JP2012083549A - Photosensitive coloring resin composition for color filter, color filter, liquid crystal display device, and organic el display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive coloring resin composition for a color filter which is excellent in image formation property even when density of a coloring material is high, excellent in balance between sensitivity and solubility, and further excellent in sharpness and adhesion of pixel edges; and to provide a color filter using the photosensitive coloring resin composition, liquid crystal display device using the color filter, and an organic EL display.SOLUTION: The photosensitive coloring resin composition for a color filter contains an alkali-soluble resin (A); at least one selected from a group consisting of an alkali-soluble resin (A'), an alkali-soluble resin (A1'), an alkali-soluble resin (A''), and an alkali-soluble resin (A1''); a photo-polymerization initiator (B); a coloring agent (C); and a thiol compound containing two or more mercapto groups, and in which a carbon atom at α position with respect to the mercapto group includes at least one hydrocarbon group as a substitution group (D).

Description

  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, even when the colorant concentration is high, the image forming property is excellent, the balance between sensitivity and solubility is excellent, the sharpness of the pixel edge, and the photosensitive coloring resin composition for color filter that is excellent in adhesion, and its Regarding usage.

Conventionally, as a method for producing a color filter using a pigment, a dyeing method, an electrodeposition method, an ink jet method, a pigment dispersion method, and the like are known.
In the case of producing a color filter by the pigment dispersion method, usually a photosensitive resin obtained by adding a binder resin, a photopolymerization initiator, a photopolymerizable monomer, etc. to a colored resin composition obtained by dispersing a pigment with a dispersant or the like. After coating with a coloring resin composition on a glass substrate, drying, exposing using a mask and developing, a colored pattern is formed by heating, and then the pattern is fixed by heating to form pixels. . These steps are repeated for each color to form a color filter.

  The photosensitive colored resin composition used for image formation of such a color filter is required to have characteristics such as sufficient resolution, good adhesion to a substrate, and low development residue. Furthermore, in recent years, a pixel having a high color density and a resin black matrix having a high optical density are required. For this reason, the photosensitive colored resin composition is required to be excellent in the above characteristics while containing a large amount of a coloring material such as a pigment or carbon black.

  In general, the photosensitive resin composition is subjected to a photolithographic process that undergoes coating, drying, exposure, and development processes. Therefore, in such a process, no residue or soiling occurs in the removed portion in the development process; There has always been a demand for the part to have sufficient solubility; to improve pixel formation such as sharpness of the pattern edge. However, when a pixel or a black matrix (hereinafter, these may be collectively referred to as a “pattern”) is formed using a photosensitive colored resin composition having a high content of the colorant as described above, development is performed. Residues and background stains occur on the substrate in the unexposed area in the process; good solubility in the unexposed area cannot be obtained; the sharpness of the pattern edge is inferior; Problems such as bad;

  In particular, the resin black matrix contains a black color material and has a light-shielding property in a wide wavelength region, so that (1) it is extremely difficult to make a difference in crosslink density between an exposed portion and an unexposed portion, and (2) exposure is performed. The difference in cross-linking density in the film thickness direction occurs even in the part where the film is cured, that is, it is hard to cure on the base surface side even if it is sufficiently cured on the light irradiation surface side, and (3) a black color material insoluble in the developer. Since a large amount of is contained, it is difficult to obtain high developability.

  Therefore, in order to solve such problems, 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 present inventors, even when this binder resin is used, since the balance between solubility and sensitivity is insufficient, the penetration of the developer into the exposed portion occurs simultaneously with the dissolution of the unexposed portion, It has been found that problems such as low linearity of the edge portion of the pattern; insufficient adhesion of the pattern to the substrate;

  Moreover, the photosensitive resin composition which uses the reaction material of the acrylic resin which has a carboxyl group, and an alicyclic epoxy group containing unsaturated compound as binder resin is proposed (refer patent document 2). However, according to the study by the present inventors, it was found that even when this binder resin was used, the sensitivity was not sufficient, so that the adhesion of the pattern to the substrate was poor and it was difficult to form a high-definition pattern. .

  Patent Document 3 discloses a photosensitive colored resin composition for a color filter using a reaction product of an epoxy resin containing a biphenyl skeleton as a binder resin, an unsaturated group-containing carboxylic acid, and a polybasic carboxylic acid anhydride. The thing is disclosed (refer patent document 3). Although the composition described in this document is excellent in adhesion to a substrate, sharpness of a pattern edge, and storage stability, there is room for improvement in sensitivity and linearity of a pixel edge.

