TWI449968B - Photosensitive coloring resin composition for color filter, color filter, liquid-crystal display device and organic el display - Google Patents

Description

Photosensitive coloring resin composition for color filter, color filter, liquid crystal display device and organic EL display

The present invention relates to a photosensitive colored resin composition for a color filter, a color filter, a liquid crystal display device, and an organic EL display. Specifically, it is excellent in image formability even when the colorant concentration is high, and the balance between sensitivity and solubility is excellent, and the photosensitive coloring resin for color filters excellent in sharpness and adhesion of the pixel edge is obtained. Composition, and its use.

Conventionally, as a method of producing a color filter using a pigment, there are a dyeing method, an electrocoating method, an inkjet method, a pigment dispersion method, and the like.

When a color filter is produced by a pigment dispersion method, a binder resin, a photopolymerization initiator, a photopolymerizable monomer, and the like are usually added to a colored resin composition obtained by dispersing a pigment by a dispersant or the like. Photosensitive to form a photosensitive colored resin composition, which is applied onto a glass substrate and dried, and then exposed to light using a photomask to develop a color pattern, and then the pattern is solidified by heating it. Forming pixels. These steps are repeated for each color to form a color filter.

The photosensitive colored resin composition used for image formation of the color filter described above is required to have sufficient resolution, good adhesion to a substrate, and low development residue. Further, in recent years, a pixel having a high color density or a resin black matrix having a high optical density is required. Therefore, the photosensitive colored resin composition is required to contain a large amount of a pigment such as a pigment or carbon black, and the above characteristics are excellent.

The photosensitive resin composition is generally supplied to the coating. dry. exposure. In the photolithography step of the step of developing, in these steps, it is generally required that no residue or scum is generated in the removed portion in the developing step; the removed portion has sufficient solubility; and the sharpness of the edge of the pattern is improved. Pixel formation. However, when a pixel or a black matrix (hereinafter, referred to as "pattern") is formed using the photosensitive colored resin composition having a high color toner content, it is easy to remarkably exhibit the following problem: in the developing step, Residue or scum is generated on the substrate of the unexposed portion; good solubility of the unexposed portion is not obtained; the sharpness of the edge of the pattern is poor; the light hardening of the exposed portion is insufficient, and the surface smoothness is poor.

In particular, the resin black matrix contains a black colorant and has a light-shielding property in a wide wavelength region, so that the following phenomenon becomes a big problem: (1) it is obviously difficult to enlarge the difference in crosslink density between the exposed portion and the unexposed portion; (2) The difference in the crosslink density in the film thickness direction is also generated in the exposed portion, that is, it is hard to be hardened on the side of the base surface even if it is sufficiently hardened on the side of the light-irradiated surface; (3) The developing solution contains a large amount of Since it is insoluble black coloring material, it is difficult to obtain high developability and the like.

Therefore, in order to solve the above problem, a photosensitive colored resin composition using a novolak epoxy acrylate resin having a carboxyl group as a binder resin has been proposed (see Patent Document 1). However, according to the study by the inventors of the present invention, it has been found that the use of the binder resin causes a problem that the balance between solubility and sensitivity is not sufficient, so that the developer is infiltrated into the exposed portion while being dissolved in the unexposed portion. The linearity of the edge portion of the pattern is low; the adhesion between the pattern and the substrate is not sufficient.

Further, it is proposed to use an acrylic resin having a carboxyl group and an alicyclic ring. The reactant of the oxy unsaturated compound is used as a photosensitive resin composition of the binder resin (see Patent Document 2). However, according to the study by the inventors of the present invention, it has been found that when the binder resin is used, there is a problem that the sensitivity is insufficient, and therefore the adhesion of the pattern on the substrate is poor, and it is difficult to form a high-definition pattern.

Further, Patent Document 3 discloses the use of a photosensitive filter using an epoxy resin represented by the following formula (1), a reaction product of an unsaturated group-containing carboxylic acid, and a polycarboxylic acid anhydride as a binder resin. A colored resin composition (refer patent document 3). The composition described in this document is excellent in adhesion to a substrate, sharpness of a pattern edge, and storage stability, but there is still room for improvement in sensitivity.

(wherein, n represents an average value, and represents a number of 0 to 10. P and R each represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and each of P and R may be the same as each other. It can also be different. G stands for epoxypropyl.)

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

An object of the present invention is to provide an image forming property which is excellent even when a toner concentration is high, and a balance between sensitivity and solubility is excellent, and further, a pixel side a photosensitive coloring resin composition for a color filter excellent in sharpness and adhesion, a color filter using the photosensitive colored resin composition, and a liquid crystal display device using the color filter and Organic EL display.

The inventors of the present invention have intensively studied and found that the above problems can be solved by using a binder resin having a predetermined structure and a high molecular weight, and the present invention has been completed.

That is, the present invention is as follows.

[1] A photosensitive colored resin composition for a color filter comprising a reaction of an epoxy resin (a) represented by the following formula (1-a) and a carboxylic acid (b) containing an unsaturated group; An alkali-soluble resin (A) which is obtained by further reacting a polybasic acid and/or an anhydride thereof (c) with an alkali-soluble resin (A), a photopolymerization initiator (B), and a colorant (C). The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC, Gel Permeation Chromatography) is 3,300 or more and 50,000 or less.

[In the above formula (1-a), n represents an average value, and represents a number of 0 to 10. R ⁴¹ represents a hydrogen atom, a halogen atom, the carbon atoms of the alkyl group having 1 to 8 carbon atoms of a cycloalkyl group having 3 to 10, a phenyl group, a naphthyl group or any one of biphenyl. Furthermore, the plurality of R ⁴¹ present in one molecule may be the same or different. G represents an epoxy propyl group. ]

[2] The photosensitive colored resin composition for a color filter according to [1], which further comprises a dispersing agent (D).

[3] The photosensitive colored resin composition for a color filter according to [1] or [2], further comprising a photopolymerizable monomer (E).

[4] The photosensitive colored resin composition for a color filter according to any one of [1] to [3] further comprising an alkali-soluble resin (A'), the alkali-soluble resin (A') An α,β-unsaturated monocarboxylic acid ester having an epoxy compound (a') represented by the following formula (1-a') and an α,β-unsaturated monocarboxylic acid and/or a carboxyl group in an ester moiety The reactant of (b') is obtained by reacting with a polybasic acid and/or its anhydride (c').

In the above formula (1-a'), p and q each independently represent an integer of 0 to 4, and R ³¹ and R ³² each independently represent an alkyl group or a halogen atom. R ³³ and R ³⁴ each independently represent an alkylene group. x and y each independently represent an integer of 0 or more. ]

[5] The photosensitive colored resin composition for a color filter according to any one of [1] to [4] further comprising an alkali-soluble resin (A"), the alkali The soluble resin (A") is a reaction product of an epoxy compound (a") represented by the following formula (1-a") and a carboxylic acid (b") containing an unsaturated group, and a polybasic acid and/or It is obtained by reacting an anhydride (c").

In the above formula (1-a"), X represents a linking group represented by the following formula (2a), (2b) or (3), wherein the molecular structure includes one or more adamantane structures. An integer of 2 or 3. (In the above formulae (2a) and (2b), R ¹ to R ⁴ and R ¹³ to R ¹⁵ each independently represent an adamantyl group which may have a substituent, a hydrogen atom, and a carbon number which may have a substituent of 1~ The alkyl group of 12 or a phenyl group which may have a substituent. In the above formula (3), R ⁵ to R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or may have a phenyl group of a substituent. Y represents a divalent linking group containing an adamantane structure which may have a substituent. In the above formulae (2a), (2b) and (3), * represents a formula (1-a" The bonding site of the epoxy propoxy group.)]

[6] The photosensitive colored resin composition for a color filter according to [5], wherein the polybasic acid and/or its anhydride (c") contains the following (i) and (ii).

(i) {tetrabasic acid and / or its anhydride} and / or {dibasic acid and / or its anhydride} (ii) a tribasic acid and/or its anhydride.

[7] The photosensitive colored resin composition for a color filter according to any one of [1] to [6] further comprising an alkali-soluble resin (A1"), the alkali-soluble resin (A1") Mixing the epoxy compound (a") represented by the following formula (1-a") with the carboxylic acid (b") containing an unsaturated group with a polyol (d") to make the mixture and the mixture It is obtained by reacting an acid and/or its anhydride (c").

In the above formula (1-a"), X represents a linking group represented by the following formula (2a), (2b) or (3), wherein the molecular structure includes one or more adamantane structures. An integer of 2 or 3. [Chem. 7] (In the above formulae (2a) and (2b), R ¹ to R ⁴ and R ¹³ to R ¹⁵ each independently represent an adamantyl group which may have a substituent, a hydrogen atom, and a carbon number which may have a substituent of 1~ The alkyl group of 12 or a phenyl group which may have a substituent. In the above formula (3), R ⁵ to R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or may have a phenyl group of a substituent. Y represents a divalent linking group containing an adamantane structure which may have a substituent. In the above formulae (2a), (2b) and (3), * represents a formula (1-a" The bonding site of the epoxy propoxy group.)]

[8] The photosensitive colored resin composition for a color filter according to any one of [7], wherein the polybasic acid and/or its anhydride (c") contains the following (i) and (ii).

(i) {tetrabasic acid and / or its anhydride} and / or {dibasic acid and / or its anhydride} (ii) a tribasic acid and/or its anhydride.

[9] The photosensitive colored resin composition for a color filter according to any one of [1] to [8] wherein the photopolymerization initiator (B) contains an oxime ester derivative.

[10] The photosensitive colored resin composition for a color filter according to any one of [1] to [9] wherein the content of the colorant (C) is based on the photosensitive colored resin The total solid content of the composition is 20 to 60% by weight.

[11] The photosensitive colored resin composition for a color filter according to any one of [1] to [10] wherein the color material (C) contains a black colorant.

[12] A color filter comprising a pixel or a black matrix formed of the photosensitive colored resin composition for a color filter according to any one of [1] to [11] on a transparent substrate.

[13] A liquid crystal display device produced by using the color filter of [12].

[14] An organic EL display produced by using the color filter of [12].

The photosensitive colored resin composition for a color filter of the present invention has high sensitivity and good adhesion to a substrate, and is excellent in balance between sensitivity and solubility even when a pigment such as a pigment or carbon black is contained at a high concentration. Further, the pixel edge is excellent in sharpness and adhesion, and has high resolution, and can form high-definition pixels. According to the present invention, by using the photosensitive colored resin composition for a color filter described above, a high-quality color filter can be obtained, and a high-quality liquid crystal display device and an organic EL display can be provided.

The embodiments of the present invention are specifically described below, but the present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention.

In the present invention, "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid", and "(meth)acrylate" and "(meth)acrylylene group" are also the same. Further, "(poly)hydroxyl" means "hydroxyl and/or polyhydroxyl".

In the present invention, "total solid content" means photosensitive coloring for color filters All components other than the solvent contained in the resin composition or the ink described later.

In the present invention, the weight average molecular weight means a weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography).

In the present invention, the "amine value" is a value expressed by the weight of KOH equivalent to the amount of alkali of the solid content per 1 g of the dispersant, unless otherwise specified. Furthermore, the measurement method will be described later.

[Photosensitive Colored Resin Composition for Color Filters]

The photosensitive colored resin composition for a color filter of the present invention (hereinafter sometimes referred to as "photosensitive colored resin composition" or "colored resin composition") contains an alkali-soluble resin (A) photopolymerization initiator ( B) and the coloring material (C) as an essential component, preferably further containing a dispersing agent (D) and a photopolymerizable monomer (E), and further containing a binder resin other than the alkali-soluble resin (A) (F) Or an organic solvent, a viscosity improving agent, a coating property improving agent, a development improving agent, a UV absorber, an antioxidant, a decane coupling agent, a surfactant, a pigment derivative, and the like, usually, an alkali-soluble resin ( A), photopolymerization initiator (B), colorant (C), and each as needed The materials are used in a state of being dissolved or dispersed in an organic solvent.

<alkali soluble resin (A)>

The alkali-soluble resin (A) is obtained by reacting a predetermined epoxy resin (a) with a reaction product of an unsaturated group-containing carboxylic acid (b) with a polybasic acid and/or an anhydride (c).

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

[In the above formula (1-a), n represents an average value, and represents a number of 0 to 10. R ⁴¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. Furthermore, the plurality of R ⁴¹ present in one molecule may be the same or different. G represents an epoxy propyl group. ]

R ⁴¹ in the formula (1-a) represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group or a biphenyl group. In the case of sensitivity and solubility, R ^{41 is} particularly preferably a hydrogen atom or a methyl group. Furthermore, the plurality of R ⁴¹ present in one molecule may be the same or different.

The epoxy resin (a) represented by the above formula (1-a) can be represented, for example, by the following formula (1-a-1) by the presence of an alkali metal hydroxide. It is obtained by reacting with an epihalohydrin.

(wherein n and R ⁴¹ represent the same as in the formula (1-a).)

The compound represented by the above formula (1-a-1) can be obtained, for example, by subjecting a compound represented by the following formula (1-a-2) to a phenol by a condensation reaction in the presence of an acid catalyst.

(wherein Z represents a halogen atom, a hydroxyl group or a lower alkoxy group. R ⁴¹ represents the same as in the above formula (1-a).)

In the Z of the above formula (1-a-2), preferred examples of the halogen atom include a chlorine atom and a bromine atom, and as the lower alkoxy group, a preferred group is a methoxy group or an ethoxy group. The alkoxy group having a carbon number of 1 to 4 is used.

On the other hand, the term "phenol" refers to an aromatic compound having one phenolic hydroxyl group in one molecule, and specific examples thereof include phenol, cresol, phenol, n-propanol, isobutyl phenol, and third butyl. Phenol, octylphenol, xylenol, methyl butyl phenol, di-tert-butyl phenol, etc., representative ortho, meta- or para-isomers of alkylphenols; or cyclopentyl phenol, cyclohexyl phenol, The cyclopentyl phenol or the like which is a representative example of a cycloalkylphenol or a phenylphenol can be exemplified by the substituted phenol which is substituted as the group of R ⁴¹ in the above formula (1-a). These phenols may be used alone or in combination of two or more.

When the condensation reaction is carried out, the amount of the phenol used is preferably from 0.5 to 20 mol, particularly preferably from 2 to 15 mol, based on 1 mol of the compound represented by the formula (1-a-2).

It is preferred to use an acid catalyst in the above condensation reaction, and various ones can be used as the acid catalyst, and preferred are: hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminum chloride, zinc chloride. Etc., especially p-toluenesulfonic acid, sulfuric acid, hydrochloric acid. The amount of the acid catalyst to be used is not particularly limited, and it is preferably 0.1 to 30% by weight based on the compound represented by the formula (1-a-2).

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

After the reaction is completed, the neutralization treatment or the water washing treatment is carried out to adjust the pH of the product to 3 to 7, preferably to 5 to 7. For the water washing treatment, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkaline earth metal hydroxide such as calcium hydroxide or magnesium hydroxide, ammonia, sodium dihydrogen phosphate, further diethylenetriamine or triethylamine is used. Various alkaline substances such as an organic amine such as tetraamine, aniline or phenylenediamine may be treated as a neutralizing agent. Further, the water washing treatment may be carried out in accordance with a usual method. For example, the following method can be employed: adding to the reaction mixture The water of the above neutralizing agent is dissolved, and the liquid separation extraction operation is repeated.

After the neutralization treatment or the water washing treatment, the unreacted dihydroxybenzenes and the solvent are distilled off under reduced pressure, and the product is concentrated to obtain the compound represented by the above formula (1-a-1).

As a method of obtaining the epoxy resin (a) of the present invention represented by the above formula (1-a), a known method can be employed as the compound represented by the above formula (1-a-1). For example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to a dissolved mixture of a compound represented by the formula (1-a-1) and an excess of epihalohydrin such as epichlorohydrin or epibromohydrin. Alternatively, the epoxy resin (a) represented by the formula (1-a) can be obtained by reacting at a temperature of 20 to 120 ° C for 1 to 10 hours while being added.

