JP4561062B2 - Photosensitive colored resin composition for color filter, color filter, and liquid crystal display device - Google Patents

Description

  The present invention relates to a photosensitive colored resin composition for a color filter, a color filter, and a liquid crystal display device. Specifically, a photosensitive colored resin composition for a color filter having excellent liquid stability and heat resistance, little background stain during development, good adhesion to a substrate and good edge shape of a pixel, and the photosensitive colored resin composition The present invention relates to a color filter using an object and a liquid crystal display device using the color filter.

  Conventionally, as a method for producing a color filter using a pigment, a dyeing method, an electrodeposition method, an ink jet method, a pigment dispersion method, and the like are known.

  In the case of the pigment dispersion method, a photosensitive colored resin composition that is usually sensitized by adding a binder resin, a photopolymerization initiator, a photopolymerizable monomer, etc. to a colored composition obtained by dispersing a pigment with a dispersant or the like. After coating on a glass substrate and drying, exposure is performed using a mask and development is performed to form a colored pattern, which is then heated to fix the pattern and form pixels. These steps are repeated for each color to form a color filter.

  A photosensitive colored resin composition used for image formation of a color filter using such a photosensitive colored resin composition is required to have sufficient resolution, adhesion to a substrate, and low development residue. ing. Furthermore, in recent years, a pixel having a high color density and a resin black matrix having a high optical density are required, and the content of a coloring material such as pigment or carbon black in the photosensitive colored resin composition tends to be high. In such a state where the colorant content is high, it is required to have excellent characteristics.

  On the other hand, in general, a photosensitive resin composition containing a component that can be polymerized by light, a photopolymerization initiator, and a binder resin, including the photosensitive colored resin composition, is generally applied, dried, exposed, and developed. Since it is used for the photolithography process that passes through the process, in such a process, no residue or scumming occurs in the removed part in the development process; the removed part has sufficient solubility; the sharpness of the pattern edge, etc. However, when a pixel is formed using a photosensitive colored resin composition having a high colorant content as described above, it is necessary to develop a pixel on the unexposed portion of the substrate during the development process. Residues and background stains occur; phenomena such as poor solubility of unexposed areas and poor edge shape of pixels; poor sensitivity of pixels formed in exposed areas; surface smoothness But There; phenomenon problem that is likely to occur remarkably, has been a major problem.

  In particular, when a light blocking ability is required in the entire wavelength region of light, such as a resin black matrix, (1) it is extremely difficult to make a difference in crosslink density between an exposed portion and an unexposed portion, and (2) exposure. The difference in cross-linking density in the film thickness direction is generated even in the part where the film is formed, that is, it is sufficiently cured on the light irradiation surface side but not cured on the base surface side, and (3) a large amount of black insoluble in the developer The deterioration in developability due to the blending of the colorant is an obstacle to imparting good photosensitive characteristics.

  Then, in order to solve such a problem, the photosensitive coloring resin composition using the novolak epoxy acrylate which has a carboxyl group as binder resin is disclosed (refer patent document 1). However, as a result of studies by the present inventors, even when this binder resin is used, since the balance between solubility and sensitivity is poor, the penetration of the developer into the exposed portion occurs simultaneously with the dissolution of the unexposed portion, and the pixel It has been found that the problem arises that the edge of the pixel is shaky; the adhesion of the pixel to the substrate is poor.

  Moreover, although the photosensitive resin composition using the reaction material of the acrylic resin which has a carboxyl group, and an alicyclic epoxy group containing unsaturated compound is disclosed as binder resin (refer patent document 2), this binder resin is disclosed. Since the sensitivity is not sufficient even when using a pixel, it has been found that the adhesion of the pixel to the substrate is poor and it is difficult to form a high-definition pixel.

  In addition, the resin composition using the reaction material of the epoxy resin represented by following General formula (1) as a binder resin, unsaturated group containing carboxylic acid, and a polybasic carboxylic acid anhydride, resist ink resin composition Although these cured products are disclosed (see Patent Document 3), this document does not show any description about the synergistic effect of the binder resin and the dispersant and application to the color filter. This document describes a solder resist as an application, and does not suggest any diversion to a color filter application in which the pigment concentration is greatly different, or a resin black matrix application having absorption in the entire wavelength region.

（式中、ｎは平均値を示し０〜１０の数を示す。Ｐ，Ｒは水素原子、ハロゲン原子、炭素数１〜８のアルキル基、アリール基のいずれかを表し、個々のＰ，Ｒはお互いに同一であっても異なっていても良い。Ｇはグリシジル基を表す。）
特開平１１−８４１２６号公報 特開平１−２８９８２０号公報 特開平９−２１１８６０号公報

(In the formula, n represents an average value and represents a number of 0 to 10. P and R each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group. May be the same as or different from each other, and G represents a glycidyl group.)
Japanese Patent Laid-Open No. 11-84126 JP-A-1-289820 JP-A-9-21860

  An object of the present invention is to provide a photosensitive colored resin composition for a color filter which is excellent in image forming property even when the colorant concentration is high, and a color filter and a liquid crystal display device using the photosensitive colored resin composition. It is in.

  The photosensitive colored resin composition for a color filter of the present invention is obtained by further reacting a reaction product of an epoxy resin (a) and an unsaturated group-containing carboxylic acid (b) with a polybasic acid and / or its anhydride (c). In the photosensitive colored resin composition containing the alkali-soluble resin (A), the photopolymerization initiator (B), the colorant (C), and the dispersant (D) obtained in this way, the epoxy resin (a) has the following general formula: It is represented by (1).

（式中、ｎは平均値を示し０〜１０の数を示す。Ｐ，Ｒは水素原子、ハロゲン原子、炭素数１〜８のアルキル基、アリール基のいずれかを表し、個々のＰ，Ｒはお互いに同一であっても異なっていても良い。Ｇはグリシジル基を表す。）

(In the formula, n represents an average value and represents a number of 0 to 10. P and R each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group. May be the same as or different from each other, and G represents a glycidyl group.)

  That is, as a result of intensive studies to achieve the above-mentioned object, the present inventors combined a specific binder resin and a dispersant to provide a good balance between sensitivity and solubility, and further, sharpness and adhesion of pixel edges. The present inventors have found that a photosensitive colored resin composition for a color filter that is excellent in color can be realized, and completed the present invention.

