals, thermotropic liquid crystals, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.

Next, although a manufacture example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded. In the following examples, “part” represents “part by weight”.
<Examples 1-6 and Comparative Examples 1-6>
(Synthesis Example 1)
Synthesis of polycaprolactone 5 parts by weight of lauryl alcohol, 95 parts by weight of caprolactone and 0.003 parts by weight of dibutyltin dilaurate were mixed and heated to 160 ° C. within 1 hour. The addition reaction was completed as soon as a solids content of 99% was obtained.

(Synthesis Example 2)
Synthesis of polycaprolactone The reaction was performed under the same conditions as in Synthesis Example 1 except that lauryl alcohol in Synthesis Example 1 was changed to methanol.
(Synthesis Example 3)
Synthesis of Urethane Dispersant A Tolylene diisocyanate trimer (Mittech GP750A manufactured by Mitsubishi Chemical Co., Ltd., resin solid content 50 wt%, 2,4: 2,6 = 8: 2 mixture, butyl acetate solution ) 32 parts by weight and 0.01 part by weight of dibutyltin dilaurate as a catalyst were diluted and dissolved in 47 parts by weight of PGMEA (propylene glycol monomethyl ether acetate). Under agitation, polycaprolactone having an average molecular weight of 2,000 (one obtained in Synthesis Example 1) having one end being a laurylalkoxy group at one end and 9.6 parts by weight of polyoxytetramethylene glycol having an average molecular weight of 1000 And the mixture was reacted at 70 ° C. for 3 hours. Next, 1 part by weight of N, N-dimethyl-1,3-propanediamine was added, and the mixture was further reacted at 40 ° C. for 1 hour. The amine value of the solution containing the dispersion resin thus obtained was determined by neutralization titration to be 32 mg KOH / g. Further, when the resin content was determined by a dry-up method (heating at 150 ° C. for 30 minutes on a hot plate, removing the solvent and calculating the resin concentration based on the weight change), the resin content was 40 wt%.

(Synthesis Example 4)
Synthesis of Urethane Dispersant B In Example 3 of synthesis, polycaprolactone having a molecular weight of 2,000 having one end of a laurylalkoxy group was changed to a polycaprolactone having a molecular weight of 2,000 having one end having a methoxy group. , N-dimethyl-1,3-propanediamine was changed to 1- (3-aminopropyl) imidazole to obtain a dispersion resin in the same manner as in Synthesis Example 3. The amine value of the solution containing this resin was 34 mgKOH / g, and the resin content was 40 wt%.

(Synthesis Example 5)
Synthesis of Urethane Dispersant C A dispersion resin was obtained in the same manner as in Synthesis Example 4 except that 1- (3-aminopropyl) imidazole in Synthesis Example 4 was changed to 3-amino-1,2,4-triazole. . The acid value of the solution containing this resin was 32 mgKOH / g, and the resin content was 40 wt%.

(Synthesis Example 6)
Synthesis of Binder Resin a 145 parts by weight of propylene glycol monomethyl ether acetate was stirred while being purged with nitrogen, and the temperature was raised to 80 ° C. 20 parts by weight of polymethyl methacrylate macromonomer, 15 parts of 2-hydroxyethyl methacrylate, 10 parts of benzyl methacrylate, and 35 parts of methacrylic acid were added dropwise, and stirring was continued for 2 hours. Next, 155 parts by weight of propylene glycol monomethyl ether acetate was added, 0.2 parts by weight of p-methoxyphenol and 1.5 parts by weight of triphenylphosphine were added and dissolved, and (3,4-epoxycyclohexyl) methyl acrylate 31 was then added. A part by weight was dropped and reacted at 85 ° C. for 24 hours to obtain a binder resin solution having an ethylenically unsaturated group in the side chain. The binder resin thus obtained had a weight average molecular weight Mw measured by GPC of about 14,000.