In the reaction for obtaining the epoxy resin (a), an alkali metal hydroxide may also be used as an aqueous solution. In this case, it may be a method of continuously adding the alkali metal hydroxide to the reaction system. The aqueous solution is continuously distilled off under reduced pressure or under normal pressure to remove water and epihalohydrin, and liquid separation is carried out to remove water, and the epihalohydrin is continuously returned to the reaction system.

Further, a method of adding tetramethylammonium chloride, tetramethylammonium bromide, or trimethyl group to the dissolved mixture of the compound represented by the above formula (1-a-1) and epihalohydrin may be used. a quaternary ammonium salt such as benzyl ammonium chloride is used as a catalyst, and is reacted at 50 to 150 ° C for 1 to 5 hours to obtain a halogenated alcohol of the compound represented by the formula (1-a-1). A solid or an aqueous solution of an alkali metal hydroxide is added to the etherified product, and the reaction is again carried out at a temperature of 20 to 120 ° C for 1 to 10 hours to carry out dehydrohalogenation (closed loop).

The amount of epihalohydrin used in the above reaction is relative to 1 equivalent of The hydroxyl group of the compound represented by the formula (1-a-1) is usually 1 to 20 moles, preferably 2 to 10 moles. Further, the amount of the alkali metal hydroxide to be used is usually 0.8 to 15 moles, preferably 0.9 to 11 moles per 1 equivalent of the hydroxyl group of the compound represented by the formula (1-a-1).

Further, in order to allow the reaction to proceed smoothly, a reaction such as an aprotic polar solvent such as dimethylhydrazine or dimethylhydrazine may be added in addition to an alcohol such as methanol or ethanol. When an alcohol is used, the amount thereof is 2 to 20% by weight, preferably 4 to 15% by weight based on the amount of the epihalohydrin. Further, when an aprotic polar solvent is used, the amount thereof is from 5 to 100% by weight, preferably from 10 to 90% by weight, based on the amount of the epihalohydrin.

After the reaction product of the epoxidation reaction is washed with water or not washed with water, the epihalohydrin and other solvent are added under heating and reduced pressure, for example, at 110 to 250 ° C and a pressure of 1.3 kPa (10 mmHg) or less. After removal, the target epoxy resin (a) is obtained.

Further, in order to obtain an epoxy resin having less hydrolyzable halogen, the obtained epoxy resin is redissolved in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added thereto. The reaction is carried out with an aqueous solution, and the closed loop can also be made. In this case, the amount of the alkali metal hydroxide used is preferably 0.01 to 0.3 mol per 1 equivalent of the hydroxyl group of the compound represented by the formula (1-a-1) used for the epoxidation. Very good is 0.05~0.2 m. The reaction temperature is 50 to 120 ° C, and the reaction time is usually 0.5 to 2 hours.

After the completion of the reaction, the salt formed is removed by filtration, washing with water, or the like, and a solvent such as toluene or methyl isobutyl ketone is distilled off under heating and reduced pressure. The epoxy resin (a) represented by the above formula (1-a) can be obtained.

(2) Carboxylic acid containing an unsaturated group (b) The unsaturated carboxylic acid (b) containing an unsaturated group may, for example, be an unsaturated carboxylic acid having an ethylenically unsaturated double bond, and specific examples thereof include (meth)acrylic acid, crotonic acid, o-, m-, p-ethylene. a monocarboxylic acid such as an α-haloalkyl group, an alkoxy group, a halogen, a nitro group or a cyano substituent of (meth)acrylic acid; 2-(meth)acryloxyethyl succinate; 2-propenyloxyethyl adipate, 2-(methyl)propenyloxyethyl phthalate, 2-(methyl)propenyloxyethyl hexahydrophthalate, maleic acid 2 -(Meth)propylene methoxyethyl ester, 2-(methyl) propylene methoxy propyl succinate, 2-(methyl) propylene methoxy propyl adipate, tetrahydro phthalic acid 2- (Meth) propylene methoxy propyl ester, 2-(methyl) propylene methoxy propyl phthalate, 2-(methyl) propylene methoxy propyl maleate, 2- succinic acid Methyl) propylene decyl butyl acrylate, 2-(methyl) propylene decyl butyl acrylate, 2-(methyl) propylene decyl hydride, 2-(methyl) phthalate Propylene oxybutyl acrylate, 2-(methyl) propylene decyl butyl methoxide; addition to (meth) acrylate a monomer such as a lactone such as caprolactone, β-propiolactone, γ-butyrolactone or δ-valerolactone; or a hydroxyalkyl (meth) acrylate or pentaerythritol tri(methyl) A monomer obtained by adding an acid (anhydride) such as succinic acid (anhydride), citric acid (anhydride) or maleic acid (anhydride) to the acrylate; a (meth)acrylic acid dimer or the like.

In terms of sensitivity, among these, (meth)acrylic acid is particularly preferred. These may be used alone or in combination of two or more.

(3) Reaction of epoxy resin (a) with carboxylic acid (b) containing an unsaturated group As the epoxy group in the epoxy resin (a) and the carboxylic acid having an unsaturated group (b) A method of the reaction, and a known method can be used. For example, a tertiary amine such as triethylamine or benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride or benzyltriethylchloride may be used. A quaternary ammonium salt such as ammonium, pyridine, triphenylphosphine or the like as a catalyst, and an epoxy resin (a) and an unsaturated group-containing carboxylic acid (b) in an organic solvent at a reaction temperature of 50 to 150 ° C The reaction is carried out for several hours to several tens of hours to thereby add a carboxylic acid to the epoxy resin.

The amount of the catalyst used is preferably 0.01 to 10% by weight, particularly preferably 0.3 to 5, based on the reaction raw material mixture (the total of the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b)). weight%.

Further, in order to prevent polymerization in the reaction, it is preferred to use a polymerization inhibitor (for example, p-methoxyphenol, hydroquinone, methyl hydroquinone, p-methoxyphenol, pyrogallol, third butyl). Catechol, phenothiphenyl And the amount thereof is preferably 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight, based on the reaction raw material mixture.

The proportion of the carboxylic acid (b) containing an unsaturated group in the epoxy group of the epoxy resin (a) is usually from 90 to 100 mol%. Since the residual of the epoxy group adversely affects the storage stability, it is preferred that the epoxy group containing the unsaturated group (b) is usually from 0.8 to 1.5 equivalents per equivalent of the epoxy group (a). In particular, the reaction is carried out at a ratio of 0.9 to 1.1 equivalents.

(4) a polybasic acid and/or its anhydride (c) as a polybasic acid and/or an anhydride thereof added to a hydroxyl group of a reactant of the epoxy resin (a) and a carboxylic acid (b) containing an unsaturated group (c) As the known one, maleic acid, succinic acid, itaconic acid, citric acid, tetrahydrofurfuric acid, hexahydrononanoic acid, methyl endomethylenetetrahydrofurfuric acid, chlorine can be used. Acid, methyltetrahydrofurfuric acid, 5-nor Aceene-2,3-dicarboxylic acid, methyl-5-lower a dicarboxylic acid such as a olefin-2,3-dicarboxylic acid or an anhydride thereof; a polyvalent carboxylic acid such as trimellitic acid, pyromellitic acid, diphenylketonetetracarboxylic acid or biphenyltetracarboxylic acid or an anhydride thereof. Among them, tetrahydrophthalic anhydride or succinic anhydride is preferred. These may be used alone or in combination of two or more.

The addition ratio of the polybasic acid and/or its anhydride (c) is usually 10 to 100 mol% of the hydroxyl group formed when the carboxylic acid (b) containing an unsaturated group is added to the epoxy resin (a). It is preferably 20 to 100% by mole, more preferably 30 to 100% by mole. If the addition ratio is too large, the residual film ratio at the time of development is lowered. If the addition ratio is too small, the solubility is insufficient or the adhesion to the substrate is insufficient.

A known method can be employed as a method of adding a polyvalent acid and/or an anhydride (c) to the epoxy resin (a) after adding the unsaturated group-containing carboxylic acid (b).

Further, in the present invention, after the polybasic acid and/or its anhydride (c) is added thereto, the epoxy group-containing compound (d) may be added to a part of the generated carboxyl group. In this case, in order to increase the photosensitivity, a glycidyl (meth)acrylate, a 3,4-epoxycyclohexyl (meth)acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added. An epoxy group-containing unsaturated compound is used as the epoxy group-containing compound (d), and in order to improve developability, a glycidyl ether compound having no polymerizable unsaturated group may be added, or the compound may be used in combination. Both. Specific examples of the epoxy propyl ether compound having no polymerizable unsaturated group include a epoxidized propyl ether compound having a phenyl group or an alkyl group (manufactured by NAGASE Chemical Industries, Ltd., trade name: DENACOL EX-111) , DENACOL EX-121, DENACOL EX-141, DENACOL EX-145, DENACOL EX-146, DENACOL EX-171, DENACOL EX-192), etc.

The alkali-soluble resin (A) of the present invention may be obtained by further reacting the above-mentioned epoxy resin (a) with a reaction product of an unsaturated group-containing carboxylic acid (b) with a polybasic acid and/or an anhydride thereof (c). A resin obtained by adding the above-mentioned epoxy group-containing compound (d) to a part of the carboxyl group of the resin.

(5) Physical properties of alkali-soluble resin (A), etc. The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the alkali-soluble resin (A) used in the present invention is usually 3,300 or more, preferably 3,500 or more, usually 50,000 or less, preferably 30,000 or less, more preferably 10,000 or less. When the weight average molecular weight of the alkali-soluble resin (A) is too small, the sensitivity is poor, and if it is too large, the solubility in the developer is insufficient, which is not preferable.

Thus, in the present invention, the sensitivity of the photosensitive colored resin composition containing the alkali-soluble resin (A) can be remarkably improved by using the alkali-soluble resin (A) having a relatively large molecular weight as compared with the conventional resin having the same skeleton. . The details of the mechanism for improving the sensitivity are not clear. However, it can be inferred from the following: (1) Usually, a part of the polymer which is subjected to high molecular weight by photopolymerization is quantitatively quantified in advance (before photopolymerization). This substantially increases the efficiency of photopolymerization; and (2) the basic skeleton is made of a higher molecular weight, so that the resistance to the developer becomes higher.

Further, the acid value of the alkali-soluble resin (A) used in the present invention (mgKOH/g) is usually 10 or more, preferably 50 or more, usually 200 or less, preferably 150 or less. When 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, the curability is insufficient and the surface properties of the coating film tend to be deteriorated.

<Other binder resin (F)>

In the photosensitive colored resin composition of the present invention, one of the alkali-soluble resin (A) may be partially replaced with another binder resin (F). That is, the alkali-soluble resin (A) and other binder resins may be used in combination.

The other binder resin (F) which can be used in combination with the alkali-soluble resin (A) is not particularly limited as long as the properties of the present invention are not impaired, and the resin is usually used in a photosensitive colored resin composition for a color filter. You can choose it. For example, a binder resin or the like described in JP-A-2007-316620, JP-A-2007-316620, and JP-A-2007-334290, etc., is particularly preferable as described below. An alkali-soluble resin (A'), an alkali-soluble resin (A"), and an alkali-soluble resin (A1").

Further, the other binder resins (F) may be used singly or in combination of two or more.

(1) alkali-soluble resin (A'): an epoxy compound (a') represented by the following formula (1-a') and a carboxyl group of an α,β-unsaturated monocarboxylic acid and/or an ester moiety a reaction product of an α,β-unsaturated monocarboxylic acid ester (b'), an alkali-soluble resin (A') obtained by reacting a polybasic acid and/or an anhydride thereof (c')

[11]

In the above formula (1-a'), p and q each independently represent an integer of 0 to 4, and R ³¹ and R ³² each independently represent an alkyl group or a halogen atom. R ³³ and R ³⁴ each independently represent an alkylene group. x and y each independently represent an integer of 0 or more. ]

(1-1) Epoxy compound (a') represented by the formula (1-a') First, the epoxy compound (a') represented by the above formula (1-a') (hereinafter sometimes referred to as "(a') component)" will be described.

In the above formula (1-a'), the alkyl group of R ³¹ and R ³² is preferably an alkyl group having 1 to 10 carbon atoms, and examples of the halogen atom include Cl, Br, and F. R ³¹ and R ^{32 are} particularly preferably an alkyl group having 1 to 5 carbon atoms.

The mechanism of action of the alkyl group and the halogen atom of R ³¹ and R ³² is not known in detail, and it is presumed that the three-dimensional structure of the molecule is affected, and the ease of dissolution of the developer is controlled.

Therefore, from the above viewpoints, p and q in the above formula (1-a') each independently represent an integer of 0 to 4, preferably 1 or 2.

The bonding position of R ³¹ and R ³² on the benzene ring is not particularly limited, but or Preferably, it is an ortho position.

Further, R ³¹ and R ³² may be the same group or different bases, but in terms of manufacturing cost, they are preferably the same.

Examples of the alkylene group of R ³³ and R ³⁴ include an alkylene group having a carbon number of 1 to 10, and each of them is particularly preferably an ethyl group or a propyl group.

x and y each independently represent an integer of 0 or more, and are usually about 0 to 6, preferably about 0 to 3. In general, the larger the x and y, the higher the solubility, but when it is too large, the sensitivity may be lowered.

Further, R ³³ and R ³⁴ may be the same group or different bases, but in terms of manufacturing cost, the same basis is preferred.

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the molecular weight of the (a') component is usually in the range of 200 to 200,000, preferably 300 to 100,000. When the molecular weight is less than the above range, there are many cases where the film formation property is problematic. Conversely, when the resin exceeds the above range, the addition reaction of α,β-unsaturated monocarboxylic acid or the like described later tends to cause gelation. It may lead to manufacturing difficulties.

(1-2) α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester (b') having a carboxyl group in the ester moiety α,β-unsaturated monocarboxylic acid and/or α,β-unsaturated monocarboxylic acid ester (b′) having a carboxyl group in the ester moiety (hereinafter sometimes referred to as “(b′) component”) Examples of the α,β-unsaturated monocarboxylic acid include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid, etc., preferably acrylic acid and methacrylic acid, and particularly acrylic acid is preferred because of reactivity. .

Examples of the α,β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety include 2-bromodecyloxyethyl acrylate, 2-butyleneoxyethyl acrylate, and acrylic acid-2- Ethyloxyethyl ester, 2-hexahydromethoxyethyl acrylate, 2-succinyloxyethyl methacrylate, 2-m-butyleneoxyethyl methacrylate, A 2-methoxyethyl acrylate, 2-hexahydromethoxyethyl methacrylate, 2-pentenyloxyethyl butyrate, etc., preferably 2-cis butyl acrylate The enedimethoxyethyl ester and the 2-methoxyethyl acrylate are particularly preferably 2-butyleneoxyethyl acrylate.

A well-known method can be used for the addition reaction of the (b') component and the said (a') component. For example, the component (b') can be reacted with the component (a) at a temperature of 50 to 150 ° C in the presence of an esterification catalyst. As the esterification catalyst used herein, a tertiary amine such as triethylamine, trimethylamine, benzyldimethylamine or benzyldiethylamine, tetramethylammonium chloride or tetraethyl can be used. A quaternary ammonium salt such as ammonium chloride or dodecyltrimethylammonium chloride.

Further, the (a') component, the (b') component, and the esterification catalyst may be used singly or in combination of two or more.

The amount of the component (b') to be used is preferably from 0.5 to 1.2 equivalents, more preferably from 0.7 to 1.1 equivalents, per equivalent of the epoxy group of the (a') component.

If the amount of the (b') component is small, the amount of introduction of the unsaturated group is insufficient, and the subsequent reaction with the polybasic acid and/or its anhydride (c') is not sufficient. Minute. Also, it is disadvantageous that a large amount of epoxy groups remain. On the other hand, if the amount used is large, the component (b') remains as an unreacted product. It is considered that there is a tendency to cause deterioration in hardening characteristics in either case.

(1-3) Polybasic acid and/or its anhydride (c') The polybasic acid and/or its anhydride (c') which is further added to the (a') component of the (b') component (hereinafter sometimes referred to as "(c') component)" may be mentioned. Selected from maleic acid, succinic acid, itaconic acid, citric acid, tetrahydrofurfuric acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, diphenylketonetetracarboxylic acid, methylhexahydrogen One or more of citric acid, endomethylenetetrahydrofurfuric acid, chloric acid, methyltetrahydrofurfuric acid, biphenyltetracarboxylic acid, and the like.