  In the present invention, the dispersant (D) preferably contains a polymer dispersant. Further, the dispersant (D) may contain a pigment derivative.

  The photosensitive colored resin composition for a color filter of the present invention is particularly suitable as a photosensitive colored resin composition for a resin black matrix of a color filter.

  The color filter of the present invention has pixels formed on the transparent substrate using such a photosensitive colored resin composition of the present invention.

  The liquid crystal display device of the present invention uses such a color filter of the present invention.

  The photosensitive colored resin composition for color filters of the present invention has good adhesion to the substrate, and has a good balance between sensitivity and solubility even when containing a coloring material such as pigment or carbon black at a high concentration. Has excellent pixel edge sharpness and adhesion, and can form high-definition pixels. According to the present invention, it is possible to provide a high-quality color filter and further a high-quality liquid crystal display device using such a photosensitive colored resin composition for a color filter.

  Hereinafter, embodiments of the present invention will be described in detail.

[Photosensitive colored resin composition]
<Alkali-soluble resin (A)>
The alkali-soluble resin (A) is obtained by further reacting a reaction product of the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b) with a polybasic acid and / or its anhydride (c). .

(1) Epoxy resin (a)
The epoxy resin (a) is represented by the following general formula (1).

（式中、ｎは平均値を示し０〜１０の数を示す。Ｐ，Ｒは水素原子、ハロゲン原子、炭素数１〜８のアルキル基、アリール基のいずれかを表し、個々のＰ，Ｒはお互いに同一であっても異なっていても良い。Ｇはグリシジル基を表す。）

(In the formula, n represents an average value and represents a number of 0 to 10. P and R each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group. May be the same as or different from each other, and G represents a glycidyl group.)

  The epoxy resin (a) represented by the general formula (1) is obtained by reacting, for example, a compound represented by the following general formula (2) with an epihalohydrin in the presence of an alkali metal hydroxide. Obtainable.

（式中、ｎ，Ｐ，Ｒは一般式（１）におけるのと同じ意味を表す。）

(In the formula, n, P and R have the same meaning as in the general formula (1).)

  The compound represented by the general formula (2) can be obtained, for example, by subjecting a compound represented by the following general formula (3) and a phenol to a condensation reaction in the presence of an acid catalyst.

（式中、Ｘはハロゲン原子、水酸基、又は低級アルコキシ基を表す。Ｒは一般式（１）におけるのと同じ意味を表す。）

(In the formula, X represents a halogen atom, a hydroxyl group, or a lower alkoxy group. R represents the same meaning as in general formula (1).)

  In X of the general formula (3), a halogen atom is a chlorine atom, a bromine atom, etc., a lower alkyl group is a methyl group, an ethyl group, a t-butyl group, etc., and a lower alkoxy group is a methoxy group, an ethoxy group. Etc. are mentioned as preferable groups. On the other hand, phenols are aromatic compounds having one phenolic hydroxyl group per molecule, and specific examples thereof include phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butylphenol, octylphenol. , Nonylphenol, xylenol, methylbutylphenol, various o-, m-, and p-isomers of alkylphenols such as di-t-butylphenol, or various o-, vinylphenol, allylphenol, propenylphenol, ethynylphenol, Examples include m-, p-isomers, or substituted phenols such as cycloalkylphenol and phenylphenol, typically cyclopentylphenol, cyclohexylphenol, cyclohexylresole and the like.These phenols can be used individually by 1 type or in combination of 2 or more types.

  When performing the said condensation reaction, the usage-amount of phenols becomes like this. Preferably it is 0.5-20 mol with respect to 1 mol of compounds represented by General formula (3), Most preferably, it is 2-15 mol.

  In the above condensation reaction, it is preferable to use an acid catalyst, and various acid catalysts can be used, such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminum chloride, zinc chloride, etc. In particular, p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid are preferable. Although the usage-amount of these acid catalysts is not specifically limited, It is preferable to use 0.1 to 30weight% with respect to the compound represented by General formula (3).

  The condensation reaction can be performed in the absence of a solvent or in the presence of an organic solvent. Specific examples in the case of using an organic solvent include toluene, xylene, methyl isobutyl ketone and the like. The amount of the organic solvent used is preferably 50 to 300% by weight, particularly preferably 100 to 250% by weight, based on the total weight of the charged raw materials. The reaction temperature is preferably in the range of 40 to 180 ° C., and the reaction time is preferably 1 to 8 hours.

  After completion of the reaction, neutralization treatment or water washing treatment is performed to adjust the pH value of the product to 3-7, preferably 5-7. When washing with water, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, ammonia, sodium dihydrogen phosphate, diethylenetriamine, What is necessary is just to process using various basic substances, such as organic amines, such as ethylenetetramine, aniline, and phenylenediamine, as a neutralizing agent. In addition, the washing treatment may be performed according to a conventional method. For example, a method in which water in which the neutralizing agent is dissolved is added to the reaction mixture and the liquid separation extraction operation is repeated can be employed.

  After the neutralization treatment or the water washing treatment, the unreacted dihydroxybenzenes and the solvent are distilled off under heating under reduced pressure to concentrate the product to obtain the compound represented by the general formula (2). be able to.

  As a method for obtaining the epoxy resin (a) according to the present invention represented by the general formula (1) from the compound represented by the general formula (2), a known method can be adopted. For example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added in advance or added to a dissolved mixture of the compound represented by the general formula (2) and an excess of epihalohydrin such as epichlorohydrin or epibromohydrin. However, the epoxy resin (a) represented by the general formula (1) can be obtained by reacting at a temperature of 20 to 120 ° C. for 1 to 10 hours.

  In the reaction for obtaining the epoxy resin (a), an aqueous solution of the alkali metal hydroxide may be used. In that case, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system and the pressure is reduced. Alternatively, water and epihalohydrin may be continuously distilled off under normal pressure, followed by liquid separation, water may be removed, and epihalohydrin may be continuously returned to the reaction system.

  Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is added as a catalyst to a dissolved mixture of the compound represented by the general formula (2) and epihalohydrin at 50 to 150 ° C. To the halohydrin etherified product of the compound represented by the general formula (2) obtained by reacting for 1 to 5 hours, a solid or aqueous solution of an alkali metal hydroxide is added, and again at a temperature of 20 to 120 ° C., 1 to A method of reacting for 10 hours to dehydrohalogenate (ring closure) may be used.