Japanese Patent Laid-Open No. 11-84126 JP-A-1-289820 JP 2005-55814 A

  An object of the present invention is to provide a photosensitive colored resin composition for a color filter, which has excellent image-forming properties even when the colorant concentration is high, excellent balance between sensitivity and solubility, and excellent pixel edge sharpness and adhesion. And a color filter using the photosensitive colored resin composition, a liquid crystal display device using the color filter, and an organic EL display.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using a plurality of types of binder resins having a specific structure and a thiol compound having a specific structure, leading to the present invention. .
That is, the first gist of the present invention includes an alkali-soluble resin (A), an alkali-soluble resin (A ′), an alkali-soluble resin (A1 ′), an alkali-soluble resin (A ″), and an alkali-soluble resin ( A1 ”) containing at least one selected from the group consisting of photopolymerization initiator (B), coloring material (C), and two or more mercapto groups, and an α-position carbon atom with respect to the mercapto group Contains a thiol compound (D) having at least one hydrocarbon group as a substituent, in a photosensitive colored resin composition for a color filter.

<Alkali-soluble resin (A)>
The reaction product of the epoxy resin (a) represented by the following general formula (1-a) and the unsaturated group-containing carboxylic acid (b) is further reacted with a polybasic acid and / or its anhydride (c). An alkali-soluble resin (A) obtained in this way.

[In the said general formula (1-a), n shows an average value and shows the number of 0-10. R ⁴¹ represents any of 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, and a biphenyl group. A plurality of R ⁴¹ present in one molecule may be the same or different. G represents a glycidyl group. ]
<Alkali-soluble resin (A ')>
An epoxy compound (a ′) represented by the following general formula (1-a ′), an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group at the ester moiety ( An alkali-soluble resin (A ′) obtained by reacting a reaction product with b ′) with a polybasic acid and / or its anhydride (c ′).

[In the general 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 represents an alkylene group. x and y each independently represents an integer of 0 or more. ]
<Alkali-soluble resin (A1 ′)>
The epoxy compound (a ′) represented by the above general formula (1-a ′) and an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group at the ester moiety ( An alkali-soluble resin (A1 ′) obtained by reacting a mixture of a reaction product with b ′) and a polyhydric alcohol (d ′) with a polybasic acid and / or its anhydride (c ′).

<Alkali-soluble resin (A ")>
A reaction product of an epoxy compound (a ″) represented by the following general formula (1-a ″) and an unsaturated group-containing carboxylic acid (b ″) is reacted with a polybasic acid and / or its anhydride (c ″). Alkali-soluble resin (A ") obtained by making it.

[In the above general formula (1-a ″), X represents a linking group represented by the following general formula (2a), (2b) or (3), provided that one or more adamantane structures are present in the molecular structure. 1 represents an integer of 2 or 3.

(In the above general formulas (2a) and (2b), R ^{1 to} R ⁴ and R ^{13 to} R ¹⁵ each independently have an adamantyl group, a hydrogen atom, and a substituent which may have a substituent. An optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted phenyl group is shown.
In the general formula (3), R ^{5 to} R ¹² may each independently have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms that may have a substituent, or a substituent. Represents a phenyl group; Y represents a divalent linking group containing an adamantane structure, which may have a substituent.

In the general formulas (2a), (2b), and (3), * represents a binding site with the glycidyloxy group in the general formula (1-a ″).
<Alkali-soluble resin (A1 ")>
A mixture of a reaction product of the epoxy compound (a ″) represented by the general formula (1-a ″) and the unsaturated group-containing carboxylic acid (b ″) and a polyhydric alcohol (d ″) is converted into a polybasic acid. And / or an alkali-soluble resin (A1 ″) obtained by reacting with the anhydride (c ″) thereof.

The second gist of the present invention resides in a color filter having a pixel or black matrix formed using the photosensitive colored resin composition on a transparent substrate.
The third gist of the present invention resides in a liquid crystal display device manufactured using the color filter.
The fourth gist of the present invention resides in an organic EL display produced using the color filter.

  The photosensitive colored resin composition for color filters of the present invention has high sensitivity, good adhesion to the substrate, and balance between sensitivity and solubility even when containing a coloring material such as pigment or carbon black at a high concentration. In addition, the pixel edge sharpness and adhesion are excellent, and the resolution is high, so that a high-definition pixel can be formed. According to the present invention, by using such a photosensitive colored resin composition for a color filter, a high-quality color filter can be obtained, and further, a high-quality liquid crystal display device and an organic EL display can be provided. it can.

It is a cross-sectional schematic diagram which shows an example of the organic EL element provided with the color filter of this invention.

Embodiments of the present invention will be specifically described below, but the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.
In the present invention, “(meth) acryl” means “acryl and / or methacryl”, and the same applies to “(meth) acrylate” and “(meth) acryloyl”.

In the present invention, the “total solid content” means all components other than the solvent contained in the photosensitive colored resin composition for a color filter or in the ink described later.
In the present invention, the weight average molecular weight refers to a polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
Further, in the present invention, the “amine value” means an amine value in terms of effective solid content, unless otherwise specified, and is a value represented by the weight of KOH equivalent to the base amount per 1 g of the solid content of the dispersant. It is. The measuring method will be described later.