Preferred are maleic acid, succinic acid, itaconic acid, citric acid, tetrahydrofurfuric acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid or the anhydrides thereof. Particularly preferred is tetrahydrofurfuric acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride or biphenyltetracarboxylic dianhydride.

The addition reaction of the component (c') can be carried out by using a known method and continuing the reaction under the same conditions as the reaction of the addition of the component (b') to the component (a').

The addition amount of the component (c') is preferably such that the acid value of the alkali-soluble resin (A') formed is in the range of 10 to 150 mgKOH/g, more preferably 20 to 140 mgKOH/g. The range is around. If the acid value of the resin is less than the above range, the alkali developability tends to be insufficient, and if it exceeds the above range, the curing property tends to be poor.

Further, when the (c') component is subjected to an addition reaction, a polyfunctional alcohol (d') such as trimethylolpropane, pentaerythritol or dipentaerythritol may be added to introduce a multi-point. Branch structure. The polyhydric alcohol (d') may, for example, be the same as those exemplified as the polyol (d") which will be described later.

The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the alkali-soluble resin (A') is usually 1,000 or more, preferably 1,500 or more, and usually 30,000 or less, preferably 20,000 or less, more preferably 10,000 or less, and particularly preferably 8,000 or less. If the weight average molecular weight is too large, the developability may be poor, and if it is too small, the alkali resistance may be poor.

(2) alkali-soluble resin (A"): a reaction product of a epoxide compound (a") represented by the following formula (1-a") and a carboxylic acid (b") containing an unsaturated group, and a polybasic acid And an alkali-soluble resin (A") and an alkali-soluble resin (A1") obtained by reacting with the anhydride (c"): an epoxy compound (a" represented by the following formula (1-a") An alkali-soluble resin (A1" obtained by reacting a reaction product with an unsaturated group-containing carboxylic acid (b") with a polyol (d") to react the mixture with a polybasic acid and/or its anhydride (c") )

In the above formula (1-a"), X represents a linking group represented by the following formula (2a), (2b) or (3), wherein one or more adamantane structures are contained in the molecular structure. Represents an integer of 2 or 3.

[化15]

(In the above formulae (2a) and (2b), R ¹ to R ⁴ and R ¹³ to R ¹⁵ each independently represent an adamantyl group which may have a substituent, a hydrogen atom, and a carbon number which may have a substituent of 1~ An alkyl group of 12 or a phenyl group which may have a substituent.

In the above formula (3), R ⁵ to R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. Y represents a divalent linking group containing an adamantane structure which may have a substituent.

In the above formulae (2a), (2b) and (3), * represents a bonding site with a glycidoxy group in the formula (1-a").

(2-1) Epoxy compound (a") represented by the formula (1-a") First, the base X in the epoxy compound (a") (hereinafter sometimes referred to as "(a") component)" represented by the above formula (1-a") will be described.

When the base X is a structure represented by the above formula (2a) or (2b), it is preferred that the above formulas (2a) and (2b) have two or more and four or less adamantane structures. When the adamantane structure is one, the development liquid resistance is lowered, and the resolution is likely to be poor.

When the above-mentioned group X is a structure represented by the above formula (3), the above formula (3) Y is not particularly limited as long as it is a "two-valent linking group containing adamantane structure which may have a substituent, and is preferably represented by the following general formula (4) or (5). Linkage base.

[The above formulae (4) and (5) may each have a substituent. * indicates a bonding site to the benzene ring in the above formula (3). ]

The epoxy compound (a") represented by the above formula (1-a") is particularly preferably represented by the following formula (6) or (7).

The adamantyl group represented by the general formulae (6) and (7) may have a substituent.

In the formula (6), R ¹⁶ to R ²³ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent.

In the formula (7), R ²⁴ and R ²⁵ each independently represent an adamantyl group which may have a substituent, a hydrogen atom, an alkyl group which may have a substituent of 1 to 12 carbon atoms or a phenyl group which may have a substituent . ]

As the alkyl group having 1 to 12 carbon atoms of R ¹ to R ^{25 in} the above formulae (2a), (2b), (3), (6) and (7), the carbon number is preferably 1 to 10 alkyl groups.

In addition, examples of the substituent which the alkyl group may have include a halogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, and a thio group. Phosphine group, amine group and nitro group.

In addition, examples of the substituent which the phenyl group of R ¹ to R ²⁵ in the above general formulae (2a), (2b), (3), (6), and (7) may have include a halogen atom, a hydroxyl group, and a carbon. The number is an alkoxy group of 1 to 10, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfonyl group, a phosphino group, an amine group, and a nitro group.

Further, as the adamantyl group of R ¹ to R ⁴ and R ¹³ to R ¹⁵ in the above formulas (2a) and (2b), the adamantane ring contained in Y of the formula (3), the formula (6) The adamantane ring, the adamantyl group in the formula (7), the adamantyl group of R ²⁴ and R ²⁵ in the formula (7), and the adamantane ring of the formulae (4) and (5) may have Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfonyl group, a phosphino group, an amine group, and a nitro group. Wait.

In the above formula (6), R ¹⁶ to R ^{23 are} particularly preferably an alkyl group, a halogen atom, an alkoxy group, an alkenyl group or a phenyl group.

Further, in the above formula (7), R ²⁴ and R ^{25 are} particularly preferably an alkyl group, a halogen atom, an alkoxy group, an alkenyl group or a phenyl group.

The molecular weight of X represented by the formula (1-a") is preferably 200 or more and 1,000 or less. If the molecular weight of X is less than 200, the chemical resistance is poor. If it exceeds 1000, it may cause low sensitivity.

Further, the epoxy compound (a") represented by the formula (1-a") preferably has an epoxy equivalent of 210 or more, more preferably 230 or more. Further, the epoxy equivalent is preferably 450 or less, more preferably 400 or less. When the epoxy equivalent of the epoxy compound (a") is less than 210, the alkali resistance may be insufficient, and if it exceeds 450, the sensitivity of the produced organic binder tends to decrease.

The epoxy compound (a") may be used alone or in combination of two or more.

The epoxy compound (a") can also be used commercially, or can be synthesized by a known method from the following phenol compounds.

[R ¹ to R ¹⁵ in the above formulae (9a), (9b) and (10) are synonymous with the formulae (2a), (2b) and (3), respectively. ]

For example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added in advance to a dissolved mixture of a compound represented by the formula (9a) or (9b) and an excess of epihalohydrin such as epichlorohydrin or epibromohydrin. Or add one side, one side The reaction is carried out at a temperature of from 20 to 120 ° C for 1 to 10 hours, whereby an epoxy compound in which the X in the formula (1-a") is a linking group represented by the above formula (2a) or (2b) can be obtained ( a").

Further, in the dissolved mixture of the compound represented by the formula (10) and the excess of the epihalohydrin such as epichlorohydrin or epibromohydrin, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added in advance or added thereto. And reacting at a temperature of 20 to 120 ° C for 1 to 10 hours, whereby an epoxy compound (a") in which X in the formula (1-a") is represented by the above formula (3) can be obtained. .

In the reaction for obtaining the epoxy compound (a"), an aqueous solution may be used as the alkali metal hydroxide. In this case, the following method may be employed: continuously adding the alkali metal hydroxide to the reaction system. The aqueous solution is continuously distilled off under reduced pressure or under normal pressure to remove water and epihalohydrin, and further liquid separation is carried out to remove the epihalohydrin continuously into the reaction system.

Further, the epoxy compound (a") represented by the formula (1-a") can be produced by the following method: a compound and a table represented by the above formula (9a), (9b) or (10) A tetrabasic ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is added as a catalyst to the dissolved mixture of the halogen alcohol, and the reaction is carried out at 50 to 150 ° C for 1 to 5 Adding a solid or aqueous solution of an alkali metal hydroxide to the haloalcohol etherate of the compound represented by the formula (9a), (9b) or (10) thus obtained, again at a temperature of 20 to 120 ° C After reacting for 1 to 10 hours, it is subjected to dehydrohalogenation (closed loop).

The amount of the epihalohydrin used in the above reaction is usually from 1 to 20 mol, preferably from 2 to 2, based on 1 equivalent of the hydroxyl group of the compound represented by the formula (9a), (9b) or (10). 10 moles. Also, the amount of alkali metal hydroxide used, The hydroxyl group of the compound represented by the formula (9a), (9b) or (10) is usually from 0.8 to 15 mol, preferably from 0.9 to 11 mol, based on 1 equivalent.

In the above reaction, in order to carry out the reaction, an alcohol such as methanol or ethanol may be added, and an aprotic polar solvent such as dimethylhydrazine or dimethylhydrazine may be added to carry out the reaction. When an alcohol is used, it is used in an amount of 2 to 20% by weight, preferably 4 to 15% by weight based on the amount of the epihalohydrin. Further, when an aprotic polar solvent is used, the amount thereof is from 5 to 100% by weight, preferably from 10 to 90% by weight, based on the amount of the epihalohydrin.

(2-2) Carboxylic acid containing unsaturated group (b") The carboxylic acid (b") (hereinafter sometimes referred to as "(b") component)) containing an unsaturated group may, for example, be an unsaturated carboxylic acid having an ethylenically unsaturated group, and specific examples thereof may be mentioned. Acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, cinnamic acid, α-position via haloalkyl, alkoxy, halogen atom, nitro group or cyano group Substituted monocarboxylic acid such as (meth)acrylic acid; 2-(methyl)propenyloxyethyl succinate; 2-(methyl)propenyloxyethyl adipate; 2-(A) Base) propylene methoxyethyl ester, 2-(methyl) propylene methoxyethyl hexahydrophthalate, 2-(methyl) propylene methoxyethyl maleate, 2- succinic acid Methyl) propylene methoxy propyl ester, 2-(methyl) propylene methoxy propyl adipate, 2-(methyl) propylene methoxy propyl tetrahydro phthalate, 2-(methyl phthalate) ) propylene methoxy propyl ester, 2-(methyl) propylene methoxy propyl maleate, 2-(methyl) propylene butyl butyl succinate, 2- (methyl) adipic acid ) propylene oxy butyl acrylate, 2-(methyl) propylene decyl hydride, 2-(methyl) propyl phthalate Binary butyl butyl acrylate, 2-(methyl) propylene butyl butyl acrylate Acid (meth) propylene oxime alkyl ester; addition of (meth)acrylic acid to lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone a monomer; a (meth)acrylic acid dimer.

Further, an acrylic acid adduct of pentaerythritol tri(meth)acrylate, dipentaerythritol penta (meth)acrylate, trimethylolpropane diacrylate, and glycidyl methacrylate may be mentioned. A compound obtained by adding an acid anhydride such as succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride or decanoic anhydride to an unsaturated compound containing a hydroxyl group such as a methacrylic acid addition product of glycidyl acrylate.

Particularly preferred is (meth)acrylic acid.

These may be used alone or in combination of two or more.

A known method can be used as a method of reacting the epoxy group in the component (a") with the component (b"). For example, a tertiary amine such as triethylamine or benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, or benzyltriethyl chloride a quaternary ammonium salt such as ammonium, pyridine, triphenylphosphine or the like as a catalyst, and reacting the above (a") component with the (b") component in an organic solvent at a reaction temperature of 50 to 150 ° C for several hours to several tens In an hour, it is possible to add a carboxylic acid to the epoxy compound.

The amount of the catalyst used is preferably 0.01 to 10% by weight, particularly preferably 0.3 to 5% by weight, based on the total amount of the reaction raw material mixture ((a") component and (b") component). Further, in order to prevent polymerization in the reaction, it is preferred to use a polymerization inhibitor (for example, p-methoxyphenol, hydroquinone, methyl hydroquinone, p-methoxyphenol, pyrogallol, third butyl). Catechol, phenothiphenyl And the amount thereof is preferably 0.01 to 1.0% by weight, particularly preferably 0.03 to 5% by weight, based on the reaction raw material mixture.

The ratio of the (b") component to the epoxy group of the (a") component is usually from 90 to 100 mol%. Since the residual of the epoxy group tends to adversely affect the storage stability, it is preferred that the (b") component is usually 0.8 to 1.5 equivalents per 100 equivalents of the epoxy group of the (a") component. The reaction is carried out at a ratio of 0.9 to 1.1 equivalents.

(2-3) Polybasic acid and/or its anhydride (c") As the polybasic acid and/or its anhydride (c") (hereinafter sometimes referred to as "(c") component" or "polybasic acid (anhydride)"), a dibasic acid and/or its anhydride (hereinafter referred to as " Dibasic acid (anhydride)", tribasic acid and/or its anhydride (hereinafter referred to as "tribasic acid (anhydride)"), tetrabasic acid and/or its anhydride (hereinafter referred to as "quaternary acid (anhydride)" ")Wait.

As a tetrabasic acid (anhydride) (tetracarboxylic acid and/or its dianhydride), a known one can be used, and examples thereof include pyromellitic acid, diphenylketonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, and the like. Tetracarboxylic acid or such dianhydride. These may be used alone or in combination of two or more.

As the tetrabasic acid (anhydride), among the above-exemplified compounds, particularly preferred is biphenyltetracarboxylic acid or an anhydride thereof.

Reacting the reactant of the (a") component and the (b") component with the tetrabasic acid (anhydride) as the component (c"), whereby the molecular weight is increased by the crosslinking reaction. Therefore, the adhesion to the substrate is improved. It is preferable to have an effect of adjusting solubility, improving sensitivity or alkali resistance.

Examples of the dibasic acid (anhydride) (dicarboxylic acid and/or an anhydride thereof) include maleic acid, succinic acid, itaconic acid, citric acid, tetrahydrofurfuric acid, and hexahydroabietic acid. Methyl endomethylenetetrahydrofurfuric acid, chloric acid, methyltetrahydrofurfuric acid or the like. Among them, tetrahydrofurfuric acid, succinic acid or the like are preferred. These may be used alone or in combination of two or more.

Reacting the reactant of the (a") component and the (b") component with the dibasic acid (anhydride) as the component (c"), thereby facilitating the adjustment of the solubility and improving the adhesion to the substrate. Therefore, it is better.

Examples of the tribasic acid (anhydride) (tricarboxylic acid and/or an anhydride thereof) include trimellitic acid, hexahydrotrimellitic acid, and the like. Particularly preferred are trimellitic anhydride and hexahydrotrimellitic anhydride. These may be used alone or in combination of two or more.

By using a tribasic acid (anhydride) as the (c") component, the molecular weight of the alkali-soluble resin (A") can be increased, and a branch can be introduced into the molecule to obtain a balance between molecular weight and viscosity. Further, the amount of introduction of the acid group in the molecule can be increased, and a resin having a balance of sensitivity, adhesion, and the like can be obtained.

It is particularly preferable to use a tetrabasic acid (anhydride) as the (c") component. In this case, the addition ratio of the tetrabasic acid (anhydride) is based on the addition of the (b") component to the (a") component. The hydroxyl group formed is usually 10 to 100 mol%, preferably 20 to 100 mol%, more preferably 30 to 100 mol%. If the (c") component is a tetrabasic acid (anhydride) addition If the ratio is too small, the solubility of the alkali-soluble resin (A") may be insufficient or the adhesion to the substrate may be insufficient.

Further, in terms of viscosity adjustment and solubility adjustment of the photosensitive colored resin composition, it is preferred to replace one of the above tetrabasic acids (anhydrides) with a dibasic acid (anhydride).

When a tetrabasic acid (anhydride) and a dibasic acid (anhydride) are used as the (c") component, Preferably, the dibasic acid (anhydride): tetrabasic acid (anhydride) = 99:1 to 20:80, more preferably 80:20 to 30:70. When the tetrabasic acid (anhydride) is too small in this range, the film properties of the obtained coating film may be lowered, and when the dibasic acid (anhydride) is too small, the viscosity of the obtained resin solution may increase, making it difficult to use. .

Further, in addition to the effect of improving adhesion to the substrate, easy adjustment of solubility, improvement in sensitivity and alkali resistance, in order to obtain various balances of molecular weight, viscosity, sensitivity, adhesion, and the like, it is preferred to use tetrabasic acid in combination ( Anhydride) and/or a dibasic acid (anhydride) and a tribasic acid (anhydride).