  The amount of epihalohydrin used in such a reaction is usually 1 to 20 mol, preferably 2 to 10 mol, relative to 1 equivalent of the hydroxyl group of the compound represented by formula (2). Moreover, the usage-amount of an alkali metal hydroxide is 0.8-15 mol normally with respect to 1 equivalent of hydroxyl groups of the compound represented by General formula (2), Preferably it is 0.9-11 mol.

  Furthermore, in order to make the reaction proceed smoothly, the reaction may be carried out by adding an aprotic polar solvent such as dimethylsulfone or dimethylsulfoxide in addition to alcohols such as methanol and ethanol. When alcohols are used, the amount used is 2 to 20% by weight, preferably 4 to 15% by weight, based on the amount of epihalohydrin. Moreover, when using an aprotic polar solvent, the usage-amount is 5 to 100 weight% with respect to the quantity of an epihalohydrin, Preferably it is 10 to 90 weight%.

  After the epoxidation reaction product is washed with water or without washing, epihalohydrin and other added solvents are removed at 110 to 250 ° C. under a pressure of 1.3 kPa (10 mmHg) under reduced pressure. In addition, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is dissolved. The reaction can be carried out by adding an aqueous solution to ensure ring closure. In this case, the amount of the alkali metal hydroxide used is preferably 0.01 to 0.3 mol, particularly preferably 0. 0 to 1 equivalent of the hydroxyl group of the compound represented by the general formula (2) used for epoxidation. It is 05-0.2 mol. The reaction temperature is 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, and the like, and further, the solvent such as toluene and methyl isobutyl ketone is distilled off under reduced pressure by heating, whereby the epoxy resin represented by the general formula (1) (a ) Is obtained.

(2) Unsaturated carboxylic acid (b)
Examples of the unsaturated group-containing carboxylic acid (b) include unsaturated carboxylic acids having an ethylenically unsaturated double bond. Specific examples thereof include (meth) acrylic acid (in this specification, “(meta ) Acrylic "," (meth) acrylate "and the like mean" acrylic or methacrylic "," acrylate or methacrylate ", for example," (meth) acrylic acid "means" acrylic acid or methacrylic acid " Crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, monocarboxylic acid such as cyano substitution, 2- (Meth) acryloyloxyethyl succinic acid, 2-acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (me ) Acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (meth) acryloyloxypropyladipic acid, 2- (meta ) Acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) Acrylroyoxybutyl adipic acid, 2- (meth) acryloyloxybutyl hydrophthalic acid, 2- (meth) acryloyloxybutyl phthalic acid, 2- (meth) acryloyloxybutyl maleic acid (meth), acrylic acid ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone Monomers to which lactones are added, or acids such as hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate, (anhydrous) succinic acid, (anhydrous) phthalic acid, (anhydrous) maleic acid, etc. Monomers to which (anhydrides) are added, (meth) acrylic acid dimers, and the like.

  Particularly preferred is (meth) acrylic acid. These may be used alone or in combination of two or more.

(3) Reaction of epoxy resin (a) with unsaturated group-containing carboxylic acid (b) Known method for reacting epoxy group in epoxy resin (a) with unsaturated group-containing carboxylic acid (b) Can be used. For example, the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b) are mixed with a tertiary amine such as triethylamine or benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, benzyltriethylammonium chloride. Carboxylic acid can be added to the epoxy resin by reacting in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours using a quaternary ammonium salt such as pyridine, triphenylphosphine or the like as a catalyst.

  The amount of the catalyst used is preferably 0.01 to 10% by weight, particularly preferably 0.3 to 0.3%, based on the reaction raw material mixture (total of epoxy resin (a) and unsaturated group-containing carboxylic acid (b)). 5% by weight. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, phenothiazine, etc.). Preferably it is 0.01 to 10 weight% with respect to a reaction raw material mixture, Most preferably, it is 0.1 to 5 weight%.

  The proportion of the unsaturated group-containing carboxylic acid (b) added to the epoxy group of the epoxy resin (a) is usually 90 to 100 mol%. Since the remaining epoxy group adversely affects storage stability, the unsaturated group-containing carboxylic acid (b) is usually 0.8 to 1.5 equivalents, particularly 0, to 1 equivalent of the epoxy group of the epoxy resin (a). It is preferable to carry out the reaction at a ratio of .9 to 1.1 equivalent.

(4) Polybasic acid and / or its anhydride (c)
As the polybasic acid and / or anhydride (c) added to the hydroxyl group of the reaction product of the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b), known ones can be used. Acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, methyl-5-norbornene-2 Dibasic carboxylic acids such as 1,3-dicarboxylic acid or anhydrides thereof; polybasic carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, or anhydrides thereof. Among these, tetrahydrophthalic anhydride or succinic anhydride is preferable. These may be used alone or in combination of two or more.

  The addition rate of the polybasic acid and / or its anhydride (c) is usually 10 to 100 mol% of the hydroxyl group produced when the unsaturated group-containing carboxylic acid (b) is added to the epoxy resin (a). , Preferably 20 to 100 mol%, more preferably 30 to 100 mol%. If the addition rate is too high, the remaining film rate during development may decrease, and if it is too low, the solubility may be insufficient or the adhesion to the substrate may be insufficient.

  As a method of adding a polybasic acid and / or its anhydride (c) after adding an unsaturated group-containing carboxylic acid (b) to the epoxy resin (a), a known method may be used. it can.

  Moreover, in this invention, after adding a polybasic acid and / or its anhydride (c) in this way, you may add an epoxy-group containing compound (d) to a part of produced | generated carboxyl group. In this case, as the epoxy group-containing compound (d), in order to improve the photosensitivity, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, a glycidyl ether compound having a polymerizable unsaturated group, etc. In order to add an epoxy group-containing unsaturated compound or to improve developability, a glycidyl ether compound having no polymerizable unsaturated group can be added, or both of these may be used in combination. . Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include a glycidyl ether compound having a phenyl group or an alkyl group (manufactured by Nagase Chemical Industries, Ltd., trade names: Denacol EX-111, Denacol EX-121, Denacol) EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192) and the like.