[Photosensitive colored resin composition for color filter]
The photosensitive colored resin composition for color filters of the present invention (hereinafter sometimes referred to as “photosensitive colored resin composition” or “colored resin composition”)
Alkali-soluble resin (A)
One or more photopolymerization initiators (B) selected from the group consisting of alkali-soluble resins (A ′), alkali-soluble resins (A1 ′), alkali-soluble resins (A ″), and alkali-soluble resins (A1 ″)
Color material (C)
And a thiol compound having two or more mercapto groups and having at least one hydrocarbon group as a substituent at a carbon atom in the α-position to the mercapto group (D)
As an essential component, preferably further,
Dispersant (E)
And photopolymerizable monomer (F)
If necessary, an alkali-soluble resin (A, A ′, A1 ′, A ″, A1
)) Other binder resins (H), organic solvents, adhesion improvers, coatability improvers, development improvers, ultraviolet absorbers, antioxidants, silane coupling agents, surfactants, pigment derivatives, etc. Other compounding components are included, and each compounding component is usually used in a state dissolved or dispersed in an organic solvent.

<Alkali-soluble resin (A)>
The alkali-soluble resin (A) is obtained by further reacting a reaction product of a specific epoxy resin (a) with an unsaturated group-containing carboxylic acid (b) with a polybasic acid and / or its anhydride (c). It is what
(1) Epoxy resin (a)
The epoxy resin (a) is represented by the following general formula (1-a).

[In the said general formula (1-a), n shows an average value and shows the number of 0-10. R ⁴¹ represents any of 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, and a biphenyl group. A plurality of R ⁴¹ present in one molecule may be the same or different. G represents a glycidyl group. ]
R ⁴¹ in the general formula (1-a) represents any of 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. As represented, from the viewpoint of sensitivity and solubility, R ⁴¹ is particularly preferably a hydrogen atom or a methyl group. A plurality of R ⁴¹ present in one molecule may be the same or different.

  The epoxy resin (a) represented by the general formula (1-a) includes, for example, a compound represented by the following general formula (1-a-1) and an epihalohydrin in the presence of an alkali metal hydroxide. It can be obtained by reacting.

(In the formula, n and R ⁴¹ represent the same meaning as in the general formula (1-a).)
The compound represented by the general formula (1-a-1) is obtained, for example, by subjecting a compound represented by the following general formula (1-a-2) and a phenol to a condensation reaction in the presence of an acid catalyst. be able to.

(In the formula, Z represents a halogen atom, a hydroxyl group, or a lower alkoxy group. R ⁴¹ represents the same meaning as in the general formula (1-a).)
In Z of the general formula (1-a-2), a halogen atom is preferably a chlorine atom, a bromine atom or the like, and a lower alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group. As a group.

On the other hand, phenols are aromatic compounds having one phenolic hydroxyl group per molecule, and specific examples thereof include phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butylphenol, octylphenol. , Various o-, m-, and p-isomers of alkylphenols typified by xylenol, methylbutylphenol, di-t-butylphenol, etc., or cycloalkylphenols typified by cyclopentylphenol, cyclohexylphenol, cyclohexylresole, etc., or Examples thereof include substituted phenols substituted with the group ^exemplified as R ⁴¹ in the general formula (1-a) such as phenylphenol. These phenols can be used individually by 1 type or in combination of 2 or more types.

When performing the said condensation reaction, Preferably the usage-amount of phenols is 0.5-20 mol with respect to 1 mol of compounds represented by general formula (1-a-2), Most preferably, it is 2-15 mol. .
In the above condensation reaction, it is preferable to use an acid catalyst, and various acid catalysts can be used, such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, anhydrous aluminum chloride, zinc chloride, etc. In particular, p-toluenesulfonic acid, sulfuric acid, and hydrochloric acid are preferable. Although the usage-amount of these acid catalysts is not specifically limited, It is preferable to use 0.1-30 weight% with respect to the compound represented by general formula (1-a-2).

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

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

After the neutralization treatment or the water washing treatment, the unreacted dihydroxybenzenes and the solvent are distilled off under heating under reduced pressure to concentrate the product, which is represented by the general formula (1-a-1). Can be obtained.
As a method for obtaining the epoxy resin (a) according to the present invention represented by the general formula (1-a) from the compound represented by the general formula (1-a-1), a known method can be adopted. 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 general formula (1-a-1) and an epihalohydrin such as excess epichlorohydrin or epibromhydrin. Or the epoxy resin (a) represented by general formula (1-a) can be obtained by making it react at the temperature of 20-120 degreeC for 1 to 10 hours, adding.