When a tetrabasic acid (anhydride) and/or a dibasic acid (anhydride) and a tribasic acid (anhydride) are used as the (c") component, if the amount of the tribasic acid (anhydride) used is too small, the effect is poor, and the alkali is resistant. The possibility of reducing the property, so the amount of the tribasic acid (anhydride) used is usually from 5 to 70 mol% relative to the hydroxyl group formed when the (b") component is added to the (a") component. Good is about 10~40%.

The total of the addition ratio of the component (c") is usually 10 to 100 mol%, preferably 20 to 100, based on the hydroxyl group formed when the component (b") is added to the component (a"). More than or equal to 30% to 100% by mole. If the addition ratio of the (c") component is too small, the solubility of the alkali-soluble resin (A") may be insufficient or the adhesion to the substrate may be insufficient. .

Further, the (c") component may be reacted with the hydroxyl group formed when the (b") component is added to the (a") component, or may be added to the (a") component (b"). The component is reacted with any of the hydroxyl groups present in the mixture in which the polyol (d" described later is mixed.

After adding (b") component to (a") component, or mixing it A well-known method can be used for the method of adding a (c") component after the polyol (d").

The reaction temperature is usually 80 to 130 ° C, preferably 90 to 125 ° C. When the reaction temperature exceeds 130 ° C, a part of the unsaturated group in the component (b") is polymerized, which may increase the molecular weight. If the temperature is less than 80 ° C, the reaction may not proceed smoothly and remain ( The possibility of c") ingredients.

(2-4) Polyol (d") In the photosensitive colored resin composition of the present invention, the other binder resin (F) used in combination with the alkali-soluble resin (A) may be an alkali-soluble resin (A1" obtained by the following method: in the above (a) Further, a polyol (d") (hereinafter sometimes referred to as "(d") component)) is added to the reactant obtained by adding the component (b") to the component, and the component (c") is present in the reactant. Any of the hydroxyl groups in the mixture is subjected to an addition reaction.

As the component (d"), for example, it is preferably selected from the group consisting of trimethylolpropane, bis(trimethylolpropane), pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. One or two or more kinds of polyols.

By using the (d" component, the molecular weight of the alkali-soluble resin (A1") can be increased, and branching can be introduced into the molecule to obtain a balance between molecular weight and viscosity. Further, the introduction rate of the acid group in the molecule can be increased, and an organic binder having a balance of sensitivity and adhesion can be obtained.

If the amount of the (d") component is too small, the effect is unsatisfactory. If too large, the viscosity may be increased or gelled. Therefore, the reactant of the (a") component and the (b") component is usually 0.01 to 0.5. The weight is about 0.02 to 0.2, preferably about 0.02 to 0.2. The amount is about.

(2-5) Acid value and molecular weight of alkali-soluble resin (A") and (A1") The acid value of the alkali-soluble resins (A") and (A1") thus obtained is usually 10 mgKOH/g or more, preferably 50 mgKOH/g or more. If the acid value is less than 10 mgKOH/g, the developability may be insufficient. Further, if the acid value is too high, there is a problem in the alkali resistance of the photosensitive colored resin composition (that is, the roughening of the surface of the pattern or the film is reduced by the alkaline developing solution), so the acid value is preferably 200 mgKOH. Below /g, it is more preferably 150 mgKOH/g or less.

The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the alkali-soluble resins (A") and (A1") is preferably 1,500 or more, and more preferably 2,000 or more. Further, it is preferably 20,000 or less, more preferably 10,000 or less. If the weight average molecular weight is too small, there is a possibility that the sensitivity, the coating film strength, and the alkali resistance may occur, and if it is too large, there is a problem in developability or resolubility.

<Photopolymerization initiator (B)>

The photopolymerization initiator (B) can be usually used as a mixture (photopolymerization initiator) with an accelerator and an additive such as a sensitizing dye added as needed. The photopolymerization initiator system has a function of directly absorbing light or performing photo-sensitization to cause a decomposition reaction or a dehydrogenation reaction, thereby generating a function of polymerizing active radicals.

Examples of the photopolymerization initiator include a metallocene compound containing a titanocene compound described in each of JP-A-59-152396, and JP-A-61-151197; The hexaaryldiimidazole derivative described in JP-A-2000-56118, and the halomethylation described in JP-A-10-39503 Diazole derivatives, halomethyl groups N-aryl-α-amino acids such as derivatives and N-phenylglycine, free radicals such as N-aryl-α-amino acid salts and N-aryl-α-amino acid esters The active agent, the α-aminoalkyl phenone derivative, and the oxime ester derivative described in JP-A-2000-80068, JP-A-2006-36750, and the like.

Specifically, for example, as the titanocene derivative, dicyclopentadienyl titanium dichloride, dicyclopentadienyl bisphenyl titanium, and dicyclopentadienyl bis (2, 3, 4,5,6-pentafluorophenyl-1-yl)titanium, dicyclopentadienylbis(2,3,5,6-tetrafluorophenyl-1-yl)titanium, dicyclopentadienyl bis ( 2,4,6-trifluorophenyl-1-yl)titanium, dicyclopentadienylbis(2,6-difluorophenyl-1-yl)titanium, dicyclopentadienyldi(2,4- Difluorophenyl-1-yl)titanium, bis(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl-1-yl)titanium, bis(methylcyclopentadiene) Bis(2,6-difluorophenyl-1-yl)titanium, dicyclopentadienyl[2,6-difluoro-3-(pyrrol-1-yl)-phenyl-1-yl]titanium, etc. .

Further, examples of the biimidazole derivative include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer and 2-(2'-chlorophenyl)-4,5-. Bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl A-4,5-diphenylimidazole dimer, (4'-methoxyphenyl)-4,5-diphenylimidazole dimer, and the like.

Halomethylation Examples of the oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuranyl)-1,3,4- Diazole, 2-trichloromethyl-5-[β-(2'-benzofuranyl)vinyl]-1,3,4- Diazole, 2-trichloromethyl-5-[β-(2'-(6"-benzofuranyl)vinyl)]-1,3,4- Diazole, 2-trichloromethyl-5-furanyl-1,3,4- Diazole and the like.

Also, as a halomethyl group Examples of derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-all , 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl) are all three , 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl) are all three , 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) are all three Wait.

Further, examples of the α-aminoalkylphenone derivatives include 2-methyl-1-[4-(methylthio)phenyl]-2- Lolinylpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4- Polinylphenyl)butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamyl benzoate, 4-diethylaminophenyl benzene Ketone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene) ring Hexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl)coumarin, 4-(diethylamino)chalcone and the like.

Further, examples of the oxime ester derivative include the following compounds.

[Chemistry 19]

In addition, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; 2-methyl hydrazine, 2-ethyl hydrazine, 2-anthracene derivatives such as tert-butyl fluorene and 1-chloroindole; diphenyl ketone, micbutone, 2-methyl diphenyl ketone, 3-methyl diphenyl ketone, 4 a diphenyl ketone derivative such as methyl diphenyl ketone, 2-chlorodiphenyl ketone, 4-bromodiphenyl ketone or 2-carboxydiphenyl ketone; 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl -(p-isopropylphenyl)one, 1-hydroxy-1-(p-dodecylphenyl)one, 2-methyl-(4'-methylthiophenyl)-2- Acetophenone derivatives such as phenyl-1-propanone, 1,1,1-trichloromethyl-(p-butylphenyl) ketone; thioxanthone, 2-ethyl thioxanthone, 2-isopropyl Thiophenone derivatives such as thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone a benzoate derivative such as p-dimethylaminobenzoic acid ethyl ester or p-diethylaminobenzoic acid ethyl ester; 9-phenyl acridine, 9-(p-methoxyphenyl) Acridine derivatives such as acridine; 9,10-dimethylbenzophene Order Derivatives; anthrone derivatives such as benzofluorenone and the like.

Among these photopolymerization initiators, oxime ester derivatives are particularly preferred in terms of sensitivity.

As the accelerator constituting the photopolymerization initiator component, for example, N,N-dialkylaminobenzoic acid alkyl ester such as N,N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzoic acid can be used. Thiazole, 2-mercaptobenzophenone A mercapto compound having a heterocyclic ring such as azole or 2-mercaptobenzimidazole or an aliphatic polyfunctional mercapto compound.

These photopolymerization initiators and accelerators may be used singly or in combination.

Specific examples of the photopolymerization initiator component include a dialkyl group described on pages 16 to 26 of "FINE CHEMICAL" (1991, March 1, vol. 20, No. 4). The hexaaryldiimidazole type described in the above-mentioned Japanese Patent Publication No. SHO-58-403023, and the like. S-trihalomethyl three The titanium pentoxide described in Japanese Patent Laid-Open No. Hei 4-221958, No. Hei 4-219756, and the like. A dye, a compound having an amine group or a urethane group and a compound containing an addition-polymerizable ethylenic saturated double bond.

In the photopolymerization initiator component, for the purpose of improving the sensitivity, a sensitizing dye corresponding to the wavelength of the image exposure light source may be blended as needed. Examples of the sensitizing dyes include those described in JP-A-4-221958 and JP-A-4-219756. The coumarin dye having a heterocyclic ring, which is described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. The 3- keto coumarin compound, the pyrrolemethylene dye described in Japanese Patent Laid-Open Publication No. Hei 6-19240, and Japanese Patent Laid-Open No. Sho 47-2528, JP-A-54-155292, and JP-A-45 -37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A 59-56403, JP-A-2-69 A dye having a dialkylaminobenzene skeleton described in JP-A-57-168088, JP-A-5-107761, JP-A No. 5-210240, and JP-A-4-288818.

Among these sensitizing dyes, an amine group-containing sensitizing dye is preferred, and a compound having an amine group and a phenyl group in the same molecule is more preferred. Particularly preferred are: 4,4'-dimethylaminodiphenyl ketone, 4,4'-diethylaminodiphenyl ketone, 2-aminodiphenyl ketone, 4-aminodiyl a diphenyl ketone compound such as phenylketone, 4,4'-diaminodiphenyl ketone, 3,3'-diaminodiphenyl ketone or 3,4-diaminodiphenyl ketone, 2 -(p-dimethylaminophenyl) benzo Azole, 2-(p-diethylaminophenyl)benzo Azole, 2-(p-dimethylaminophenyl)benzo[4,5]benzo Oxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzo Azole, 2,5-bis(p-diethylaminophenyl) 1,3,4- Oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-Diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl) 1,3,4-thiadiazole, (p-dimethylaminophenyl) Pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl) a compound containing a p-dialkylaminophenyl group such as pyrimidine or (p-diethylaminophenyl)pyrimidine.

Among them, the most preferred is 4,4'-dialkylaminodiphenyl ketone.

Further, the sensitizing dye may be used alone or in combination of two or more.

<Colorant (C)>

The coloring matter (C) means a coloring of the photosensitive colored resin composition of the present invention. As the coloring material, a dye can be used. However, in terms of heat resistance, light resistance and the like, a pigment is preferred.

As the pigment, pigments of various colors such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a violet pigment, an orange pigment, a brown pigment, and a black pigment can be used. Further, as the structure, in addition to the azo system, the phthalocyanine system, the quinophthalone type, the benzimidazolone type, the isoindolinone type, and the second In addition to organic pigments such as phthalic acid, indanthrene, and lanthanide, various inorganic pigments and the like can be used.

Hereinafter, specific examples of the pigment which can be used in the present invention are indicated by a Pigment number. In addition, the term "C.I. Pigment Red 2" as used hereinafter refers to a dye index (C.I.).

Examples of the red pigment include CI 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, 179, 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. Among them, C.I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242, and 254 are preferable, and C.I. Pigment Red 177, 209, 224, and 254 are more preferable.

As the blue pigment, CI Pigment Blue 1, 1, 2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25 can be cited. , 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. Among them, preferred are C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6, and more preferably C.I. Pigment Blue 15:6.

As the green pigment, C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 is exemplified. Among them, C.I. Pigment Green 7, 36 is preferable.

As the yellow pigment, C.1. 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, 173, 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. Among them, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, and 185 are preferable, and C.I. Pigment Yellow 83, 138, 139, 150, and 180 are more preferable.

As the orange pigment, CI 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. Among them, preferred are C.I. Pigment Oranges 38 and 71.

As the purple pigment, CI 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. Among them, C.I. Pigment Violet 19 and 23 are preferable, and C.I. Pigment Violet 23 is more preferable.

Further, when the photosensitive colored resin composition of the present invention is a photosensitive colored resin composition for a resin black matrix of a color filter, a black coloring material can be used. As colorant (C). The black coloring material may be a black coloring material alone, or may be a mixture of red, green, and blue. Further, the coloring materials can be suitably selected from inorganic or organic pigments and dyes.

As a coloring material which can be used in combination for preparing a black coloring material, Victoria Pure Blue (42595), Goldamine O (41000), Cathilon brilliant flavin (basic 13), Rose Red 6GCP (45160), Rose Red B (45170), Safranin OK70: 100 (50240), Epilepsy X (42080), No. 120 / Leonor Yellow (21090), Leonor Yellow GRO (21090), SYMULER FAST Yellow 8GF (21105), Union Benzidine yellow 4T-564D (21095), SYMULER FAST RED4015 (12355), LIONOL RED 7B4401 (15850), FIRSTGEN 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 Yellow 36), etc. (Further, the number in the above () indicates the dye index (CI)).

Further, other pigments which can be used in combination are indicated by CI numbers, and examples thereof include CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, and 154. 166, CI orange pigments 36, 43, 51, 55, 59, 61, CI red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, CI violet pigments 19, 23, 29, 30, 37, 40, 50, CI blue pigment 15, 15:1, 15:4, 22, 60, 64, CI green pigment 7, CI brown pigments 23, 25, 26, etc.

Further, examples of the black coloring material which can be used alone include carbon black and acetylene black. Lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black, and the like.

Among these, carbon black is preferred from the viewpoint of light blocking ratio and image characteristics. Examples of the carbon black include carbon black shown below.

Mitsubishi Chemical Corporation: MA 7, MA 8, MA 11, MA 100, MA 100R, MA 220, MA 230, MA 600, #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, OIL 7B, OIL 9B, OIL 11B, OIL 30B, OIL 31B

DEGUSSA company: Printex 3, Printex 30P, Printex 30, Printex 300P, Printex 40, Printex 45, Printex 55, Printex 60, Printex 75, Printex 80, Printex 85, Printex 90, Printex A, Printex L , Printex G, Printex P, Printex U, Printex V, Printex G, Special Black 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW 1, Color Black FW 2, Color Black FW 2V, Color Black FW 18, Color Black FW 18, Color Black FW 200, Color Black S160, Color Black S170

CABOT company: Monarch 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R, BLACK PEARL S480, PEARLS 130, VULCANXC 72R, ELFTEX-8

COLUMBIAN CARBON company: RAVEN 11, RAVEN 14, RAVEN 15, RAVEN 16, RAVEN 22, RAVEN 30, RAVEN 35, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, RAVEN 500, RAVEN 780, RAVEN 850, RAVEN 890H, RAVEN 1000, RAVEN 1020, RAVEN 1040, RAVEN 1060U, RAVEN 1080U, RAVEN 1170, RAVEN 1190U, RAVEN 1250, RAVEN 1500, RAVEN 2000, RAVEN 2500U, RAVEN 3500, RAVEN 5000, RAVEN 5250, RAVEN 5750, RAVEN 7000

As an example of other black pigments, titanium black, aniline black, iron oxide black pigment, and red, green, and blue organic pigments may be mixed and used as a black pigment.

Further, as the pigment, barium sulfate, lead sulfate, titanium oxide, lead yellow, iron oxide, chromium oxide or the like can be used.

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

Further, it is preferred that the pigments are dispersed to have an average particle diameter of usually 1 μm, preferably 0.5 μm or less, more preferably 0.25 μm or less.

Furthermore, in the present invention, the average particle diameter of the pigment is based on the particle diameter of the pigment measured by Dynamic Light Scattering (DLS). And find the value. The particle size measurement is performed on a sufficiently diluted colored resin composition (usually diluted to prepare a pigment concentration of about 0.005 to 0.2% by weight. However, if it is a concentration recommended by a measuring machine, it can be carried out according to the concentration). The measurement was carried out at 25 °C.