  In the alkali-soluble resin (A) according to the present invention, the reaction product of the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b) is further reacted with a polybasic acid and / or its anhydride (c). A resin obtained by adding such an epoxy group-containing compound (d) to a part of the carboxyl group of the resin obtained in this way may be used.

(5) Physical Properties of Alkali-Soluble Resin (A), etc. The polystyrene-equivalent weight average molecular weight (Mw) measured by GPC of the alkali-soluble resin (A) used in the present invention is usually 700 or more, preferably 1000 or more, and usually 50000 or less. , Preferably 30000 or less. If the weight average molecular weight of the alkali-soluble resin (A) is too small, the heat resistance and the film strength are inferior, and if it is too large, the solubility in the developer is insufficient.

  The acid value (mg-KOH / g) of the alkali-soluble resin (A) used in the present invention is usually 10 or more, preferably 50 or more, and usually 200 or less, preferably 150 or less. If the acid value of the alkali-soluble resin (A) is too low, sufficient solubility cannot be obtained, and if the acid value is too high, curability is insufficient and surface properties are deteriorated.

<Photoinitiator (B)>
The photopolymerization initiator (B) used in the present invention is not particularly limited as long as it is a compound that polymerizes an ethylenically unsaturated group with actinic rays, but the photosensitive colored resin composition of the present invention contains a polymerizable group. When an ethylenic compound is included as the compound having, a photopolymerization initiator that has a function of directly absorbing light or photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical is used. Is preferred.

  Specific examples of the photopolymerization initiator (B) 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-trichloromer-5- [β- (2'-benzofuryl) vinyl] -1,3,4-oxadi Azole, -trichloromethyl-5- [β- (2 '-(6 "-benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5 monofuryl-1,3,4 Halomethylated oxadi, such as oxadiazole Azole derivatives; 2- (2'-chlorophenyl) -4,5-diphenylimidazolol dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl)- Imidazole derivatives such as 4,5-diphenylimidazole dimer; Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; 2-methylanthraquinone, 2-ethylanthraquinone, 2-t- Anthraquinone derivatives such as butylanthraquinone and 1-chloroanthraquinone; benzophenone, Michler's Benzophenone derivatives such as t, 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 Acetophenone derivatives such as -dodecylphenyl) ketone, 2-methyl- (4 '-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; 2-ethylthioxanthone, 2-isopropyl Thioxanthone derivatives such as oxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; benzoic acid such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate Ester derivatives; acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine; phenazine derivatives such as 9,10-dimethylbenzphenazine; anthrone derivatives such as benzanthrone; dicyclopentadienyl-Ti-dichloride Dicyclopentadienyl-Ti-bisphenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis- 2,3,5,6-tetrafluorophenyl-1-yl, dicyclopenta Enyl-Ti-bis-2,4,6-trifluorophen-1-yl, dicyclopentadienyl-Ti-2,6-diplorophen-1-yl, dicyclopentadienyl-Ti-2,4- Difluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6- Titanocene derivatives such as difluorophen-1-yl and dicyclopentagenyl-Ti-2,6-difluoro-3- (pyr-1-yl) -phen-1-yl. Further, oxime initiators described in JP-A-2000-80068 can be used particularly preferably.

  In addition, the photopolymerization initiator (B) that can be used in the present invention is a fine chemical, March 1, 1991, Vol. 20, no. 4, P. 16-P26, JP-A-59-152396, JP-A-61-151197, JP-B-45-37377, JP-A-58-40302, JP-A-10-39503 Has been.

<Coloring material (C)>
The color material (C) refers to a colorant for the photosensitive colored resin composition of the present invention. As the coloring material, dyes and pigments can be used, but pigments are 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, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene and perylene, various inorganic pigments can be used. It is. Specific examples of pigments that can be used are shown below by pigment numbers. Note that terms such as “CI Pigment Red 2” described below mean 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, 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. And CI 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, 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. And CI 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, 23, more preferably C.I. I. And CI Pigment Violet 23.

  Moreover, when the photosensitive coloring resin composition of this invention is the photosensitive coloring resin composition for resin black matrices of a color filter, a black coloring material can be used as a coloring material (C). The black color material may be a single black color material or a mixture of red, green, blue, and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, it is preferable to use the pigment dispersed in an average particle size of 1 μm or less, preferably 0.5 μm or less.

  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. (The numbers in parentheses above mean the color index (CI)).

  Further, other pigments that can be used in combination are 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.

  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 is preferable from the viewpoints of light shielding rate and image characteristics. Examples of carbon black include the following carbon black.

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

Degussa: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, C lor Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

Cabot Corporation: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130 , VULCAN XC72R, ELFTEX-8

Made by Colombian Carbon: Raven11, Raven14, Raven15, Raven16, Raven22, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10 , RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

  As examples of other black pigments, titanium black, aniline black, iron oxide black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments.

  In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, or the like can also be used as the pigment.

  These various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

  The average particle size of these pigments is usually 1 μm, 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.

  Other examples of the phthalocyanine dye 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.

<Dispersant (D)>
In the present invention, since it is important for quality stability to finely disperse the color material (C) and stabilize the dispersion state, it is essential to contain the dispersant (D).

  The dispersant (D) is preferably a polymer dispersant having a functional group, and further, from the viewpoint of dispersion stability, a carboxyl group, a phosphate group, a sulfonate group and salts thereof, primary, secondary, A polymer dispersant having a functional group such as a tertiary amino group, a quaternary ammonium salt, a nitrogen-containing heterocycle such as pyridine, pyrimidine and pyrazine is advantageously used.

  Examples of the polymer dispersant include a urethane dispersant, an acrylic dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, Aliphatic modified polyester dispersants and the like can be mentioned. As specific examples, EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by BYK Chemie), Dispalon (manufactured by Enomoto Kasei Co., Ltd.) )), SOLSPERSE (manufactured by Zeneca), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and the like. These may be used alone or in combination of two or more.

  The weight average molecular weight (Mw) in terms of polystyrene by GPC of these polymer dispersants is 700 or more, preferably 1000 or more and 100,000 or less, preferably 50,000 or less.

  It is particularly preferable that the dispersant (D) has a urethane-based and acrylic-based polymer dispersant having a functional group in terms of adhesion and linearity. Examples of urethane-based and acrylic-based polymer dispersants include Disperbyk 160 to 166 series, Disperbyk 2000, 2001, and the like (both manufactured by Big Chemie).