In the reaction for obtaining the epoxy resin (a), an aqueous solution of the alkali metal hydroxide may be used. In that case, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system and the pressure is reduced. Alternatively, water and epihalohydrin may be continuously distilled off under normal pressure, followed by liquid separation, water may be removed, and epihalohydrin may be continuously returned to the reaction system.
Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is added as a catalyst to a dissolved mixture of the compound represented by the general formula (1-a-1) and epihalohydrin, and 50 To the halohydrin etherified compound of the compound represented by the general formula (1-a-1) obtained by reacting at ~ 150 ° C for 1 to 5 hours, an alkali metal hydroxide solid or an aqueous solution is added, and again 20 A method of dehydrohalogenating (ring closure) by reacting at a temperature of ˜120 ° C. for 1 to 10 hours may be used.

The amount of epihalohydrin used in such a reaction is usually 1 to 20 mol, preferably 2 to 10 mol, relative to 1 equivalent of the hydroxyl group of the compound represented by formula (1-a-1). Moreover, the usage-amount of an alkali metal hydroxide is 0.8-15 mol normally with respect to 1 equivalent of hydroxyl groups of the compound represented by general formula (1-a-1), Preferably it is 0.9-11 mol.
Furthermore, in order to make the reaction proceed smoothly, the reaction may be carried out by adding an aprotic polar solvent such as dimethylsulfone or dimethylsulfoxide in addition to alcohols such as methanol and ethanol. When alcohols are used, the amount used is 2 to 20% by weight, preferably 4 to 15% by weight, based on the amount of epihalohydrin. Moreover, when using an aprotic polar solvent, the usage-amount is 5 to 100 weight% with respect to the quantity of an epihalohydrin, Preferably it is 10 to 90 weight%.

After washing the reaction product of such an epoxidation reaction with water or without washing with water, epihalohydrin and other added solvents under heating and reduced pressure, for example, under conditions of 110 to 250 ° C. and a pressure of 1.3 kPa (10 mmHg) or less. Are removed to obtain the desired epoxy resin (a).
In addition, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is dissolved. The reaction can be carried out by adding an aqueous solution to ensure ring closure. In this case, the amount of the alkali metal hydroxide used is preferably 0.01 to 0.3 mol, particularly preferably 1 equivalent to the hydroxyl group of the compound represented by the general formula (1-a-1) used for the epoxidation. Preferably it is 0.05-0.2 mol. The reaction temperature is 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

After completion of the reaction, the generated salt is removed by filtration, washing with water, and the like, and the epoxy represented by the general formula (1-a) is removed by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure. Resin (a) can be obtained.
(2) Unsaturated carboxylic acid (b)
As unsaturated group containing carboxylic acid (b), the unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned, As a specific example, (meth) acrylic acid, crotonic acid, o-, m-, p -Monocarboxylic acid such as vinyl benzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substitution, 2- (meth) acryloyloxyethyl succinic acid, 2-acryloyloxyethyl adipic acid 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid 2- (meth) acryloyloxypropyl adipic acid, 2- (meth) acryloyloxypropyl tetrahydrophthalic acid, 2- (Meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyladipic acid, 2- (meth) Acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid, 2- (meth) acryloyloxybutylmaleic acid (meth), acrylic acid with ε-caprolactone, β-propiolactone, γ- Monomers to which lactones such as butyrolactone and δ-valerolactone are added, or hydroxyalkyl (meth) acrylate, pentaerythritol tri (meth) acrylate, (anhydrous) succinic acid, (anhydrous) phthalic acid, ( Monomer) to which acid (anhydride) such as maleic acid is added, (meth) acrylic acid dye Chromatography and the like.

Of these, (meth) acrylic acid is particularly preferable from the viewpoint of sensitivity. These may be used alone or in combination of two or more.
(3) Reaction of epoxy resin (a) with unsaturated group-containing carboxylic acid (b) Known method for reacting epoxy group in epoxy resin (a) with unsaturated group-containing carboxylic acid (b) Can be used. For example, an epoxy resin (a) and an unsaturated group-containing carboxylic acid (b) are converted into a tertiary amine such as triethylamine or benzylmethylamine, dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, benzyltriethylammonium chloride, etc. Carboxylic acid can be added to the epoxy resin by reacting in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours using a quaternary ammonium salt, pyridine, triphenylphosphine or the like as a catalyst.

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

The proportion of the unsaturated group-containing carboxylic acid (b) added to the epoxy group of the epoxy resin (a) is usually 90 to 100 mol%. Since the remaining epoxy group adversely affects storage stability, the unsaturated group-containing carboxylic acid (b) is usually 0.8 to 1.5 equivalents, particularly 0, to 1 equivalent of the epoxy group of the epoxy resin (a). It is preferable to carry out the reaction at a ratio of .9 to 1.1 equivalents.
(4) Polybasic acid and / or its anhydride (c)
As the polybasic acid and / or anhydride (c) added to the hydroxyl group of the reaction product of the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b), known ones can be used. Acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, methyl-5-norbornene-2 Dibasic carboxylic acids such as 1,3-dicarboxylic acid or anhydrides thereof; polybasic carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, or anhydrides thereof. Among these, tetrahydrophthalic anhydride or succinic anhydride is preferable. These may be used alone or in combination of two or more.