(Synthesis Example 7)
Synthesis of Binder Resin b 145 parts by weight of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 80 ° C. 20 parts by weight of styrene, 15 parts by weight of glycerol monomethacrylate, 10 parts by weight of N-phenylmaleimide, 10 parts of benzyl methacrylate and 35 parts of methacrylic acid were added dropwise thereto, and stirring was further continued for 2 hours. Next, 155 parts by weight of propylene glycol monomethyl ether acetate was added, 0.2 parts by weight of p-methoxyphenol and 1.5 parts by weight of triphenylphosphine were added and dissolved, and (3,4-epoxycyclohexyl) methyl acrylate 31 was then added. A part by weight was dropped and reacted at 85 ° C. for 24 hours to obtain a binder resin solution having an ethylenically unsaturated group in the side chain. The binder resin thus obtained had a weight average molecular weight Mw measured by GPC of about 15,000.

(Synthesis Example 8)
Synthesis of Binder Resin c 145 parts by weight of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 80 ° C. 20 parts by weight of styrene, 15 parts by weight of glycerol monomethacrylate, 10 parts by weight of N-phenylmaleimide, 10 parts by weight of benzyl methacrylate, 20 parts by weight of mono (2-methacryloyloxyethyl) succinate, and 15 parts by weight of methacrylic acid The solution was added dropwise and stirring was continued for another 2 hours. Next, 155 parts by weight of propylene glycol monomethyl ether acetate was added, 0.2 parts by weight of p-methoxyphenol and 1.5 parts by weight of triphenylphosphine were added and dissolved, and (3,4-epoxycyclohexyl) methyl acrylate 31 was then added. A part by weight was dropped and reacted at 85 ° C. for 24 hours to obtain a binder resin solution having an ethylenically unsaturated group in the side chain. The binder resin thus obtained had a weight average molecular weight Mw measured by GPC of about 14,000.

(Synthesis Example 9)
Synthesis of Binder Resin d 145 parts by weight of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 80 ° C. 30 parts by weight of styrene and 34 parts by weight of methacrylic acid were added dropwise thereto, and stirring was further continued for 2 hours. Next, 155 parts by weight of propylene glycol monomethyl ether acetate was added, 0.2 parts by weight of p-methoxyphenol and 1.5 parts by weight of triphenylphosphine were added and dissolved, and (3,4-epoxycyclohexyl) methyl acrylate 31 was then added. A part by weight was dropped and reacted at 85 ° C. for 24 hours to obtain a binder resin solution having an ethylenically unsaturated group in the side chain. The binder resin thus obtained had a weight average molecular weight Mw measured by GPC of about 18,000.

(Synthesis Example 10)
Synthesis of Binder Resin e 145 parts by weight of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 80 ° C. To this, 53 parts by weight of benzyl methacrylate, 40 parts by weight of methyl methacrylate and 26 parts by weight of methacrylic acid were added dropwise, and stirring was continued for 2 hours. Next, 155 parts by weight of propylene glycol monomethyl ether acetate was added, 0.2 parts by weight of p-methoxyphenol and 1.5 parts by weight of triphenylphosphine were added and dissolved, and (3,4-epoxycyclohexyl) methyl acrylate 31 was then added. A part by weight was dropped and reacted at 85 ° C. for 24 hours to obtain a binder resin solution having an ethylenically unsaturated group in the side chain. The binder resin thus obtained had a weight average molecular weight Mw measured by GPC of about 16000.

<Preparation of Red pigment dispersion>
As a coloring material, C.I. I. 10.00 parts by weight of Pigment Red 177, 33.75 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 5.25 parts by weight of the dispersant described in Table-1 as a dispersant, and 8 binder resins described in Table-2 A stainless steel container was filled with 0.000 parts by weight of zirconia beads having a diameter of 0.5 mm and dispersed in a stainless steel container for 6 hours to prepare a red pigment dispersion.

<Preparation of Blue Pigment Dispersion>
As a coloring material, C.I. I. Pigment Blue 15: 6 10.00 parts by weight, 33.75 parts by weight of propylene glycol monomethyl ether acetate as a solvent, 5.25 parts by weight of the dispersant described in Table-1 as a dispersant, and the binder resin described in Table-2 Was packed in a stainless steel container and dispersed in a paint shaker for 6 hours to prepare a blue pigment dispersion.