  If a chemical structure preferable as a urethane polymer dispersant is specifically exemplified, for example, the same as a polyisocyanate compound and a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule Examples thereof include a dispersion resin having a weight average molecular weight of 1,000 to 200,000, which is obtained by reacting an active hydrogen with a compound having a tertiary amino group in the molecule.

  Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω Alicyclic diisocyanates such as '-diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α', α'-tetramethyl Aliphatic diisocyanates having aromatic rings such as luxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate , Triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, and trimers thereof, water adducts, and polyol adducts thereof. Preferred as the polyisocyanate are trimers of organic diisocyanate, and most preferred are trimerene of tolylene diisocyanate and trimer of isophorone diisocyanate. These may be used alone or in combination of two or more.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. 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.

  Examples of the compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, and one terminal hydroxyl group of these compounds has a carbon number. Examples thereof include those alkoxylated with 1 to 25 alkyl groups and mixtures of two or more thereof.

  Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing alkylene oxide, 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 a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or 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 glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene 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 diol or carbon number 1 to 25 monovalent Polylactone diol or polylactone monool obtained by using an alcohol as an initiator, for example, polycaprolactone glycol, polymethyl valerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone starting with an alcohol having 1 to 25 carbon atoms.

  Examples of polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Is mentioned. The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

  A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described. Examples of the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. The hydrogen atom of the amino group is preferable. The tertiary amino group is not particularly limited. Moreover, as a tertiary amino group, the amino group which has a C1-C4 alkyl group, or a heterocyclic structure, More specifically, an imidazole ring or a triazole ring is mentioned.

  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. Preferred as these nitrogen-containing heterocycles are an imidazole ring or a triazole ring.

  Specific examples of these compounds having an imidazole ring and an amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. Further, specific examples of the compound having a triazole ring and an 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-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 preferable.

  A preferred blending ratio of the urethane-based polymer dispersant raw material is 10 to 200 parts by weight of a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. Preferably 20 to 190 parts by weight, more preferably 30 to 180 parts by weight, and 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight of the compound having an active hydrogen and a tertiary amino group in the same molecule. is there.

  The weight-average molecular weight in terms of GPC of the urethane-based polymer dispersant is usually 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and if it exceeds 200,000, the solubility is lowered and the dispersibility is poor, and at the same time, it becomes difficult to control the reaction. Manufacture of a urethane type polymer dispersing agent 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.

  In the above production, a urethanization reaction catalyst is usually used. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. Secondary amine type and the like can be mentioned.

  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 mg-KOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mg-KOH / g. The amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and representing the acid value in mg of KOH. When the amine value is lower than the above range, the dispersing ability tends to be lowered, and when it exceeds the above range, the developability tends to be lowered.

  In addition, when an isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time is increased.

  As the acrylic polymer dispersant, an unsaturated group-containing monomer having a functional group (the functional group here is the functional group described above as the functional group contained in the polymer dispersant); It is preferable to use a random copolymer, a graft copolymer, or a block copolymer with an unsaturated group-containing monomer having no functional group. These copolymers can be produced by a known method.

  Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acrylic acid. Tertiary amino groups such as unsaturated monomers having a carboxyl group such as leuoxyethyl hexahydrophthalic acid and acrylic acid dimer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof; Specific examples include unsaturated monomers having a quaternary ammonium base.

  Examples of the unsaturated group-containing monomer having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, isobornyl (meth) acrylate, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohe N-substituted maleimides such as silmaleimide, N-phenylmaleimide, N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly-2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol Examples thereof include macromonomers, polypropylene glycol macromonomers, and macromonomers such as polycaprolactone macromonomers.

  The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer composed of an A block having a functional group and a B block having no functional group. In addition to the unsaturated group-containing monomer containing the functional group, the block may contain an unsaturated group-containing monomer that does not contain the functional group. It may be contained in any form of polymerization or block copolymerization. Further, the content of the partial structure containing no functional group in the A block is usually 80% by weight or less, preferably 50% by weight or less, and more preferably 30% by weight or less.

  The B block is composed of an unsaturated group-containing monomer that does not contain the above functional group. However, two or more types of monomers may be contained in one B block. It may be contained in any form of random copolymerization or block copolymerization in the block.

  The AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below.

  The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Among these, the anion living polymerization method has a polymerization active species as an anion, and is represented by the following scheme, for example.

  In the radical living polymerization method, the polymerization active species is a radical, and is represented by the following scheme, for example.

  In synthesizing this acrylic polymer dispersant, JP-A-9-62002, P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), BC Anderson, GD Andrews et al. , Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Right hand, Koichi Hatada, Polymer processing, 36 , 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Journal, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida Inoue Shohei, Synthetic Organic Chemistry, 43, 300 (1985), DYSogoh, WRHertler et al, Macromolecules, 20, 1473 (1987), etc. can be employed.

  Whether the acrylic polymer dispersant used in the present invention is an AB block copolymer or a B-A-B block copolymer, the A block / B block ratio constituting the copolymer Is preferably 1/99 to 80/20, and more preferably 5/95 to 60/40 (weight ratio). Outside this range, it may not be possible to combine good heat resistance and dispersibility.

  In addition, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and the BAB block copolymer according to the present invention is preferably 0.1 to 10 mmol, and outside this range. In some cases, good heat resistance and dispersibility cannot be combined.

  Such a block copolymer usually contains an amino group produced in the production process, but its amine value is about 1 to 100 mg-KOH / g. The amine value is a value expressed in mg of KOH corresponding to the acid value after neutralizing titration of the basic amino group with an acid as described above.

  Moreover, although the acid value of this block copolymer depends on the presence and type of the acid group that is the basis of the acid value, it is generally preferable that the acid value is low, and is usually 10 mg-KOH / g or less, and its molecular weight is A range of 1000 to 100,000 in terms of weight average in terms of polystyrene is preferred. When the molecular weight of the block copolymer is less than 1,000, the dispersion stability decreases, and when it exceeds 100,000, the developability and resolution tend to decrease.