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

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

The alkali-soluble resin (A) according to the present invention is obtained by reacting the reaction product of the epoxy resin (a) and the unsaturated group-containing carboxylic acid (b) with a polybasic acid and / or its anhydride (c). The resin obtained by adding such an epoxy group-containing compound (d) to a part of the carboxyl group of the resin obtained by the above process may be used.
(5) Physical Properties of Alkali-Soluble Resin (A) 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 1500 or more, preferably Is 2000 or more, usually 50000 or less, preferably 30000 or less, more preferably 10,000 or less. If the weight average molecular weight of the alkali-soluble resin (A) is too small, the sensitivity is inferior.

Moreover, the acid value (mgKOH / g) of the alkali-soluble resin (A) used in the present invention is usually 10 or more, preferably 50 or more, and usually 200 or less, preferably 150 or less. If the acid value of the alkali-soluble resin (A) is too low, sufficient solubility may not be obtained. If the acid value is too high, curability is insufficient and the surface properties of the coating film tend to deteriorate.
<Alkali-soluble resin (A ′), alkali-soluble resin (A1 ′)>
The alkali-soluble resin (A ′) includes an epoxy compound (a ′) represented by the following general formula (1-a ′), an α, β-unsaturated monocarboxylic acid and / or an α having a carboxyl group in the ester moiety. It is obtained by reacting a reaction product with a β-unsaturated monocarboxylic acid ester (b ′) with a polybasic acid and / or its anhydride (c ′).

  The alkali-soluble resin (A1 ′) includes an epoxy compound (a ′) represented by the following general formula (1-a ′), an α, β-unsaturated monocarboxylic acid and / or an α having a carboxyl group in the ester moiety. What is obtained by reacting a mixture of a reaction product with a β-unsaturated monocarboxylic acid ester (b ′) and a polyhydric alcohol (d ′) with a polybasic acid and / or its anhydride (c ′) It is.

[In the general 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 represents an alkylene group. x and y each independently represents an integer of 0 or more. ]
(1) Epoxy compound (a ′) represented by general formula (1-a ′)
First, the epoxy compound (a ′) represented by the general formula (1-a ′) (hereinafter sometimes referred to as “(a ′) component”) will be described.

In the general formula (1-a ′), the alkyl group of R ³¹ and R ³² is preferably an alkyl group having 1 to 10 carbon atoms, and the halogen atom includes Cl, Br, F, and the like. R ³¹ and R ³² are each particularly preferably an alkyl group having 1 to 5 carbon atoms.
Although details of the mechanism of action of the alkyl groups and halogen atoms of R ³¹ and R ³² are not clear, it is assumed that they affect the three-dimensional structure of the molecule and control the solubility in the developer. Is done.

Therefore, from the above viewpoint, p and q in the general 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 to} the benzene ring is not particularly limited,

Or

The o-position is preferred.
R ³¹ and R ³² may be the same group or different groups, but are preferably the same group from the viewpoint of production cost.
Examples of the alkylene group of R ³³ and R ³⁴ include an alkylene group having 1 to 10 carbon atoms, and it is particularly preferable that they are each independently an ethylene group or a propylene group.

x and y each independently represents an integer of 0 or more, but is usually about 0 to 6, preferably about 0 to 3. In general, the larger x and y, the higher the solubility, but if it is too large, the sensitivity may decrease.
R ³³ and R ³⁴ may be the same group or different groups, but are preferably the same group from the viewpoint of production cost.

  The molecular weight of these components (a ′) is usually in the range of 200 to 200,000, preferably 300 to 100,000, as polystyrene-reduced weight average molecular weight (Mw) as measured by gel permeation chromatography (GPC). If the molecular weight is less than the above range, there are many cases where a problem occurs in the film-forming property. Conversely, in the case of a resin exceeding the above range, gelation occurs during the addition reaction of α, β-unsaturated monocarboxylic acid and the like described later. It may be difficult and difficult to manufacture.

(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”) Among them, the α, β-unsaturated monocarboxylic acid includes itaconic acid, crotonic acid, cinnamic acid, acrylic acid, methacrylic acid, etc., preferably acrylic acid and methacrylic acid, and particularly acrylic acid is reactive. It is preferable because of its richness.