Moreover, examples of the dye usable as the coloring material include an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinone dye, a quinoline dye, a nitro dye, a hydroxy dye, and a dye. Methyl dyes, etc.

Examples of the azo dye include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, and CI Direct Yellow 12 , CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI disperse blue 165, CI alkaline blue 41, CI alkaline red 18, CI mordant red 7, CI mordant yellow 5, CI mord black 7, and the like.

Examples of the lanthanide dyes include CI reduction blue 4, CI acid blue 40, CI acid green 25, CI reactive blue 19, CI reactive blue 49, CI dispersion red 60, CI dispersion blue 56, and CI dispersion. Blue 60 and so on.

Other examples of the phthalocyanine-based dye include CI-reduced blue 5; and examples of the quinone-based dye include CI basic blue 3 and CI basic blue 9; and the quinoline dye is, for example, Examples include CI Solvent Yellow 33, CI Acid Yellow 3, and CI Disperse Yellow 64; and examples of the nitro dye include CI Acid Yellow 1, CI Acid Orange 3, and CI Disperse Yellow 42. Wait.

<Dispersant (D)>

In the present invention, it is preferable to contain the dispersing agent (D) by dispersing the coloring material (C) finely and stabilizing the dispersed state to ensure the stability of the quality.

The dispersing agent (D) is preferably a polymer dispersing agent having a functional group, and further preferably has a carboxyl group; a phosphate group; a sulfonic acid group; or the bases; Secondary or tertiary amine; quaternary ammonium; from pyridine, pyrimidine, pyr A polymer dispersant such as a functional group such as a nitrogen-containing heterocyclic group. Among them, it is particularly preferred to have a primary, secondary or tertiary amine group; a quaternary ammonium salt group; from pyridine, pyrimidine, pyridyl A polymer dispersing agent such as a basic functional group such as a nitrogen-containing heterocyclic group.

In addition, examples of the polymer dispersant include a urethane dispersant, an acrylic dispersant, a polyethyleneimine dispersant, a polyallylamine dispersant, and a monomer having an amine group. Dispersant with macromonomer, polyoxyethylene alkyl ether dispersant, polyoxyethylene diester dispersant, polyether phosphate dispersant, polyester phosphate dispersant, sorbitan fatty ester dispersion Agent, aliphatic modified polyester-based dispersant, and the like.

Specific examples of the dispersing agent include EFKA (made by EFKA Chemicals BV (EFKA) Co., Ltd.), Disperbyk (made by BYK-CHEMIE Co., Ltd.), DISPARLON (made by Nanben Chemical Co., Ltd.), and SOLSPERSE. (manufactured by LUBRIZOL Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoei Chemical Co., Ltd.), AJISPER (manufactured by Ajinomoto Co., Ltd.), and the like.

These polymer dispersants may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the polymer dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less.

In the above, the dispersing agent (D) is particularly preferably an urethane-based polymer dispersing agent having a functional group and/or an acrylic polymer dispersing agent in terms of adhesion and linearity.

Examples of the urethane-based and acrylic-based polymer dispersing agents include Disperbyk 160 to 166 and 182 series (all of which are amine-based acetate), and Disperbyk 2000, 2001 (all of which are acrylic) (above). All are BYK-CHEMIE company).

When a preferred chemical structure is exemplified as the urethane-based polymer dispersant, for example, a polyisocyanate compound having one or two hydroxyl groups in the molecule has an average molecular weight of 300 to 10,000. The compound and a dispersion resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting a compound having an active hydrogen and a tertiary amino group in the same molecule.

Examples of the polyisocyanate compound include p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene-1,5-. Aromatic diisocyanate such as diisocyanate or tolidine diisocyanate, hexamethylene diisocyanate, methyl isocyanate diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer Aliphatic diisocyanate such as acid diisocyanate, isophorone diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), ω, ω'-diisocyanate Alicyclic diisocyanate having an aromatic ring such as alicyclic diisocyanate such as ester dimethylcyclohexane, xylene diisocyanate, α,α,α',α'-tetramethylxylene diisocyanate, or lysine Ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane a triisocyanate such as an alkane triisocyanate, a sulfonate (isocyanate phenylmethane) or a ginseng (isocyanate phenyl) thiophosphate, and the like, a terpolymer, a water adduct, and a polyol adduct thereof. As the polyisocyanate, a terpolymer of an organic diisocyanate is preferred, and a trimer of toluene diisocyanate and a terpolymer of isophorone diisocyanate are preferred. These may be used alone or in combination of two or more.

Examples of the method for producing the isocyanate trimer include the use of a suitable trimerization catalyst such as a tertiary amine, a phosphine, an alkoxide, a metal oxide or a carboxylate. The polyisocyanate is subjected to partial trimerization of an isocyanate group, and after trimerization is stopped by adding a catalyst poison, the unreacted polyisocyanate is removed by solvent extraction and thin film distillation, thereby obtaining a target containing isomeric cyanide. Acid-based polyisocyanate.

Examples of the compound having one or two hydroxyl groups in the same molecule and having an average molecular weight of 300 to 10,000 include polyether diol, polyester diol, polycarbonate diol, polyolefin diol, and the like. The single terminal hydroxyl group of the compound is alkoxylated with a carbon number of 1 to 25 and a mixture of two or more of these.

The polyether diol may, for example, be a polyether diol, a polyether ester diol, or a mixture of two or more of these. The polyether diol is obtained by homopolymerizing or copolymerizing an alkylene oxide, and examples thereof include polyethylene glycol, polypropylene glycol, and polycondensation. Ethylene glycol-propylene glycol, polyoxybutylene glycol, polyoxyhexanediol, polyoxyoctanediol, and a mixture of two or more thereof.

Examples of the polyether ester diol include reacting a mixture of an ether group-containing diol or another diol with a dicarboxylic acid or an anhydride, or reacting a polyester diol with an alkylene oxide. The winner may, for example, be poly(polyoxytetramethylene) adipate or the like. The polyether diol is preferably a compound in which a polyethylene glycol, a polypropylene glycol, a polyoxybutylene glycol or a single terminal hydroxyl group of the compound is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Examples of the polyester diol include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, citric acid, etc.) or the like. Anhydride and diol (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-pentanediol, 2 , 2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8- An aliphatic diol such as octanediol, 2-methyl-1,8-octanediol or 1,9-nonanediol, an alicyclic diol such as bishydroxymethylcyclohexane or xylylene glycol; Examples of the polycondensation of an aromatic diol such as bishydroxyethoxybenzene or an N-alkyl dialkanolamine such as N-methyldiethanolamine can be exemplified by polyethylene diadipate and polyhexamethylene glycol. Dibutyl succinate a polylactone diol or a polylactone obtained by using the above diol or a monohydric alcohol having a carbon number of 1 to 25 as a starter. Monool, for example, polycaprolactone a diol, a polymethyl valerolactone, and a mixture of two or more thereof. As the polyester diol, polycaprolactone diol or polycaprolactone having a carbon number of 1 to 25 as a starter is preferred.

Examples of the polycarbonate diol include poly(1,6-exexhexyl)carbonate and poly(3-methyl-1,5-exopentyl)carbonate, and examples of the polyolefin diol include polycondensation. Butadiene diol, hydrogenated polybutadiene diol, hydrogenated polyisoprene diol, and the like.

These may be used alone or in combination of two or more.

The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually from 300 to 10,000, preferably from 500 to 6,000, more preferably from 1,000 to 4,000.

A compound having active hydrogen and a tertiary amino group in the same molecule as used in the present invention will be described. The active hydrogen, that is, the hydrogen atom directly bonded to the oxygen atom, the nitrogen atom or the sulfur atom, may be a hydrogen atom in a functional group such as a hydroxyl group, an amine group or a hydrogenthio group, and among them, a hydrogen atom of an amine group is preferable. Particularly preferred is a primary amine-based hydrogen atom.

The tertiary amino group is not particularly limited, and examples thereof include an amine group having an alkyl group having 1 to 4 carbon atoms or a heterocyclic ring structure, and more specifically, an imidazole ring or a triazole ring.

When the above compound having an active hydrogen and a tertiary amino group in the same molecule is exemplified, N,N-dimethyl-1,3-propanediamine and N,N-diethyl-1,3- Propylenediamine, 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-butyl Diamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1,4-butanediamine Wait.

Further, examples of the nitrogen-containing heterocyclic ring in the case of a tertiary amino group-containing nitrogen-containing heterocyclic ring include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an anthracene ring, an indazole ring, and an indazole ring. , benzimidazole ring, benzotriazole ring, benzo Nitrogen-containing 5-membered heterocyclic ring such as azole ring, benzothiazole ring, benzothiadiazole ring, pyridine ring, hydrazine Ring, pyrimidine ring, three A nitrogen-containing 6-membered heterocyclic ring such as a ring, a quinoline ring, an acridine ring or an isoquinoline ring. Among these nitrogen-containing heterocyclic rings, an imidazole ring or a triazole ring is preferred.

Specific examples of the compound having the imidazole ring and the amine group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, and 1-(2-aminoethyl). Imidazole and the like. Further, specific examples of the compound having a triazole ring and an amine group include 3-amino-1,2,4-triazole and 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, etc. . Among them, preferred are N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, 3- Amino-1,2,4-triazole.

These may be used alone or in combination of two or more.

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

The production of the urethane-based polymer dispersant can be carried out in accordance with a known method for producing a polyurethane resin. As the solvent at the time of production, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone, ethyl acetate, butyl acetate, and acetic acid can be usually used. Esters such as Lusu, hydrocarbons such as benzene, toluene, xylene, and hexane; some alcohols such as diacetone alcohol, isopropanol, second butanol, and third butanol; chlorides such as dichloromethane and chloroform; An ether such as tetrahydrofuran or diethyl ether; an aprotic polar solvent such as dimethylformamide, N-methylpyrrolidone or dimethylhydrazine. These may be used alone or in combination of two or more.

In the above production, a urethane reaction catalyst can usually be used. Examples of the catalyst include tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannous octoate, and irons such as iron acetylate pyruvate and ferric chloride. One or two or more kinds of tertiary amines such as ethylamine and triethylenediamine.

The amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled to be in the range of 1 to 100 mgKOH/g, based on the amine value after the reaction. More preferably, it is in the range of 5 to 95 mgKOH/g. The amine value is neutralized by neutralization of the basic amine group by an acid to correspond to the acid value, which is expressed in terms of the number of mg of KOH. When the amine value is less than the above range, the dispersibility is lowered, and if it exceeds the above range, the developability is liable to lower.

In addition, in the above reaction, when the isocyanate group remains in the polymer dispersant, and if the isocyanate group is destroyed by the alcohol or the amine compound, the stability with time of the product becomes high, which is preferable.

The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. When the molecular weight is less than 1,000, the dispersibility and the dispersion stability are inferior. When the molecular weight exceeds 200,000, the solubility is lowered, the dispersibility is poor, and it becomes difficult to control the reaction.

As the acrylic polymer dispersant, it is preferred to use an unsaturated group-containing single having a functional group (the functional group referred to herein as the functional group as a functional group contained in the polymer dispersant). A random copolymer, a graft copolymer, or a block copolymer of a monomer having an unsaturated group without a 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-(methyl)acryloxyethyl succinic acid, and 2-(methyl)acryloxyethyloxy group. An unsaturated monomer having a carboxyl group such as citric acid, 2-(meth)acryloxyethyl hexahydrophthalic acid or an acrylic acid dimer, dimethylaminoethyl (meth)acrylate, (methyl) Specific examples of the unsaturated monomer having a tertiary amino group and a quaternary ammonium salt group such as diethylaminoethyl acrylate and such a quaternary compound are exemplified. These may be used alone or in combination of two or more.

Examples of the unsaturated group-containing monomer having no functional group include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. N-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylic acid ring Hexyl ester, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylic acid Base ester, tricyclodecane (meth) acrylate, methyl (meth) methacrylate, N-vinyl pyrrolidone, styrene and its derivatives, α-methyl styrene, N-cyclohexyl cis N-substituted maleimide, acrylonitrile, vinyl acetate and polybutene such as butylene diimine, N-phenyl maleimide, N-benzyl maleimide Methyl (meth) acrylate macromonomer, polystyrene macromonomer, poly(methyl methacrylate) 2-hydroxyethyl macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, poly-caprol Giant monomers such as ester macromonomers. These may be used alone or in combination of two or more.

The acrylic polymer dispersant is particularly preferably an A-B or B-A-B block copolymer comprising an A block having a functional group and a B block having no functional group, in which case, in addition to the A block. In addition to the unsaturated group-containing monomer having the above functional group, an unsaturated group-containing monomer not containing the above functional group may be contained, and these may be in any of random copolymerization or block copolymerization. Contained in the A block. Further, the content of the functional group-free portion in the A block is usually 80% by weight or less, preferably 50% by weight or less, more preferably 30% by weight or less.

The B block is composed of a monomer containing an unsaturated group containing no such functional group, and may contain two or more kinds of monomers in one B block, and these may also be randomly copolymerized or block-coordinated. Any of the polymerizations is contained in the B block.

The A-B or B-A-B block copolymer can be produced, for example, by the living polymerization method shown below.

In the living polymerization method, there are an anionic living polymerization method, a cationic living polymerization method, a radical living polymerization method, and among the anionic living polymerization methods, polymerization The active species is an anion, for example, represented by the following scheme.

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

When synthesizing the acrylic polymer dispersant, a known method described in the following documents may be employed: Japanese Patent Laid-Open No. Hei 9-62002, or 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), Right Hand Hao Yi, Putian Gengyi, Polymer Processing, 36, 366 (1987), Dongcun Min Yan, Ze Benguang, Molecular Proceedings, 46, 189 (1989), M. Kuroki , T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Xiangtian Zhuo San, Inoue Xiangping, Organic Synthetic Chemistry, 43, 300 (1985), DY Sogoh, WR Hertler et al, Macromolecules, 20, 1473 (1987) )Wait.

The acrylic polymer dispersing agent used in the present invention may be an A-B block copolymer or a B-A-B block copolymer, and the A block/B block constituting the copolymer is preferably used. It is 1/99 to 80/20, and particularly preferably 5/95 to 60/40 (weight ratio). If it is out of this range, it may not have good heat resistance and dispersibility.

Further, the amount of the quaternary ammonium salt group in the A-B block copolymer of the present invention and the B-A-B block copolymer of 1 g is usually preferably 0.1 to 10 mmol, and if it is not within the range There is a case where it is impossible to combine good heat resistance and dispersibility.

Further, in the case where the block copolymer contains an amine group which is usually produced in the production process, the amine value is about 1 to 100 mgKOH/g.

Here, the amine value of the dispersing agent such as the block copolymer is expressed by the weight of KOH equivalent to the amount of base of the solid content of the dispersant sample in 1 g of the dispersant sample, and is measured by the following method.

Accurately weigh 0.5 to 1.5 g of the dispersant sample in a 100 mL beaker and dissolve it with 50 mL of acetic acid. The solution was titrated with a 0.1 mol/L HClO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. The bending point of the titration pH curve was taken as the end point of the titration, and the amine value was determined according to the following formula.

Amine value [mgKOH/g] = (561 × V) / (W × S)

[Where, W represents the dispersant sample weighing amount [g], V represents the titration end point titer [mL], and S represents the solid content concentration [% by weight] of the dispersant sample. ]

Further, the acid value of the block copolymer varies depending on the presence or absence of the acidic group which is the source of the acid value, and generally, the lower one is preferable, and usually it is 10 mgKOH/g or less, and the weight average molecular weight thereof. (Mw) is preferably in the range of 1,000 to 100,000. When the weight average molecular weight of the block copolymer is less than 1,000, the dispersion stability tends to be lowered, and when it exceeds 100,000, developability and resolution tend to be lowered.

Further, in terms of improving the dispersion stability, the dispersant (D) is preferably used in combination with a pigment derivative described later.

<Photopolymerizable monomer (E)>

In the present invention, it is preferred to use a photopolymerizable monomer (E) (photopolymerizable compound) in terms of sensitivity and the like.