  The dispersant (D) of the present invention may be a pigment derivative. Examples of the pigment derivative include azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, and anthraquinone. , Indanthrene, perylene, perinone, diketopyrrolopyrrole, and dioxazine derivatives, among which quinophthalone is preferable. 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, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton. Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. These may be used alone or in combination of two or more. Further, it is preferable to use a polymer dispersant and a pigment derivative in combination as the dispersant.

<Photopolymerizable monomer>
In the present invention, it is preferable to use a photopolymerizable monomer (photopolymerizable compound) in addition to the alkali-soluble resin (A) and the photopolymerization initiator (B) in terms of sensitivity and the like. Examples of the photopolymerizable monomer used in the present invention include compounds having at least one ethylenically unsaturated group. Specific examples of the compound having an ethylenically unsaturated group in the molecule include (meth) acrylic acid, alkyl ester of (meth) acrylic acid, acrylonitrile, styrene, carboxylic acid having one ethylenically unsaturated bond and many ( And monoesters of monohydric alcohols.

  In the present invention, it is desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. Examples of such polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatics Examples thereof include esters obtained by an esterification reaction of a polyvalent hydroxy compound such as a polyhydroxy compound with an unsaturated carboxylic acid and a polybasic carboxylic acid.

  Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. In the same way, itaconic acid ester instead of itaconate, Maleic acid esters in which instead of the crotonic acid ester or maleate was changed to and the like.

  Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. Etc.

  The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but typical examples include acrylic acid, phthalic acid, and ethylene. Condensates of glycols, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

  In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylate ester are reacted. Urethane (meth) acrylates as obtained; epoxy acrylates such as addition reaction product of polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylenebisacrylamide; diallyl phthalate Allyl esters such as: vinyl group-containing compounds such as divinyl phthalate are useful.

<Other compounding components of photosensitive colored resin composition>
In addition to the above-mentioned components, the photosensitive colored resin composition of the present invention appropriately contains an organic solvent, an adhesion improver, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant, a silane coupling agent, and the like. can do.

(1) Organic solvent Although there is no restriction | limiting in particular as an organic solvent, For example, diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate , N-octane, Valsol # 2, Apco # 18 solvent, diisobutylene, amyl acetate, butyl butyrate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, Socal solvent No. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, butyl acetate (n, sec, t), 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, Amylformate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methylamino 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, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3- Ethoxypropionic acid , Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, dipropylene glycol monomethyl ether, ethylene glycol acetate, ethyl carb Specific organic solvents such as Tol, butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate Can be mentioned.

  The solvent is capable of dissolving or dispersing each component, and it is preferable to select a solvent having a boiling point in the range of 100 to 250 ° C. More preferably, it has a boiling point of 120-170 ° C. These may be used alone or in combination of two or more.

(2) Silane coupling agent A silane coupling agent can be added to improve adhesion to the substrate. Various types of silane coupling agents such as epoxy, methacrylic, amino and the like can be used, and epoxy silane coupling agents are particularly preferable.

<Method for producing photosensitive colored resin composition>
The photosensitive colored resin composition of the present invention is produced according to a conventional method. For example, first, a predetermined amount of each of the color material (C), the solvent, and the dispersant (D) is weighed, and in the dispersion treatment step, the color material is dispersed to obtain a liquid colored 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 fine particles, so that the coating characteristics of the photosensitive colored resin composition are improved, and the transmittance of the product color filter substrate is improved.

  When dispersing the color material, the alkali-soluble resin (A) may be used in combination. For example, when the dispersion treatment is performed 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 for the dispersion treatment is usually set in the range of 0 ° C to 100 ° C, preferably in the range of room temperature to 80 ° C. The dispersion time varies depending on the composition of the ink-like liquid (coloring material, solvent, dispersant), the size of the sand grinder apparatus, and the like.

  The ink-like liquid obtained by the above dispersion treatment is mixed with a solvent, an alkali-soluble resin (A), a photopolymerization initiator (B), and, in some cases, other components other than the above, to obtain a uniform dispersion solution. In addition, in each process of a dispersion | distribution process and mixing, since fine refuse may mix, it is preferable to filter-process the obtained photosensitive colored resin composition with a filter.

<Ingredient compounding amount in photosensitive colored resin composition>
The alkali-soluble resin (A) is usually 5% by weight or more, preferably 10% by weight or more, and usually 85% by weight or less, preferably 80% by weight based on the total solid content of the photosensitive colored resin composition of the present invention. % Or less. When the content of the alkali-soluble resin (A) is remarkably small, the solubility of the unexposed portion in the developer is lowered, and it becomes easy to induce development failure. On the contrary, when there is too much content of alkali-soluble resin (A), the permeability of the developing solution to an exposure part will become high, and the sharpness and adhesiveness of a pixel will deteriorate.

  In the present invention, the “total solid content” means all components other than the solvent, and the total solid content in the photosensitive colored resin composition of the present invention is usually 10% by weight or more and 90% by weight or less. is there.

  The content of the photopolymerization initiator (B) is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 0%, based on the total solid content of the photosensitive colored resin composition of the present invention. 0.7% or more, usually 30% by weight or less, preferably 10% by weight or less. If the content of the photopolymerization initiator (B) is too small, the sensitivity may be lowered. On the other hand, if the content is too large, the solubility of the unexposed portion in the developer is lowered, and development failure is likely to be induced.

  Content of a color material (C) can be normally selected in the range of 1 to 70 weight% with respect to the total solid content in the photosensitive colored resin composition. In this range, 10 to 70% by weight is more preferable, and 20 to 60% by weight is particularly preferable. If the content of the color material (C) is too small, the film thickness with respect to the color density becomes too large, which adversely affects the gap control when forming a liquid crystal cell. Conversely, if the content of the color material (C) is too large, sufficient image forming properties may not be obtained.

  In addition, as a ratio with respect to the coloring material (C) of alkali-soluble resin (A) in the photosensitive coloring resin composition, it is 20 to 500 weight% normally, Preferably it is 30 to 300 weight%, More preferably, it is 50 to 200 weight%. % Range. If the content of the alkali-soluble resin (A) with respect to the color material (C) is too low, the solubility of the unexposed part in the developing solution is lowered, and it is easy to induce development failure. It becomes difficult to obtain.