<Preparation of Green pigment dispersion>
As a coloring material, C.I. I. Pigment Green 36 10.00 parts by weight, propylene glycol monomethyl ether acetate 33.75 parts by weight as a solvent, 6.25 parts by weight of the dispersant described in Table 1 as the dispersant, and 8 binder resins described in Table 2 A stainless steel container was filled with 0.000 parts by weight of zirconia beads having a diameter of 0.5 mm and dispersed in a stainless steel container for 6 hours to prepare a green pigment dispersion.

<Preparation of colored resin composition>
The pigment dispersion was mixed with other components to prepare colored resin compositions shown in Table-2.

<Viscosity change of colored resin composition>
The viscosity (20 rpm) immediately after preparation of the colored resin composition and after standing in a thermostatic bath at 23 ° C. for 7 days
) Was measured using an E-type viscometer “RE-80L” manufactured by Toki Sangyo Co., Ltd. Table 4 shows the viscosity and the rate of change in viscosity over 7 days for the colored resin compositions of Examples and Comparative Examples.

<Manufacture of color filters>
Metallic chromium was deposited on a glass substrate (Asahi Glass Co., Ltd., AN100) having a length of 370 mm, a width of 470 mm, and a thickness of 0.7 mm. After forming a matrix pattern with a positive photoresist, ceric nitrate The chromium film was etched using an etching solution in which ammonium and perchloric acid were mixed. Finally, the positive photoresist was peeled off with a 5% aqueous sodium hydroxide solution to form a black matrix.

On the glass substrate with a black matrix thus obtained, a coloring composition containing a red color material was applied with a die coater. In addition, the die coater used the stainless steel die coater of width 360mm, the lip space | interval was 200 micrometers and the gap with the glass substrate surface was 100 micrometers. At the time of coating, the discharge amount of the coating liquid exhibiting an ink shape was adjusted so that the dry film thickness was 1.3 μm. Then, after drying at 60 degreeC for 1 minute, it heat-dried at 110 degreeC for 2 minutes. Next, using a negative photomask repeated at a pitch of 30 μm in width, 330 μm in length and 110 μm in width, exposure processing was performed with a 2 kW high-pressure mercury lamp at an exposure amount of 300 mJ / cm ² .
Thereafter, development was performed using a 0.1 wt% aqueous sodium carbonate solution at a developer temperature of 23 ° C. Subsequently, the spray water washing process was performed for 30 seconds with the water pressure of 3 kg / cm < ² >, and the red pixel was formed. Then, the thermosetting process for 7 minutes was performed at the temperature of 230 degreeC.

Next, the coloring composition containing the blue and green coloring materials is subjected to the following procedures in the same manner as described above: coating, preliminary drying, heat drying, exposure, development, washing, and thermosetting, and each color pattern is sequentially formed. A color filter was obtained. In this way, 100 color filters were prepared using the curable resin compositions having the compositions of Examples 1 to 6 and Comparative Examples 1 to 5.
<Evaluation of foreign matter defects in color filter>
About the obtained color filter, the presence or absence of the foreign material defect generation | occurrence | production was measured, and the foreign material defect generation rate was shown in Table-5. In Table-5, red, blue, and green mean that foreign matter exists on each color pixel. A foreign substance defect is defined as a foreign substance having a square root of [(major axis) ² + (minor axis) ² ] of 40 μm or more, and the number of color filters in which a foreign substance defect is recognized in any color is defined as The value divided by the number of manufactured sheets (100 sheets) was defined as the foreign substance defect occurrence rate. The evaluation results are shown in Table-5.