The photopolymerizable monomer (E) used in the present invention may be a compound having at least one ethylenically unsaturated group in the molecule (hereinafter sometimes referred to as "ethylenic monomer"). Specific examples thereof include (meth)acrylic acid, alkyl (meth)acrylate, acrylonitrile, styrene, and a monocarboxylic ester of a carboxylic acid having one ethylenically unsaturated bond and a polyhydric or monohydric alcohol.

In the present invention, especially for use in one molecule having two or more A polyfunctional ethylenic monomer having an ethylenically unsaturated group is preferred.

Examples of the polyfunctional ethylenic monomer include esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid; esters of an aromatic polyhydroxy compound with an unsaturated carboxylic acid; aliphatic polyhydroxy compounds; and aromatic poly An ester obtained by esterification reaction of a polyvalent hydroxy compound such as a hydroxy compound with an unsaturated carboxylic acid or a polyvalent 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, and trimethylolethane triacrylate. An acrylate of an aliphatic polyhydroxy compound such as ester, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerin acrylate, etc. The acrylate of the exemplified compound is replaced by the methacrylate of the methacrylate, and the acrylate of the exemplified compounds is similarly replaced with the itaconate of the iconate, and the crotonic acid of the butyrate. The ester is replaced by maleic acid ester of maleic acid ester or the like.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, and resorcinol dimethyl. Acrylates and methacrylates of aromatic polyhydroxy compounds such as acrylate and pyrogallol triacrylate.

The ester obtained by the esterification reaction of a polyvalent carboxylic acid and an unsaturated carboxylic acid with a polyvalent hydroxy compound is not necessarily a single compound, and specific examples thereof include acrylic acid, citric acid, and ethylene glycol. Condensate, C a condensate of an olefinic acid, a maleic acid and a diethylene glycol, a condensate of methacrylic acid, terephthalic acid and pentaerythritol, a condensate of acrylic acid, adipic acid, butanediol and glycerin, and the like.

As another example of the polyfunctional ethylenic monomer used in the present invention, the following compounds are useful: a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate, or a polyisocyanate compound and a polyol and a hydroxyl group ( Ethylene acrylate (meth) acrylate obtained by reacting methyl acrylate; epoxy acrylate such as addition reaction of polyvalent epoxy compound with hydroxy (meth) acrylate or (meth) acrylate An acrylamide such as ethylene bis acrylamide; an allyl ester such as diallyl phthalate; a vinyl group-containing compound such as divinyl phthalate.

These may be used alone or in combination of two or more.

<Other compounding components of photosensitive colored resin composition>

In addition to the above-mentioned components, an organic solvent, a tackifier, a coating enhancer, a development improver, an ultraviolet absorber, an antioxidant, a decane coupling agent, and the like may be suitably blended in the photosensitive colored resin composition of the present invention. Surfactants, pigment derivatives, and the like.

(1) Organic solvents The photosensitive colored resin composition of the present invention is usually in a state in which an alkali-soluble resin (A), a photopolymerization initiator (B), a colorant (C), and various materials used as needed are dissolved or dispersed in an organic solvent. use.

As the organic solvent, those having a boiling point of from 100 to 300 ° C are preferably selected. More preferably, it is a solvent having a boiling point of 120 to 280 °C.

Examples of the organic solvent include the following.

Such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl Ether, propylene glycol, tert-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl Ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether glycol monoalkane Ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethyl Glycol dibutyl ether, dipropylene glycol dimethyl ether glycol dialkyl ether; such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol single positive Butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, Acid methoxypentyl ester, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether Acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, glycol methyl ether acetate of 3-methyl-3-methoxybutyl acetate ; glycol diacetate such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate; alkyl acetic acid such as cyclohexanol acetate An ester; an ether such as pentyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dipentyl ether, ethyl isobutyl ether, dihexyl ether; Such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexyl Ketones, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl decyl ketone, ketone of methoxy methyl pentanone; such as ethanol, propanol, butanol, hexanol, cyclohexyl Alcohol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, benzyl alcohol or a polyol; such as n-pentane, An aliphatic hydrocarbon of n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene or dodecane; such as cyclohexane, methylcyclohexane, methylcyclohexene, and a ring An alicyclic hydrocarbon of hexane; an aromatic hydrocarbon such as benzene, toluene, xylene, or cumene; such as amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate Methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate Ethyl benzoate, 3-B Methyl oxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methyl a chain or cyclic ester of butyl oxypropionate or γ-butyrolactone; an alkoxycarboxylic acid such as 3-methoxypropionic acid or 3-ethoxypropionic acid; such as chlorobutane or chlorine Halogenated hydrocarbons of pentane; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile; as a commercially available solvent in accordance with the above, mineral spirits, varsol #2, APCO #18 Solvent, APCO Diluent, SOKAL Solvent No.1 and No.2, SOLVESSO #150, SHELL TS28 Solvent, Carbitol, Ethyl Alcohol, Butyl Alcohol, Methyl Cyrus, B Kesailusu, ethyl sirolimus acetate, methyl sarbuta acetate, diethylene glycol dimethyl ether (all trade names) and the like.

These organic solvents may be used singly or in combination of two or more.

(1-1) Organic solvent when forming a color filter pixel or a black matrix by photolithography When a pixel or a black matrix of a color filter is formed by photolithography, it is preferable to select a boiling point of 100 to 200 ° C (pressure 1013.25 [hPa], and the same boiling point is the same as the organic solvent). By. More preferably, it has a boiling point of 120 to 170 °C.

Among the above organic solvents, the balance between coatability and surface tension is good, and the solubility of the constituent components in the composition is preferably diol alkyl ether acetate.

Further, the glycol alkyl ether acetates may be used singly or in combination with other organic solvents. As the organic solvent to be used in combination, a glycol monoalkyl ether is particularly preferred. Among them, propylene glycol monomethyl ether is particularly preferred in terms of solubility of the constituent components in the composition. Further, the diol monoalkyl ether has a high polarity, and if the amount of addition is too large, the pigment tends to aggregate, and the storage stability of the colored resin composition obtained thereafter is lowered, and the storage stability is lowered. The proportion of the monoalkyl ethers is preferably from 5% by weight to 30% by weight, more preferably from 5% by weight to 20% by weight.

Further, an organic solvent having a boiling point of 150 ° C or higher is used in combination (hereinafter sometimes It is called "high boiling point solvent". ) is also preferred. By using the above-mentioned high-boiling solvent in combination, the colored resin composition is difficult to dry, and has an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, it has the prevention of, for example, the front end of the slit nozzle due to the deposition of coloring materials and the like. Curing to produce foreign matter defects. In terms of the high effect, among the above various solvents, particularly preferred are diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether B. Acid ester.

The content of the high boiling point solvent in the organic solvent is preferably from 3% by weight to 50% by weight, more preferably from 5% by weight to 40% by weight, particularly preferably from 5% by weight to 30% by weight. If the amount of the high boiling point solvent is too small, for example, there is a front end of the slit nozzle due to coloring or the like. When the solidification is caused by the solidification, the drying temperature of the composition is increased, and in the color filter manufacturing step to be described later, the operation of the vacuum drying process is poor, or the pre-baked pore marks are caused. The problem.

Further, the high boiling point solvent having a boiling point of 150 ° C or higher may be a glycol alkyl ether acetate or a glycol alkyl ether. In this case, the boiling point may be 150 ° C or higher. High boiling point solvent.

Examples of preferred high-boiling point solvents include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, and dipropylene glycol methyl ether acetate in various solvents described above. 1,3-butylene glycol diacetate, 1,6-hexanol diacetate, triacetin or the like.

(1-2) An organic solvent when a pixel of a color filter is formed by an inkjet method When a pixel of a color filter is formed by an inkjet method, the boiling point of the organic solvent is usually 130 ° C or more and 300 ° C or less, preferably 150 ° C or more. And 280 ° C or less is more suitable. If the boiling point of the organic solvent is too low, the uniformity of the obtained coating film tends to be poor. On the other hand, when the boiling point of the solvent is too high, as described later, the effect of suppressing the drying of the colored resin composition is high, and even after the hot baking, a large amount of residual solvent is present in the coating film, resulting in poor quality or vacuum. The drying time such as drying becomes longer and the working time increases.

Further, from the viewpoint of the uniformity of the obtained coating film, the vapor pressure of the organic solvent to be used is usually 10 mmHg or less, preferably 5 mmHg or less, more preferably 1 mmHg or less.

Further, when the color filter is manufactured by the ink jet method, the ink ejected from the nozzle is very fine, and is in the range of pL to several tens of pL, so that the organic solvent evaporates and causes the ink before being sprayed to the periphery of the nozzle opening or the pixel array. concentrate. The tendency to dry. In order to avoid this phenomenon, it is preferred that the organic solvent contained in the colored resin composition has a higher boiling point. Specifically, the colored resin composition preferably contains a solvent having a boiling point of 180 ° C or higher. More preferably, the colored resin composition contains an organic solvent having a boiling point of 200 ° C or higher, and particularly preferably an organic solvent having a boiling point of 220 ° C or higher. In addition, the high-boiling solvent having a boiling point of 180 ° C or higher is preferably 50% by weight or more, and more preferably 70% by weight of all the organic solvents contained in the colored resin composition for inks and/or color filters to be described later. The weight % or more is preferably 90% by weight or more. When the ratio of the high boiling point solvent having a boiling point of 180 ° C or more in all the organic solvents is less than 50% by weight, the effect of preventing evaporation of the solvent from the droplets may not be sufficiently exhibited.

As a preferred example of the high boiling point solvent having a boiling point of 180 ° C or higher, for example, Among the above various solvents, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diethyl ether An acid ester, 1,6-hexanol diacetate, triacetin or the like.

Further, in order to adjust the viscosity of the ink or the colored resin composition to be described later or to adjust the solubility of the solid portion, it is also effective to contain a part of the organic solvent having a boiling point of less than 180 °C. The organic solvent is preferably a low viscosity and a high solubility, and a low surface tension is preferably an ether, an ester or a ketone. Among them, cyclohexanone, dipropylene glycol dimethyl ether, cyclohexanol acetate, and the like are particularly preferred.

On the other hand, when the organic solvent contains an alcohol, the discharge stability in the inkjet method may be deteriorated. Therefore, the alcohol is preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less in all the organic solvents.

(2) decane coupling agent In order to improve the adhesion to the substrate, a decane coupling agent may also be added. As the type of the decane coupling agent, one type or a mixture of two or more types may be used, and various decane coupling agents such as epoxy-based, methacrylic-based, and amine-based compounds may be used, and an epoxy-based decane coupling agent is particularly preferable.

(3) Surfactant As the surfactant, one or two or more kinds of various surfactants such as an anionic, cationic, nonionic or amphoteric surfactant can be used, and the possibility of adversely affecting the properties is low. It is preferred to use a nonionic surfactant.

As the above surfactant, for example, a Japanese patent special opening can be suitably used. It is described in Japanese Patent Publication No. 2003-322716.

(4) Pigment derivatives Examples of the pigment derivatives include azo, phthalocyanine, quinophthalone, benzimidazolone, quinophthalone, isoindolinone, and Department, lanthanide, indanthrene, lanthanide, piperidone, diketopyrrolopyrrole, two A derivative such as a quinacridone.

Examples of the substituent of the pigment derivative include a sulfonic acid group, a sulfonylamino group and a quaternary salt thereof, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, and a decylamino group. The sulfonic acid group is preferably bonded directly or via an alkyl group, an aryl group, a heterocyclic group or the like to the pigment skeleton. Further, the substituents may be substituted for a plurality of pigment skeletons. Specific examples of the pigment derivative include a sulfonic acid derivative of phthalocyanine, a sulfonic acid derivative of quinacridone, a sulfonic acid derivative of hydrazine, a sulfonic acid derivative of quinacridone, and a diketopyrrole. Pyrrole sulfonic acid derivative, two Sulfonic acid derivatives and the like. These may be used alone or in combination of two or more.

<Component Composition in Photosensitive Colored Resin Composition>

The content of 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, based on the total solid content of the photosensitive colored resin composition of the present invention. 80% by weight 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 development failure is liable to occur. On the other hand, when the content of the alkali-soluble resin (A) is too large, the permeability of the developer to the exposed portion becomes high, and the sharpness and adhesion of the pixel are deteriorated.

As described above, in the present invention, the alkali-soluble resin (A) can also be used. Part of it is replaced with other binder resin (F).

In this case, the photosensitive colored resin composition of the present invention contains 90% by weight or less, for example, 10 to 90% by weight, preferably 20 to 80% by weight, based on the alkali-soluble resin (A) contained in the above ratio. More preferably, it is replaced by 30 to 70% by weight of other binder resin (F), that is, preferably other binder resin (F) relative to the total of alkali-soluble resin (A) and other binder resin (F). The ratio is 90% by weight or less, for example, 10 to 90% by weight, preferably 20 to 80% by weight, more preferably 30 to 70% by weight, and other binder resin (F) and alkali-soluble resin (A) are used together. .

In other words, as the other binder resin (F), by using the alkali-soluble resin (A') in combination, it is possible to obtain an effect of improving the linearity of the obtained pattern, and the adjustment of the development time and the taper angle is easy. By using an alkali-soluble resin (A") or an alkali-soluble resin (A1"), it is possible to obtain an effect of improving the linearity of the obtained pattern, and the adjustment of the development time and the taper angle is easy, but if the content is such If the amount is too small, the effect of the present invention by using the other binder resin (F) cannot be sufficiently obtained. If the amount is too large, the ratio of the alkali-soluble resin (A) of the present invention is lowered, thereby impairing the alkali-soluble resin (A). The effect.

Therefore, when the alkali-soluble resin (A) and the other binder resin (F) are used in combination, the combined ratio is preferably in the above range.

The content of the photopolymerization initiator (B) is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 0.7% by weight or more, based on the total solid content of the photosensitive colored resin composition of the present invention. It is 30% by weight or less, preferably 20% by weight or less. If the photopolymerization initiator (B) is contained If the amount is too small, the sensitivity is lowered. On the other hand, if the amount is too large, the solubility of the unexposed portion in the developer is lowered, and development failure is liable to occur.

When the accelerator is used together with the photopolymerization initiator (B), the content of the accelerator is usually 0% by weight or more, preferably 0.02% by weight or more based on the total solid content of the photosensitive colored resin composition of the present invention. It is usually 10% by weight or less, preferably 5% by weight or less, and preferably the accelerator is used in an amount of 0.1 to 50% by weight, particularly 0.1 to 10% by weight, based on the photopolymerization initiator (B).

When the proportion of the photopolymerization initiator component including the photopolymerization initiator (B) and the accelerator is remarkably low, the sensitivity to the exposure light is lowered, and if it is remarkably high, it is not exposed. Part of the solubility in the developer is lowered, resulting in poor development.

Further, the proportion of the sensitizing dye in the photosensitive colored resin composition of the present invention is usually 0 to 20% by weight, preferably 0 to 15% by weight based on the total solid content of the photosensitive colored resin composition. %, more preferably 0 to 10% by weight.

The content of the coloring matter (C) is usually selected in the range of from 1 to 70% by weight based on the total solid content in the photosensitive colored resin composition. In this range, it is more preferably 10 to 70% by weight, and particularly preferably 20 to 60% by weight. When the content of the coloring material (C) is too small, the film thickness with respect to the color density becomes too large, and there is a case where the gap control during liquid crystal cell formation is adversely affected. On the contrary, if the content of the color material (C) is too large, sufficient image formation properties cannot be obtained.

Further, in the photosensitive colored resin composition, the alkali-soluble resin (A) The amount relative to the colorant (C) is usually 20 to 500% by weight, preferably 30 to 300% by weight, more preferably 50 to 200% by weight. When the content of the alkali-soluble resin (A) relative to the coloring matter (C) is too low, the solubility of the unexposed portion in the developing solution is lowered, and development failure is liable to occur, and if it is remarkably high, it is difficult to obtain a desired pixel film thickness.