  The content of the dispersant (D) is usually 50% by weight or less, preferably 30% by weight or less, usually 1% by weight or more, preferably 5% by weight or more in the solid content of the photosensitive colored resin composition. Further, it is usually 5% by weight or more, particularly 10% by weight or more, preferably 200% by weight or less, particularly preferably 80% by weight or less based on the coloring material (C). If the content of the dispersant (D) is too small, sufficient dispersibility cannot be obtained. If the content is too large, the proportion of other components is relatively reduced, and the color density, sensitivity, film formability, and the like are lowered.

  When using a photopolymerizable monomer, the content is 90 weight% or less normally with respect to the total solid of a photosensitive colored resin composition, Preferably it is 80 weight% or less. When there is too much content of a photopolymerizable monomer, the permeability of the developing solution to an exposed part will become high and it will become difficult to obtain a favorable image. In addition, the minimum of content of a photopolymerizable monomer is 0 weight% or more normally, Preferably it is 5 weight% or more.

<Color filter>
(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, silane coupling agents, thin film formation treatment of various resins such as urethane resins, etc. May be performed.

  The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

(2) Black matrix By providing a black matrix on a transparent substrate and usually forming red, green, and blue pixel images, the color filter of the present invention can be produced, and the photosensitive colored resin of the present invention. The composition is used as at least one resist forming coating solution of black, red, green, and blue. For black resist, on the transparent glass substrate glass surface, for red, green and blue, on the resin black matrix forming surface formed on the transparent substrate, or metal black formed using a chromium compound or other light shielding metal material A pixel image of each color is formed on the matrix forming surface by performing coating, heat drying, image exposure, development, and thermosetting.

  The black matrix is formed on a transparent substrate using a light-shielding metal thin film or a photosensitive colored resin composition for resin black matrix. As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide and chromium nitride, nickel and tungsten alloy, etc. are 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 with a positive photoresist, ceric ammonium nitrate, perchloric acid and / or nitric acid are added to chromium. Other materials are etched using an etching solution according to the material, and finally a positive photoresist is stripped with a special stripping agent 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 photosensitive colored resin composition on the thin film, the coating film is exposed and developed using a photomask having a repetitive 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 photosensitive colored resin composition for resin black matrix, the black matrix is formed using the photosensitive colored resin composition of the present invention containing a black coloring material. For example, black color material such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black or the like, or red, green, blue or 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 photosensitive colored resin composition containing a black color material by mixing.

(3) Pixel formation (application of photosensitive colored resin composition)
A photosensitive colored resin composition containing a color material of one of red, green, and blue is applied on a transparent substrate provided with a black matrix, dried, and a photomask is layered on the coating film. A pixel image is formed through image exposure, development, and thermal curing or photocuring as necessary through a mask to create a colored layer. A color filter image can be formed by performing this operation for each of the three colored photosensitive colored resin compositions of red, green, and blue.

  The photosensitive colored 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. In particular, the die coating method significantly reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. To preferred.

  If the thickness of the coating film is too thick, pattern development becomes difficult, and it may be difficult to adjust the gap in the liquid crystal cell forming process. May become impossible. The thickness of the coating film is preferably in the range of 0.2 to 20 μm, more preferably in the range of 0.5 to 10 μm, and still more preferably in the range of 0.5 to 5 μm, as the film thickness after drying. It is a range.

(Drying the coating)
The coating film after the photosensitive 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. Drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected in a range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably 50 to 130 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes.

  The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. 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, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.

(exposure)
Image exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive colored resin composition and irradiating an ultraviolet or visible light source through the mask pattern. At this time, if necessary, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film 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.

(developing)
The color filter according to the present invention is a film formed of a photosensitive colored resin composition, image-exposed with the above light source, and then developed with an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. An image can be formed on a substrate. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

  Examples of 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 may be used alone or in a mixture with an aqueous solution.

  There are no particular limitations on the conditions for the development treatment, and usually the development temperature is in the range of 10 to 50 ° C., especially 15 to 45 ° C., particularly preferably 20 to 40 ° C. The development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.

(Thermosetting)
The color filter substrate after development is subjected to thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes. 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.

(Formation of transparent electrode)
Color filters are used as part of parts such as color displays and liquid crystal displays by forming transparent electrodes such as ITO on the image as they are, but they are necessary to improve surface smoothness and durability. Accordingly, a top coat layer such as polyamide or polyimide can be provided on the image. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

<Liquid crystal display device>
A liquid crystal display device usually forms an alignment film on a color filter, spreads spacers on the alignment film, and then bonds to a counter substrate to form a liquid crystal cell, injects liquid crystal into the formed liquid crystal cell, Complete by connecting to the counter electrode. As the alignment film, a resin film such as polyimide is suitable. 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 be processed into a surface state in which the tilt of the liquid crystal can be adjusted.

  As the spacer, a spacer having a size corresponding to the gap (gap) with the counter substrate is used, and usually a spacer having a size of 2 to 8 μm is preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter substrate by photolithography, 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 to 8 μm. 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 reduced pressure in the liquid crystal cell is usually 1 × 10 ⁻² to 1 × 10 ⁻⁷ Pa, preferably 1 × 10 ⁻³ to 1 × 10 ⁻⁶ Pa. Moreover, it is preferable to heat a liquid crystal cell at the time of pressure reduction, and heating temperature is 30-100 degreeC normally, More preferably, it is 50-90 degreeC. The warming hold during decompression is usually in the range of 10 to 60 minutes, 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 is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of lyotropic liquid crystal, thermotropic liquid crystal, 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 synthesis 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, “part” represents “part by weight”.

<Synthesis Example 1>
“NC3000” manufactured by Nippon Kayaku Co., Ltd. (in the general formula (1), P = H, R = H, n = 1 to 7, weight average molecular weight 1900, epoxy equivalent 288) 400 parts, acrylic acid 102 parts, 0.3 parts of p-methoxyphenol, 5 parts of triphenylphosphine, and 264 parts of propylene glycol monomethyl ether acetate were charged into a reaction vessel and stirred at 95 ° C. until the acid value became 3 mg-KOH / g or less. It took 9 hours for the acid value to reach the target (acid value 2.2). Subsequently, 151 parts of tetrahydrophthalic anhydride was further added and reacted at 95 ° C. for 4 hours to obtain an alkali-soluble resin (AI) solution having an acid value of 102 and a polystyrene-equivalent weight average molecular weight of 3200 measured by GPC.