<Evaluation of re-solubility (measurement of volume average particle diameter mv)>
The colored resin compositions of each Example and Comparative Example were each applied to a 50 mm square glass substrate by a spin coating method with a dry film thickness of 2.5 μm and air-dried for 60 minutes. Thereafter, it was immersed in 6.25 g of the solvent for forming the colored composition for 3 minutes, redispersed, and after 10 minutes from the start of immersion, the particle size distribution was measured with Nikkiso Microtrac UPA, and the volume average particle size mv was determined. Calculated. The results are shown in Table-5.

In addition, the foreign matter defect occurrence rate in each color is 0%, the volume average particle diameter mv in re-dissolution is 140 nm or less, and the foreign matter defect occurrence rate is 1% or less, mv is 200 nm or less. It was equivalent.
<Evaluation of undissolved material (residue) in non-pixel part of color filter>
The obtained color filter was wiped 10 times with a Toray-made Toraysee MK clean cloth impregnated with ethanol in a 30 × 100 mm portion of the non-pixel portion (on the raw glass). The Toraysee MK clean cloth was fixed at the tip of a 1 cm × 1 cm resin square and impregnated with 0.1 cc of ethanol using a dropper. When the adhesion of the pigment to the Toraysee was not visually recognized, it was evaluated as “◯”, and when it was recognized even in a small amount, “X” was evaluated. In addition, the spectral reflectance of a 1 cm × 1 cm portion of the wiped tressy was measured with a spectrophotometer UV-3100S manufactured by Shimadzu Corporation under the condition using an integrating sphere. Table 6 shows spectral reflectances at λ = 500 nm (corresponding to red residue), 450 nm (corresponding to green residue), and 550 nm (corresponding to blue residue).

  In addition, the boundary of ○ × judgment in visual evaluation was equivalent to 95% in spectral reflectance.

From the above results, the following is clear.
(1) Since the colored resin composition according to the present invention can control the interaction between the dispersant and the binder resin, it is possible to suppress the occurrence of foreign matter defects.
(2) Since the coloring composition according to the present invention can control the interaction between the dispersant and the binder resin, the undissolved matter remains in the non-pixel portion on the substrate after development.

The present invention has the following useful effects, and its industrial utility value is extremely large.
1. When the colored resin composition according to the present invention is applied on the substrate, the undissolved material does not remain in the non-pixel portion on the substrate, and the adhesion with the substrate is high. The color pixels can be formed uniformly.
2. When the colored resin composition according to the present invention is applied on a substrate by a die coating method, dry aggregation at the tip of the die lip is suppressed, so that there is little generation of foreign matter and a color filter can be produced with a high yield. .
3. The color filter according to the present invention has a very high quality since the undissolved colored resin composition does not remain in the non-pixel portion on the substrate.
4). The liquid crystal display device according to the present invention has an extremely high quality because it uses an extremely high quality color filter in which an undissolved material of the colored resin composition does not remain in the non-pixel portion on the substrate.

Claims (7)

A colored resin composition containing a colorant, a solvent, a dispersant, and a binder resin, wherein the binder resin is a macromonomer, a monomer having an alcoholic hydroxyl group, a monomer having a carboxyl group, a monomer having an N-substituted maleimide, a dicarboxylic acid A resin comprising a copolymer of at least one of the acid mono (2- (meth) acryloyloxyethyl) and another copolymerizable monomer, and the dispersant is a urethane-based dispersant A colored resin composition comprising:   Urethane dispersant is (1) a polyisocyanate compound, (2) a compound having one or two hydroxyl groups in the same molecule, and (3) a compound having an active hydrogen and a tertiary amino group in the same molecule. The colored resin composition according to claim 1, wherein the colored resin composition is obtained.   The colored resin composition according to claim 1 or 2, wherein the tertiary amino group is a dimethylamino group and / or an imidazole ring.   The colored resin composition according to any one of claims 1 to 3, wherein the monomer having an alcoholic hydroxyl group contained in the binder resin is glycerol (meth) acrylate.   The colored resin composition according to claim 1, comprising an organic carboxylic acid and / or an organic carboxylic acid anhydride having a molecular weight of 1000 or less.   A color filter formed using the colored composition according to claim 1. A liquid crystal display device formed using the color filter substrate according to claim 8.