  The α, β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester portion includes acrylic acid-2-succinoyloxyethyl, acrylic acid-2-malenoyloxyethyl, acrylic acid-2-phthaloyloxyethyl, Acrylic acid-2-hexahydrophthaloyloxyethyl, methacrylic acid-2-succinoyloxyethyl, methacrylic acid-2-malenoyloxyethyl, methacrylic acid-2-phthaloyloxyethyl, methacrylic acid-2-hexahydrophthalo Yloxyethyl, crotonic acid-2-succinoyloxyethyl, and the like. Preferred are acrylic acid-2-malenoyloxyethyl acrylate and 2-phthaloyloxyethyl acrylate, and particularly acrylic acid-2-maleic acid. Noyloxyethyl is preferred.

  A known method can be used for the addition reaction between the component (b ′) and the component (a ′). For example, the component (b ′) and the component (a ′) can be reacted at a temperature of 50 to 150 ° C. in the presence of an esterification catalyst. As the esterification catalyst used here, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrimethylammonium chloride, and the like can be used. .

In addition, as for (a ') component, (b') component, and an esterification catalyst, all may be used individually by 1 type and may use 2 or more types together.
The amount of component (b ′) used is preferably in the range of 0.5 to 1.2 equivalents, more preferably in the range of 0.7 to 1.1 equivalents, relative to 1 equivalent of the epoxy group of component (a ′). .
When the amount of component (b ′) used is small, the amount of unsaturated groups introduced is insufficient, and the subsequent reaction with polybasic acid and / or anhydride (c ′) becomes insufficient. Also, it is not advantageous that a large amount of epoxy groups remain. On the other hand, when the amount used is large, the component (b ′) remains as an unreacted product. In either case, there is a tendency for the curing properties to deteriorate.

(3) Polybasic acid and / or its anhydride (c ′)
The polybasic acid and / or anhydride (c ′) to be further added to the component (a ′) added by the component (b ′) (hereinafter sometimes referred to as “component (c ′)”) Maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid, chlorendic acid, methyl Examples thereof include one or more selected from tetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

  Preferred are maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or their anhydrides. Particularly preferred is tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

A known method can also be used for the addition reaction of the component (c ′), and it can be obtained by a continuous reaction under the same conditions as the addition reaction of the component (b ′) to the component (a ′).
The amount of component (c ′) added is preferably such that the acid value of the produced alkali-soluble resin (A ′) is in the range of 10 to 150 mgKOH / g, and more preferably in the range of 20 to 140 mgKOH / g. It is preferable that the degree is as follows. When the resin acid value is less than the above range, the alkali developability tends to be poor, and when it exceeds the above range, the curing performance tends to be inferior.

  In the addition reaction of component (c ′), a polyfunctional alcohol (d ′) such as trimethylolpropane, pentaerythritol, dipentaerythritol or the like is added to introduce a multi-branched structure (alkali-soluble resin (A1 ′ )). Examples of the polyhydric alcohol (d ′) include the same compounds as those exemplified as examples of the polyhydric alcohol (d ″) described below. The alkali-soluble resin (A1 ′) is usually a component (a ′). And the component (b ′) are mixed with the component (c ′) and the component (d ′) and then heated, in which case the components (c ′) and (d ′) There is no particular limitation on the mixing order of the above, with respect to any hydroxyl group present in the mixture of the reaction product of the component (a ′) and the component (b ′) and the component (d ′) by heating. Component (c ′) undergoes an addition reaction.

  The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the alkali-soluble resin (A ′) and the alkali-soluble resin (A1 ′) is usually 1,000 or more, preferably 1,500 or more. In general, it is 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 deteriorated. Conversely, if the weight average molecular weight is too small, the alkali resistance may be inferior.

<Alkali-soluble resin (A ″), alkali-soluble resin (A1 ″)>
The alkali-soluble resin (A ″) is obtained by reacting an epoxy compound (a ″) represented by the following general formula (1-a ″) with an unsaturated group-containing carboxylic acid (b ″), a polybasic acid and / or It is obtained by reacting with its anhydride (c ″).
The alkali-soluble resin (A1 ″) includes a reaction product of an epoxy compound (a ″) represented by the following general formula (1-a ″) and an unsaturated group-containing carboxylic acid (b ″), a polyhydric alcohol (d ″). ) And a polybasic acid and / or its anhydride (c ″).

[In the above general formula (1-a ″), X represents a linking group represented by the following general formula (2a), (2b) or (3), provided that one or more adamantane structures are present in the molecular structure. 1 represents an integer of 2 or 3.

(In the above general formulas (2a) and (2b), R ^{1 to} R ⁴ and R ^{13 to} R ¹⁵ each independently have an adamantyl group, a hydrogen atom, and a substituent which may have a substituent. An optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted phenyl group is shown.
In the general formula (3), R ^{5 to} R ¹² may each independently have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms that may have a substituent, or a substituent. Represents a phenyl group; Y represents a divalent linking group containing an adamantane structure, which may have a substituent.