The content of the dispersing agent (D) is usually 50% by weight or less, preferably 30% by weight or less, usually 1% by weight or more, and preferably 3% by weight or more based on the solid content of the photosensitive colored resin composition. Further, the content of the dispersing agent (D) is usually 5% by weight or more, particularly preferably 10% by weight or more, usually 200% by weight or less, and particularly preferably 80% by weight or less based on the coloring matter (C). When the content of the dispersant (D) is too small, sufficient dispersibility may not be obtained. If the content of the dispersant (D) is too large, the ratio of the other components may decrease, and the color density, the sensitivity, the film formability, and the like tend to be lowered.

It is particularly preferable to use a polymer dispersant and a pigment derivative as a dispersing agent (D) in combination. In this case, the blending ratio of the pigment derivative is usually 0 by weight with respect to the total solid content of the photosensitive colored resin composition of the present invention. % or more is preferably 1% by weight or more, usually 10% by weight or less, preferably 5% by weight or less.

When the photopolymerizable monomer (E) is used, the content thereof is usually 90% by weight or less, preferably 80% by weight or less based on the total solid content of the photosensitive colored resin composition. When the content of the photopolymerizable monomer (E) is too large, the permeability of the developer to the exposed portion becomes high, and it becomes difficult to obtain a good image. In addition, the lower limit of the content of the photopolymerizable monomer (E) is usually 1% by weight or more, preferably 5% by weight or more.

When the surfactant is used, the content thereof is usually 0.001 to 10% by weight, preferably 0.005 to 1% by weight, more preferably 0.01 to 0.5% by weight, based on the total solid content of the photosensitive colored resin composition. It is 0.03 to 0.3% by weight. When the content of the surfactant is less than the above range, the smoothness and uniformity of the coating film may not be exhibited, and if it is too large, not only the smoothness and uniformity of the coating film but also other characteristics may not be exhibited. deterioration.

Further, in the photosensitive colored resin composition of the present invention, the solution is adjusted using the above organic solvent so that the solid content concentration is usually 5 to 50% by weight, preferably 10 to 30% by weight.

<Method for Producing Photosensitive Colored Resin Composition>

The photosensitive colored resin composition of the present invention (hereinafter sometimes referred to as "photoresist") is produced by a usual method.

In general, it is preferred to disperse the colorant (C) in advance using a paint conditioner, a sand mill, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. Since the color material (C) is finely divided by the dispersion treatment, the coating property of the photoresist is improved. Moreover, when a black coloring material is used as a coloring material (C), it can contribute to the improvement of a light-shielding capability.

The dispersion treatment is usually preferably carried out by using a coloring matter (C), an organic solvent, and optionally a dispersing agent (D), and an alkali-soluble resin (A) and/or other binder resin (F). The system is carried out (hereinafter, the mixture supplied to the dispersion treatment and the composition obtained by the treatment may be referred to as "ink"). In particular, when a polymer dispersant is used as the dispersing agent (D), it is preferable to suppress the time-dependent thickening of the obtained ink and the photoresist (excellent dispersion stability).

Further, when the solution containing all the components blended in the colored resin composition is subjected to dispersion treatment, there is a possibility that the highly reactive component is deteriorated due to heat generation during the dispersion treatment. Therefore, it is preferred to carry out the dispersion treatment by a system comprising the above components.

When the coloring material (C) is dispersed by a sand mill, it is preferred to use glass beads or zirconia beads having a diameter of about 0.1 to 8 mm. In the dispersion treatment conditions, the temperature is usually from 0 ° C to 100 ° C, preferably from room temperature to 80 ° C. The dispersion time is different depending on the composition of the liquid and the size of the dispersion processing apparatus, and the like, and it is necessary to adjust it appropriately. The standard of dispersion is to control the gloss of the ink so that the 20 degree specular gloss (JIS Z8741) of the photoresist is in the range of 100 to 200. When the glossiness of the photoresist is low, the dispersion treatment may be insufficient, and the coarse pigment (colorant) particles may remain in a large amount, and the developability, the adhesion, the resolution, and the like may be insufficient. Further, when the dispersion treatment is carried out until the gloss value exceeds the above range, the pigment is broken and a large amount of ultrafine particles are generated, so that the dispersion stability tends to be impaired.

Then, the ink obtained by the above dispersion treatment is mixed with the above-mentioned other components contained in the photoresist to prepare a uniform solution. In the manufacturing step of the photoresist, fine impurities are often mixed in the liquid, so it is desirable to filter the obtained photoresist by a filter or the like.

[Color Filter]

Next, a color filter using the photosensitive colored resin composition of the present invention will be described in accordance with the production method thereof.

(1) Transparent substrate (support) As a transparent substrate of a color filter, if it is transparent and moderately strong The material is not particularly limited. The material may, for example, be a polyester resin such as polyethylene terephthalate, a polyolefin resin such as polypropylene or polyethylene, or a thermoplastic resin sheet such as polycarbonate, polymethyl methacrylate or polyfluorene. A thermosetting resin sheet such as an epoxy resin, an unsaturated polyester resin or a poly(meth)acrylic resin; or various glasses. Among them, from the viewpoint of heat resistance, glass or a heat resistant resin is preferred.

In order to improve the surface physical properties such as adhesion, the transparent substrate and the black matrix-forming substrate may be subjected to a film forming treatment of various resins such as a corona discharge treatment, an ozone treatment, a decane coupling agent, or a urethane-based resin.

The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. Further, when the film formation treatment of various resins is carried out, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.

(2) Black matrix The color filter of the present invention can be produced by providing a black matrix on a transparent substrate and generally forming a pixel image of red, green, and blue. The photosensitive colored resin composition of the present invention can be used as black, red, and green. And at least one coating liquid for forming a photoresist in blue. The black photoresist is formed on the surface of the blank glass on the transparent substrate, and the red, green, and blue colors are formed on the resin black matrix forming surface formed on the transparent substrate or using a chromium compound and other light shielding metal materials. On the metal black matrix forming surface, each process of coating, heat drying, image exposure, development, and heat hardening is performed to form pixel images of respective colors.

Black matrix is made of light-shielding metal film or resin black matrix The resin composition is colored on the transparent substrate. As the light-shielding metal material, a chromium compound such as metal chromium, chromium oxide or chromium nitride, nickel or a tungsten alloy or the like may be used, or the laminate may be formed in a plurality of layers.

The metal light-shielding film is generally formed by a sputtering method, and after forming a desired pattern in a film shape by a positive-type photoresist, a mixture of ammonium cerium nitrate and perchloric acid and/or nitric acid is used for chromium. The etching solution is etched using an etching liquid corresponding to the material for other materials, and finally the positive photoresist is peeled off by a dedicated stripping agent, thereby forming a black matrix.

In this case, first, the metal or metal is formed on the transparent substrate by evaporation or sputtering. A film of metal oxide. Then, after forming a coating film of the photosensitive colored resin composition on the film, the film is exposed by using a mask having a repeating pattern such as a stripe, a mosaic, or a triangle. Develop to form a photoresist image. Thereafter, the coating film may be subjected to an etching treatment to form a black matrix.

When a photosensitive colored resin composition for a resin black matrix is used, a photosensitive colored resin composition of the present invention containing a black colorant is used to form a black matrix. For example, a black color material containing or containing a plurality of kinds of carbon black, graphite, iron black, aniline black, cyanine black, titanium black, or the like, or a red, green, blue, etc. selected from inorganic or organic pigments and dyes is used. The photosensitive colored resin composition of the black color material obtained by mixing can form a black matrix by the same method as the method of forming the pixel image of red, green, and blue described below.

(3) Formation of pixels (3-1) Coating of photosensitive colored resin composition A photosensitive colored resin composition containing any one of red, green, and blue color materials is applied onto a transparent substrate provided with a black matrix, dried, and a photomask is superposed on the coating film, and the photomask is patterned through the photomask. For example, exposure, development, thermal hardening or photohardening as necessary, thereby forming a pixel image, and producing a colored layer. This operation is performed on the photosensitive colored resin compositions of the three colors of red, green, and blue, respectively, whereby a color filter image can be formed.

The application of the photosensitive colored resin composition for a color filter can be carried out by a spin coating method, a wire bar coating method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. In particular, the amount of the coating liquid used can be drastically reduced by the die-coating method, and the influence of mist or the like adhered by the spin coating method is not obtained at all, and the generation of foreign matter can be suppressed, and it is preferable from the viewpoint of the overall viewpoint.

If the thickness of the coating film is too thick, pattern development becomes difficult, and the gap adjustment in the liquid crystal unitization step becomes difficult. If it is too thin, it is difficult to increase the pigment concentration and the desired color cannot be expressed. The thickness of the coating film is a film thickness after drying, and is usually preferably in the range of 0.2 to 20 μm, more preferably in the range of 0.5 to 10 μm, still more preferably in the range of 0.8 to 5 μm.

(3-2) Drying of the coating film The drying of the coating film after applying the photosensitive colored resin composition onto the substrate is preferably carried out by a drying method using a hot plate, an infrared (IR) infrared oven or a convection oven. The drying conditions can be appropriately selected depending on the kind of the solvent component described above, the performance of the dryer to be used, and the like. The drying time is selected according to the kind of the solvent component and the performance of the dryer to be used, and is usually selected from the range of drying at a temperature of 40 to 200 ° C for 15 seconds to 5 minutes, preferably at a temperature of 50 to 130 ° C. Dry for 30 seconds to 3 minutes Range selection.

The higher the drying temperature, the higher the adhesion between the coating film and the transparent substrate. However, if the drying temperature is too high, the binder resin is decomposed and thermal polymerization is caused to cause development failure. Further, the drying step of the coating film may be a vacuum drying method in which drying is performed in a decompression chamber without increasing the temperature.

(3-3) exposure Image exposure is performed by laminating a negative mask pattern on a coating film of a photosensitive colored resin composition, and irradiating a light source of ultraviolet rays or visible rays through the mask pattern. In this case, in order to prevent the sensitivity of the photopolymerizable layer due to oxygen from being lowered, it is also possible to form an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film, followed by exposure. The light source used in the above image exposure is not particularly limited. Examples of the light source include 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 lamp, a fluorescent lamp, and the like, or an argon ion laser. , YAG laser, excimer laser, nitrogen laser, xenon-cadmium laser, semiconductor laser and other laser sources. An optical filter can also be used when irradiating light of a predetermined wavelength.

(3-4) Development The color filter of the present invention can be formed by subjecting a coating film of a photosensitive colored resin composition to image exposure by the above-mentioned light source, by using an organic solvent, or comprising a surfactant and a basic compound. The development of the aqueous solution forms an image on the substrate.

The aqueous solution may further contain an organic solvent, a buffer, a binder, a dye or a pigment.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium citrate, potassium citrate, sodium metasilicate, and sodium phosphate. An inorganic basic compound such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate or ammonium hydroxide, or a single. Di- or triethanolamine, single. Di- or trimethylamine, single. Di- or triethylamine, mono or diisopropylamine, n-butylamine, single. An organic basic compound such as diisopropanolamine, ethyleneimine, ethylenediamine, tetramethylammonium hydroxide (TMAH), choline or the like. These basic compounds may also be a mixture of two or more kinds.

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceryl alkyl esters. Anionic interfacial activity such as nonionic surfactants, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinates Amphoteric surfactants such as alkylbetaines and amino acids.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl sirolius, butyl siroli, phenyl siroli, propylene glycol, diacetone alcohol, and the like. The organic solvent may be used singly or in combination with an aqueous solution.

The conditions of the development treatment are not particularly limited. Usually, the development temperature is in the range of 10 to 50 ° C, preferably 15 to 45 ° C, particularly preferably 20 to 40 ° C, and the development method can be carried out by a dip development method or a spray development method. Any method such as a brush development method or an ultrasonic development method.

(3-5) Thermal hardening treatment The developed color filter substrate is subjected to a heat hardening treatment. Heat at this time The curing treatment conditions are as follows: the temperature is selected in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is selected in the range of 5 to 60 minutes. Patterned image formation of one color is accomplished via the series of steps. This step is repeated in sequence, and black, red, green, and blue are patterned to form a color filter. Furthermore, the order of patterning of the four colors is not limited to the above order.

(3-6) Formation of transparent electrode For the color filter, a transparent electrode such as indium tin oxide (ITO) is formed on the image directly in this state, and is used as a part of a component such as a color display or a liquid crystal display device, however, in order to improve surface smoothing For the sake of durability and durability, it is also possible to provide an outer coating such as polyamine or polyimine on the image. Further, there is a case where a transparent electrode is not formed in some applications such as a planar alignment type driving (IPS (In-Plane Switching) mode).

[Liquid Crystal Display Device]

The liquid crystal display device of the present invention is produced by using the above-described color filter of the present invention.

The liquid crystal display device is usually formed by forming an alignment film on a color filter, dispersing a spacer on the alignment film, and bonding the substrate to the opposite substrate to form a liquid crystal cell in the formed liquid crystal cell. The liquid crystal is injected and the wires are connected to the counter electrode. As the alignment film, a resin film such as polyimide or the like is preferable. The formation of the alignment film is usually performed by a gravure printing method and/or a flexographic printing method, and the thickness of the alignment film is several tens of nm. After the hardening treatment of the alignment film by thermal baking, irradiation with ultraviolet rays or use of an alignment cloth The surface treatment is performed by the treatment, and the surface state is adjusted to adjust the inclination of the liquid crystal.

As the spacer, a size corresponding to the gap (void) with the counter substrate can be used, and it is usually 2 to 8 μm. A photosensitive spacer (PS, photo spacer) for forming a transparent resin film on the color filter substrate by photolithography can also be used as a substitute for the spacer. As the counter substrate, an array substrate, in particular, a thin film-transistor (TFT) substrate is generally used.

The gap to be bonded to the counter substrate differs depending on the application of the liquid crystal display device, and is usually selected in the range of 2 to 8 μm. After bonding to the counter substrate, the portion other than the liquid crystal injection port is sealed by a sealing material such as an epoxy resin. The sealing material is cured by ultraviolet (UV) irradiation and/or heating to seal the periphery of the liquid crystal cell.

After the liquid crystal cell sealed in the periphery is cut into the panel unit, the pressure is reduced in the vacuum chamber, and the liquid crystal injection port is immersed in the liquid crystal, and then the inside of the chamber is deflated, thereby injecting the liquid crystal into the liquid crystal cell. The degree of pressure reduction in the liquid crystal cell is usually from 1 × 10 ^-2 to 1 × 10 ^-7 Pa, preferably from 1 × 10 ^-3 to 1 × 10 ^-6 Pa. Further, it is preferable to heat the liquid crystal cell at the time of pressure reduction, and the heating temperature is usually 30 to 100 ° C, more preferably 50 to 90 ° C. The heating at the time of pressure reduction is usually maintained in the range of 10 to 60 minutes, and thereafter immersed in the liquid crystal. The liquid crystal cell in which the liquid crystal is injected is filled, and the liquid crystal injection port is sealed by curing the UV hardening resin, thereby completing the liquid crystal display device (panel).

The type of the liquid crystal is not particularly limited, and may be a conventional liquid crystal such as an aromatic system, an aliphatic system or a polycyclic compound, or may be a lyotropic liquid crystal, which is thermally induced. Any of liquid crystals, etc. Among the thermotropic liquid crystals, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like are known, and any of them may be used.

[Organic EL Display]

The organic EL display of the present invention is produced by using the color filter of the present invention.

When the organic EL display is produced by using the color filter of the present invention, for example, as shown in FIG. 1, first, a pattern formed of a coloring resin composition is formed on the transparent supporting substrate 10 (ie, the pixel 20, and a color filter formed by a resin black matrix (not shown) provided between the adjacent pixels 20, and the organic light-emitting body 500 is laminated on the color filter via the organic protective layer 30 and the inorganic oxide film 40. This makes it possible to produce the organic EL element 100. Further, at least one of the pixel 20 and the resin black matrix is produced by using the photosensitive colored resin composition of the present invention. As a method of laminating the organic light-emitting body 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light-emitting layer 53, an electron injection layer 54, and a cathode 55 are successively formed on the upper surface of the color filter. A method of bonding an organic light-emitting body 500 formed on another substrate to the inorganic oxide film 40 or the like. The organic EL device 100 produced by the method can be used, for example, the method described in "Organic EL Display" (OHM Corporation, issued on August 20, 2004, at the time of Jing Shi, Anda Chiba, and Murata Yuki). , making organic EL displays.