<Synthesis Example 2>
180 parts of “NC3000” manufactured by Nippon Kayaku Co., Ltd., 54.9 parts of methacrylic acid, 0.2 part of p-methoxyphenol, 2.4 parts of triphenylphosphine, and 124 parts of propylene glycol monomethyl ether acetate were charged in a reaction vessel. The mixture was stirred at 95 ° C. until the acid value became 5.0 mg-KOH / g or less. It took 10 hours for the acid value to reach the target (acid value 5.0). Next, 96 parts of tetrahydrophthalic anhydride was further added and reacted at 95 ° C. for 4 hours to obtain an alkali-soluble resin (A-II) solution having an acid value of 121 and a weight average molecular weight of 3200 in terms of polystyrene measured by GPC.

<Synthesis Example 3>
32 g of tolylene diisocyanate trimer (Mittech GP750A manufactured by Mitsubishi Chemical Co., Ltd., resin solid content 50% by weight, butyl acetate solution) and 0.02 g of dibutyltin laurate as a catalyst with 47 g of propylene glycol monomethyl ether acetate Diluted and dissolved. Under agitation, 14.4 g of polyethylene glycol having a number average molecular weight of 1000 having a methoxy group at one end (“Uniox M-1000” manufactured by NOF Corporation) and polypropylene glycol having a number average molecular weight of 1000 (Sanyo Kasei) A mixture of 9.6 g of “SANNICS PP-1000” manufactured by Kogyo Co., Ltd. was added dropwise, and the mixture was further reacted at 70 ° C. for 3 hours. Next, 1 g of N, N-dimethylamino-1,3-propanediamine was added, and the mixture was further reacted at 40 ° C. for 1 hour to obtain a urethane polymer dispersant (DI). The amine value of the solution containing the polymer dispersant (D-I) thus obtained was determined by neutralization titration and found to be 14 mg-KOH / g. The resin content was 40% by weight as determined by the dry-up method (at 150 ° C. for 30 minutes, the solvent was removed on a hot plate, and the resin concentration was calculated from the weight change). Moreover, the weight average molecular weight in GPC was 24,000.

<Example 1>
49 parts by weight (35 parts by weight in terms of solid content) of the alkali-soluble resin (AI) solution obtained in Synthesis Example 1, 5 parts by weight of dipentaerythritol hexaacrylate, “CGI-124” (Ciba Specialty Chemical) (The structural formula is as follows.) 4 parts by weight, 224 parts of a carbon black dispersion solution dispersed using the urethane polymer dispersant (D-I) obtained in Synthesis Example 3 (solid content) 56 parts by weight of conversion, of which 43 parts by weight of carbon black and 13 parts by weight of polymer dispersant) were mixed with 218 parts by weight of propylene glycol monomethyl ether acetate to obtain a photosensitive black resin composition.

  The photosensitive black resin composition thus obtained was spin-coated on a 10 cm square glass substrate and dried on a hot plate at 90 ° C. for 150 seconds. The film thickness after drying was 1 μm. Next, this sample was image-exposed with a high-pressure mercury lamp through a mask, and then subjected to spray development using a KOH aqueous solution at a temperature of 23 ° C. and a concentration of 0.1% by weight to form a black pixel (black matrix).

<Example 2>
In Example 1, a black pixel was formed by performing the same treatment as in Example 1 except that the alkali-soluble resin (AI) was changed to the alkali-soluble resin (A-II).

<Example 3>
A black pixel was obtained by performing the same treatment as in Example 1 except that the polymer dispersant (D-I) was changed to the following commercially available acrylic polymer dispersant (D-II) in Example 1. Formed.
Dispersant (D-II): having a block structural unit derived from a methacrylic acid ester (B block) and a block structural unit derived from a monomer having a quaternary ammonium base having the following structure in the side chain derived from methacrylic acid (A block) A polymer dispersant containing an AB block copolymer. An amine value of 29 and an acid value of 19. Moreover, the weight average molecular weight in GPC was 10,000.

<Comparative Example 1>
Example 1 is the same as Example 1 except that the alkali-soluble resin (AI) is changed to “EA4805” (cresol novolak-type epoxy acrylate tetrahydrophthalic anhydride adduct. Acid value 100) manufactured by Mitsubishi Chemical Corporation. Similar processing was performed to form black pixels.

  The photosensitive black resin compositions prepared in Examples 1 to 3 and Comparative Example 1 and the formed pixels were evaluated on the following items, and the results are shown in Table 1.

<Adhesion>
The minimum pattern size of a resist that can be resolved at an exposure amount that faithfully reproduces a 20 μm mask pattern was observed with a microscope at a magnification of 200 times. The minimum pattern dimension was 10 μm or less, and the adhesion was ◯, and the one exceeding 10 μm was rated as x.

<Pixel sharpness>
The shape of the fine black pixel at an exposure amount that faithfully reproduces a 20 μm mask pattern was observed with a microscope at a magnification of 1000 times. Those having good linearity are indicated by sharpness ◯, and resist patterns having protrusions and irregularities are indicated by ×.

<Storage stability>
The photosensitive black resin composition was stored at 35 ° C. for 2 weeks, and the storage stability was evaluated based on the change in viscosity.

Claims (6)

Alkali-soluble resin (A) obtained by further reacting a reaction product of epoxy resin (a) with unsaturated group-containing carboxylic acid (b) with polybasic acid and / or anhydride (c) thereof, photopolymerization initiator In the photosensitive colored resin composition for color filters containing (B), the color material (C), and the dispersant (D), the epoxy resin (a) is represented by the following general formula (1). A photosensitive colored resin composition for a color filter.

(In the formula, n represents an average value and represents a number of 0 to 10. P and R each represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group. May be the same as or different from each other, and G represents a glycidyl group.)   The photosensitive coloring resin composition for a color filter according to claim 1, wherein the dispersant (D) contains a polymer dispersant.   The photosensitive coloring resin composition for a color filter according to claim 1 or 2, wherein the dispersant (D) contains a pigment derivative.   The photosensitive colored resin composition for a color filter according to any one of claims 1 to 3, which is a photosensitive colored resin composition for a resin black matrix of a color filter.   The color filter which has the pixel formed using the photosensitive coloring resin composition of any one of Claim 1 thru | or 4 on the transparent substrate.   A liquid crystal display device using the color filter according to claim 5.