In the general formulas (2a), (2b), and (3), * represents a binding site with the glycidyloxy group in the general formula (1-a ″).
(1) Epoxy compound (a ″) represented by general formula (1-a ″)
First, the group X in the epoxy compound (a ″) represented by the general formula (1-a ″) (hereinafter sometimes referred to as “(a ″) component”) will be described.

When the group X has the structure represented by the general formula (2a) or (2b), it is preferable that the general formulas (2a) and (2b) both have an adamantane structure of 2 or more and 4 or less. When the adamantane structure is 1, the developer resistance tends to decrease and the resolution tends to be inferior.
When the group X is a structure represented by the general formula (3), Y in the general formula (3)
Is a “divalent linking group containing an adamantyl structure which may have a substituent”, but is not particularly limited. For example, it is represented by the following general formula (4) or (5). It is preferable that it is a coupling group.

[All of the above general formulas (4) and (5) may have a substituent. * Represents a binding site with the benzene ring in the general formula (3). ]
In particular, the epoxy compound (a ″) represented by the general formula (1-a ″) is preferably represented by the following general formula (6) or (7).

[The adamantyl group represented by the general formulas (6) and (7) may have a substituent.
In General Formula (6), R ^{16 to} R ²³ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an optionally substituted phenyl group. Indicates a group.
In General Formula (7), R ²⁴ and R ²⁵ are each independently an adamantyl group that may have a substituent, a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms that may have a substituent. Or a phenyl group which may have a substituent. ]
The alkyl group having 1 to 12 carbon atoms of R ^{1 to} R ^{25 in} the general formulas (2a), (2b), (3), (6) and (7) is preferably an alkyl group having 1 to 10 carbon atoms. Is mentioned.

Examples of the substituent that these alkyl groups may have include a halogen atom, a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfanyl group, A phosphino group, an amino group, a nitro group, etc. are mentioned.
In addition, examples of the substituent that the phenyl group of R ^{1 to} R ^{25 in} the general formulas (2a), (2b), (3), (6), and (7) may have include a halogen atom, a hydroxyl group, Examples thereof include an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfanyl group, a phosphino group, an amino group, and a nitro group.

Similarly, the general formula (2a) and adamantyl groups ^R 1 to R ⁴ and ^R 13 ^{to R 15} in (2b), adamantane ring in the Y in the general formula (3), adamantane ring in the general formula (6), The adamantyl group in the general formula (7), the adamantyl group of R ²⁴ and R ²⁵ in the general formula (7), and the adamantane ring in the general formulas (4) and (5) may have a halogen Examples thereof include an atom, a hydroxyl group, an alkoxyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a phenyl group, a carboxyl group, a sulfanyl group, a phosphino group, an amino group, and a nitro group.

In the general formula (6), R ^{16 to} R ²³ are particularly preferably an alkyl group, a halogen atom, an alkoxyl group, an alkenyl group, or a phenyl group.
In the general formula (7), R ²⁴ and R ²⁵ are particularly preferably an alkyl group, a halogen atom, an alkoxyl group, an alkenyl group, or a phenyl group.
The molecular weight of X represented by the general formula (1-a ″) is preferably 200 or more and 1000 or less. When the molecular weight of X is less than 200, the chemical resistance tends to be inferior, and when it exceeds 1000, the sensitivity is low. there is a possibility.

  The epoxy equivalent of the epoxy compound (a ″) represented by the general formula (1-a ″) is preferably 210 or more, and more preferably 230 or more. The epoxy equivalent is preferably 450 or less, and 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 when it exceeds 450, the sensitivity of the organic binder to be produced tends to decrease.

As the epoxy compound (a ″), one type may be used alone, or two or more types may be used in combination.
As the epoxy compound (a ″), a commercially available product may be used, or it may be synthesized from a phenol compound as described below by a known method.

[R ^{1 to} R ¹⁵ in the general formulas (9a), (9b), and (10) have the same meanings as in the general formulas (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 the compound represented by the general formula (9a) or (9b) and an excess of epihalohydrin such as epichlorohydrin or epibromhydrin. The connecting group in which X in the general formula (1-a ″) is represented by the general formula (2a) or (2b) by adding or reacting at a temperature of 20 to 120 ° C. for 1 to 10 hours while adding. An epoxy compound (a ″) can be obtained.

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

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

Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like is catalyzed to a dissolved mixture of the compound represented by the general formula (9a), (9b) or (10) and epihalohydrin. To the halohydrin etherified product of the compound represented by the general formula (9a), (9b), or (10) obtained by reacting at 50 to 150 ° C. for 1 to 5 hours. The epoxy compound (a) represented by the general formula (1-a ″) can also be obtained by adding a solid or aqueous solution of the product and reacting again at a temperature of 20 to 120 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure).
)) Can be manufactured.