Furthermore, the color filter of the present invention can be applied to an organic EL display of a passive driving mode, and can also be applied to an organic EL display of an active driving mode.

[Examples]

The present invention will be more specifically described by way of Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited by the following examples as long as they do not go beyond the gist of the invention.

<Synthesis Example 1: Synthesis of alkali-soluble resin (II)>

Into the reaction vessel, 400 parts by weight of "NC3000" manufactured by Nippon Kayaku Co., Ltd. (in the above formula (1-a), R ⁴¹ = H, weight average molecular weight: 1900, epoxy equivalent: 288), 102 was charged. Parts by weight of acrylic acid, 0.3 parts by weight of p-methoxyphenol, 5 parts by weight of triphenylphosphine, and 264 parts by weight of propylene glycol monomethyl ether acetate, were stirred at 95 ° C until the acid value became 3 mg KOH / g below. It takes 9 hours (acid value 2.2 mgKOH/g) until the acid value reaches the target. Then, 151 parts by weight of tetrahydrofurfuric anhydride was further added and reacted at 95 ° C for 4 hours to obtain a polystyrene-equivalent weight average molecular weight (Mw) having an acid value of 102 mgKOH/g and measured by GPC. It is a solution of 3200 alkali soluble resin (II).

<Synthesis Example 2: Synthesis of alkali-soluble resin (III)>

Into the reaction vessel, 400 parts by weight of "NC3000H" manufactured by Nippon Kayaku Co., Ltd. (in the above formula (1-a), R ⁴¹ = H, epoxy equivalent of 288, softening point of 69 ° C), 102 was charged. Parts by weight of acrylic acid, 0.3 parts by weight of p-methoxyphenol, 5 parts by weight of triphenylphosphine, and 264 parts by weight of propylene glycol monomethyl ether acetate, were stirred at 95 ° C until the acid value became 3 mg KOH / g below. It takes 9 hours (acid value 2.2 mgKOH/g) until the acid value reaches the target. Then, 151 parts by weight of tetrahydrofurfuric anhydride was further added and reacted at 95 ° C for 4 hours to obtain a polystyrene-equivalent weight average molecular weight (Mw) having an acid value of 102 mgKOH/g and measured by GPC. It is a 3900 alkali soluble resin (III) solution.

<Synthesis Example 3: Synthesis of alkali-soluble resin (IV)>

An epoxy resin having a weight average molecular weight of 3,900 (R ⁴¹ =H in the above formula (1-a)) was used instead of "NC3000H", and an acid value of 102 mgKOH/g was obtained by the synthesis method in Synthesis Example 2. Further, the polystyrene-equivalent weight average molecular weight (Mw) measured by GPC was 6800, an alkali-soluble resin (IV) solution.

<Synthesis Example 4: Preparation of Ink>

50 parts by weight of color carbon black ("MA-8" manufactured by Mitsubishi Chemical Corporation, average particle diameter of 24 μm, dibutyl phthlate (DBP, Dibutyl phthlate) oil absorption of 58 ml / 100 g) Propylene Glycol methyl Ether Acetate (PGMEA) and a urethane polymer dispersant "Disperbyk-182" (manufactured by BYK-CHEMIE Co., Ltd.) so that the solid content of the dispersant is The ratio of 10 parts by weight, and the solid content concentration was 30% by weight. The total weight of the dispersion was 181 g.

The mixture was thoroughly stirred by a mixer to carry out premixing. Next, dispersion treatment was carried out for 6 hours in the range of 25 to 45 ° C by a coating shaker. As beads, use 0.5 mm The zirconia beads are added in the same weight as the dispersion. After the completion of the dispersion (the 20 degree specular gloss of 170 in JIS Z8741), the beads were separated from the dispersion by a filter to prepare Ink 1.

<Synthesis Example 5: Synthesis of alkali-soluble resin (V)>

Use 140 parts by weight of "NC3000H" and 260 parts by weight of "NC3000" In place of 400 parts by weight of "NC3000H", a synthesis method of Synthesis Example 2 was carried out to obtain a base having an acid value of 102 mgKOH/g and a polystyrene-equivalent weight average molecular weight (Mw) of 3,450 as measured by GPC. Soluble resin (V) solution.

<Synthesis Example 6: Synthesis of alkali-soluble resin (VI)>

160 parts by weight of an epoxy resin having a weight average molecular weight of 3,900 (R ⁴¹ = H in the above formula (1-a)) and 240 parts by weight of "NC3000H" used in Synthesis Example 3 were used instead of 400 parts by weight. "NC3000H", by the synthesis method in Synthesis Example 2, an alkali-soluble resin (VI) having an acid value of 102 mgKOH/g and a polystyrene-equivalent weight average molecular weight (Mw) of 5100 as measured by GPC was obtained. Solution.

<Synthesis Example 7: Synthesis of alkali-soluble resin (VII)>

40 g of the epoxy compound (epoxy equivalent 231) represented by the above formula, 12.7 g of acrylic acid, 47.8 g of methoxybutyl acetate, and 1.00 g were placed in a flask equipped with a thermometer, a stirrer, and a condenser. Triphenylphosphine and 0.025 g of p-methoxyphenol were reacted at 90 ° C while stirring until the acid value became 5 mgKOH/g or less. Reaction needs 15 An epoxy acrylate solution was obtained in an hour.

25 parts of the above epoxy acrylate solution and 0.76 parts by weight of trimethylolpropane and 3.7 parts by weight of biphenyltetracarboxylic dianhydride (BPDA) were placed in a flask equipped with a thermometer, a stirrer, and a condenser. And 3.9 parts by weight of tetrahydrophthalic anhydride (THPA), and the mixture was gradually heated to 105 ° C while stirring to cause a reaction.

After the resin solution became transparent, it was diluted with methoxybutyl acetate to prepare a solid content of 50% by weight to obtain an acid value of 131 mgKOH/g, and a polystyrene-equivalent weight average molecular weight measured by GPC. (Mw) is an alkali-soluble resin (VII) of 3,000.

Further, the alkali-soluble resin (VII) corresponds to the "alkali-soluble resin (A')" in the present invention.

<Synthesis Example 8: Synthesis of alkali-soluble resin (VIII)>

50 g of the above-structured epoxy compound (epoxy equivalent: 264), 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, and 0.936 g of triphenyl were placed in a flask equipped with a thermometer, a stirrer, and a condenser. a phosphine, and 0.032 g of p-methoxyphenol, while stirring, at 90 ° C The reaction is carried out until the acid value becomes 5 mgKOH/g or less. The reaction took 12 hours to obtain an epoxy acrylate solution.

25 parts by weight of the above epoxy acrylate solution and 0.76 parts by weight of trimethylolpropane (TMP) and 3.3 parts by weight of biphenyltetracarboxylic dianhydride (BPDA) were placed in a flask equipped with a thermometer, a stirrer, and a condenser. 3.5 parts by weight of tetrahydrophthalic anhydride (THPA) was gradually heated to 105 ° C while stirring to cause a reaction.

After the resin solution became transparent, it was diluted with methoxybutyl acetate to prepare a solid content of 50% by weight to obtain an acid value of 131 mgKOH/g, and a polystyrene-equivalent weight average molecular weight measured by GPC. (Mw) is an alkali soluble resin (VIII) of 2,600.

In addition, the alkali-soluble resin (VIII) corresponds to the "alkali-soluble resin (A1")" in the present invention.

[Examples 1 to 6 and Comparative Examples 1 to 3]

(1) Preparation of photoresist (photosensitive colored resin composition) Using the ink 1 prepared in Synthesis Example 4, each component was added in the following blending ratio, and the mixture was stirred and dissolved by a stirrer to prepare a black photoresist.

<mixing ratio>

Ink 1 prepared in Synthesis Example 4: solid content was 50 g of each alkali-soluble resin solution prepared in Synthesis Examples 1 to 3 and 5 to 8: solid content was 30 g of photopolymerizable monomer (dipentaerythritol hexaacrylate) ): 10 g of a solution containing a polymer dispersant ("byk-182" manufactured by BYK-CHEMIE Co., Ltd.): 5 g of a photopolymerization initiator (CGI242) manufactured by Ciba Specialty Chemicals Co., Ltd., the following structure An oxime ester compound represented by the formula: 5 g Organic solvent (PGMEA): 300 g of surfactant ("FC-430" fluorine-based surfactant manufactured by Sumitomo 3M): The concentration in the photoresist becomes 100 ppm.

(2) Evaluation of photoresist The black photoresist prepared in (1) was applied onto a glass substrate ("7059" manufactured by Corning Co., Ltd.) by a spin coater, and dried at 80 ° C for 1 minute with a hot plate. The film thickness of the photoresist after drying was measured by a stylus type film thickness meter ("α-STEP" manufactured by Tencor Corporation) to be 1 μm. Then, the exposure amount was changed by a high pressure mercury lamp through a photomask, and image exposure was performed on the sample. Thereafter, spray development was carried out using a sodium carbonate aqueous solution having a concentration of 0.8% by weight at a temperature of 25 ° C, whereby a photoresist pattern was obtained.

With respect to the formed resist pattern, the sensitivity, the resolution, and the light blocking property were evaluated by the following criteria, and the results are shown in Table-1.

1. Sensitivity The sensitivity of a reticle pattern having a size of 20 μm is expressed in a suitable exposure amount (mJ/cm ² ) at which a corresponding size can be formed. That is, the photoresist having a small amount of exposure can form an image with a low exposure amount, and thus exhibits high sensitivity.

2. Resolution The minimum pattern size of the resolvable photoresist in the exposure amount of the reticle pattern having a size of 20 μm was completely observed under a microscope at a magnification of 200 times.

The minimum pattern size is 10 μm or less: ◎ The minimum pattern size exceeds 10 μm and is 15 μm or less: ○ The minimum pattern size exceeds 15 μm: ×

3. Shading The optical density (OD, Optical Density) of the image portion was measured with a Macbeth reflection densitometer ("TR927" manufactured by Kollmorgen Co., Ltd.). Further, the OD value indicates the value of the light blocking ability, and the larger the value indicates the higher the light blocking property.

4. Linearity The shape of the thin black pixel in the exposure amount of the reticle pattern having a size of 20 μm was completely observed by a microscope at a magnification of 1000 times.

The linearity of the edge is excellent: ◎ The linearity of the edge is relatively good: ○ There are a number of protrusions or irregularities at the edge: △ The edge of the protrusion or the unevenness is quite: X

As apparent from Table 1, according to the present invention, it is possible to provide a photosensitive colored resin composition which is high in sensitivity, excellent in resolution and light-shielding property.

The present invention has been described in detail with reference to the preferred embodiments of the present invention, and various modifications may be made without departing from the spirit and scope of the invention.

In addition, the present application is based on a Japanese patent application filed on Jun.

10‧‧‧Transparent support substrate

20‧‧ ‧ pixels

30‧‧‧Organic protective layer

40‧‧‧Inorganic oxide film

50‧‧‧Transparent anode

51‧‧‧ hole injection layer

52‧‧‧ hole transport layer

53‧‧‧Lighting layer

54‧‧‧Electronic injection layer

55‧‧‧ cathode

100‧‧‧Organic EL components

500‧‧‧Organic emitters

Fig. 1 is a schematic cross-sectional view showing an example of an organic EL device including the color filter of the present invention.

Claims (14)

A photosensitive colored resin composition for a color filter comprising a reaction product of an epoxy resin (a) represented by the following formula (1-a) and a carboxylic acid (b) containing an unsaturated group; The alkali-soluble resin (A), the photopolymerization initiator (B), and the colorant (C) obtained by reacting a polybasic acid and/or an anhydride thereof (c), characterized in that the alkali-soluble resin (A) is used for coagulation The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) is 3,300 or more and 50,000 or less. [In the above formula (1-a), n represents an average value, and represents a number of 0 to 10; and R ⁴¹ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, and a ring having a carbon number of 3 to 10. Any one of an alkyl group, a phenyl group, a naphthyl group or a biphenyl group; further, a plurality of R ⁴¹ present in one molecule may be the same or different; G represents a glycidyl group]. A photosensitive coloring resin composition for a color filter according to the first aspect of the invention, further comprising a dispersing agent (D). The photosensitive colored resin composition for a color filter according to the first or second aspect of the invention, further comprising a photopolymerizable monomer (E). The photosensitive colored resin composition for a color filter according to the first aspect of the invention, further comprising an alkali-soluble resin (A'), wherein the alkali-soluble resin (A') has the following formula (1) a reaction of the epoxy compound (a') represented by -a') with an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester (b') having a carboxyl group at the ester moiety Obtained by reacting with a polybasic acid and/or its anhydride (c'), [In the above formula (1-a'), p and q each independently represent an integer of 0 to 4, and R ³¹ and R ³² each independently represent an alkyl group or a halogen atom; and R ³³ and R ³⁴ each independently represent an extension. An alkyl group; x and y each independently represent an integer of 0 or more]. The photosensitive colored resin composition for a color filter according to the first aspect of the invention, further comprising an alkali-soluble resin (A"), wherein the alkali-soluble resin (A") has the following formula (1) A reaction product of the epoxy compound (a") represented by -a") and a carboxylic acid (b") containing an unsaturated group, which is obtained by reacting with a polybasic acid and/or an anhydride thereof (c"), In the above formula (1-a"), X represents a linking group represented by the following formula (2a), (2b) or (3); wherein the molecular structure includes one or more adamantane structures; An integer of 2 or 3; (In the above formulae (2a) and (2b), R ¹ to R ⁴ and R ¹³ to R ¹⁵ each independently represent an adamantyl group which may have a substituent, a hydrogen atom, and a carbon number which may have a substituent of 1~ a 12-alkyl group or a phenyl group which may have a substituent; in the above formula (3), R ⁵ to R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent; Y represents a divalent linking group containing an adamantane structure which may have a substituent; in the above formulas (2a), (2b) and (3), * represents a formula (1) The bonding site of the glycidoxy group in a"))]. The photosensitive colored resin composition for color filters of claim 5, wherein the polybasic acid and/or its anhydride (c") comprises the following (i) and (ii), (i) {four yuan Acid and/or its anhydride} and/or {dibasic acid and/or its anhydride} (ii) tribasic acid and/or its anhydride. The photosensitive colored resin composition for a color filter according to the first aspect of the invention, further comprising an alkali-soluble resin (A1"), wherein the alkali-soluble resin (A1") has the following formula (1) a reaction product of the epoxy compound (a") represented by -a") and a carboxylic acid (b") containing an unsaturated group, and a polyol (d"), the mixture and the polybasic acid and/or its anhydride Obtained by (c") reaction, In the above formula (1-a"), X represents a linking group represented by the following formula (2a), (2b) or (3); wherein the molecular structure includes one or more adamantane structures; An integer of 2 or 3; (In the above formulae (2a) and (2b), R ¹ to R ⁴ and R ¹³ to R ¹⁵ each independently represent an adamantyl group which may have a substituent, a hydrogen atom, and a carbon number which may have a substituent of 1~ a 12-alkyl group or a phenyl group which may have a substituent; in the above formula (3), R ⁵ to R ¹² each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent; Y represents a divalent linking group containing an adamantane structure which may have a substituent; in the above formulas (2a), (2b) and (3), * represents a formula (1) The bonding site of the glycidoxy group in a"))]. The photosensitive colored resin composition for color filters of claim 7, wherein the polybasic acid and/or its anhydride (c") comprises the following (i) and (ii), (i) {four yuan Acid and/or its anhydride} and/or {dibasic acid and/or its anhydride} (ii) tribasic acid and/or its anhydride. The photosensitive coloring resin composition for a color filter according to the first aspect of the invention, wherein the photopolymerization initiator (B) comprises an oxime ester derivative. The photosensitive colored resin composition for a color filter according to the first aspect of the invention, wherein the content of the colorant (C) is 20 to 60% by weight based on the total solid content of the photosensitive colored resin composition. A photosensitive coloring resin composition for a color filter according to the first aspect of the invention, wherein the color material (C) contains a black coloring material. A color filter comprising a pixel or a black matrix formed using the photosensitive colored resin composition according to any one of claims 1 to 11 on a transparent substrate. A liquid crystal display device produced by using a color filter of claim 12 of the patent application. An organic EL display produced by using a color filter of claim 12 of the patent application.