  The amount of epihalohydrin used in such a reaction is usually 1 to 20 mol, preferably 2 to 10 mol, relative to 1 equivalent of the hydroxyl group of the compound represented by general formula (9a), (9b), or (10). It is. Moreover, the usage-amount of an alkali metal hydroxide is 0.8-15 mol normally with respect to 1 equivalent of hydroxyl groups of the compound represented by general formula (9a), (9b), or (10), Preferably 0.9- 11 moles.

  In the above-mentioned reaction, in addition to alcohols such as methanol and ethanol, an aprotic polar solvent such as dimethyl sulfone and dimethyl sulfoxide may be added to perform the reaction smoothly. When alcohols are used, the amount used is 2 to 20% by weight, preferably 4 to 15% by weight, based on the amount of epihalohydrin. Moreover, when using an aprotic polar solvent, the usage-amount is 5 to 100 weight% with respect to the quantity of an epihalohydrin, Preferably it is 10 to 90 weight%.

(2) Unsaturated group-containing carboxylic acid (b ″)
Examples of the unsaturated group-containing carboxylic acid (b ″) (hereinafter sometimes referred to as “(b ″) component”) include unsaturated carboxylic acids having an ethylenically unsaturated group, and specific examples include ( (Meth) acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, cinnamic acid, α-position substituted with haloalkyl group, alkoxyl group, halogen atom, nitro group, or cyano group Monocarboxylic acids such as (meth) acrylic acid; 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2 -(Meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, -(Meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (Meth) acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutyl hydrophthalic acid, 2- (meth) acryloyloxybutyl phthalic acid, 2- ( (Meth) acryloyloxybutylmaleic acid and the like (meth) acryloyloxyalkyl esters of dibasic acids; (meth) acrylic acid such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, etc. Monomers to which lactones are added; (meth) acrylic acid dimers, etc. That.

  Also, anhydrous hydroxyl-containing unsaturated compounds such as pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane diacrylate, acrylic acid adduct of glycidyl methacrylate, and methacrylic acid adduct of glycidyl methacrylate. The compound which added acid anhydrides, such as succinic acid, maleic anhydride, tetrahydrophthalic anhydride, and phthalic anhydride, is also mentioned.

Particularly preferred is (meth) acrylic acid.
These may be used alone or in combination of two or more.
As a method of reacting the epoxy group in the component (a ″) with the component (b ″), a known method can be used. For example, the component (a ″) and the component (b ″) are combined with tertiary amines such as triethylamine and benzylmethylamine, quaternary compounds such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, and benzyltriethylammonium chloride. Carboxylic acid can be added to the epoxy compound by reacting ammonium salt, pyridine, triphenylphosphine or the like in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours.

  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 reaction raw material mixture (the sum of the components (a ″) and (b ″)). is there. In order to prevent polymerization during the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, phenothiazine, etc.). Preferably it is 0.01 to 10 weight% with respect to the reaction raw material mixture, Most preferably, it is 0.03 to 5 weight%.

The ratio of adding the (b ″) component to the epoxy group of the (a ″) component is usually 90 to 100 mol%. Since the remaining epoxy group tends to adversely affect storage stability, the component (b ″) is usually 0.8 to 1.5 equivalents, particularly 0, relative to 1 equivalent of the epoxy group of the component (a ″). It is preferable to carry out the reaction at a ratio of .9 to 1.1 equivalents.
(3) Polybasic acid and / or its anhydride (c ″)
As the polybasic acid and / or anhydride (c ″) (hereinafter, sometimes referred to as “(c ″) component” or “polybasic acid (anhydride)”), the dibasic acid and / or anhydride thereof Product (hereinafter referred to as “dibasic acid (anhydride)”, 3 basic acid and / or anhydride thereof (hereinafter referred to as “3 basic acid (anhydride)”), 4 basic acid and / or anhydride thereof (Hereinafter referred to as “4-basic acid (anhydride)”) and the like.

  As the 4-basic acid (anhydride) (tetracarboxylic acid and / or dianhydride thereof), known ones can be used, such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, etc. Tetracarboxylic acid, or these dianhydrides are mentioned. These may be used alone or in combination of two or more.

As the 4-basic acid (anhydride), among the above exemplified compounds, biphenyltetracarboxylic acid or an anhydride thereof is particularly preferable.
By reacting a reaction product of the component (a ″) and the component (b ″) with a tetrabasic acid (anhydride) as the component (c ″), the molecular weight increases due to a crosslinking reaction. It is preferable because of the effects such as improvement of adhesion, adjustment of solubility, improvement of sensitivity and alkali resistance.

  Examples of the dibasic acid (anhydride) (dicarboxylic acid and / or anhydride thereof) include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, and chlorende. An acid, methyltetrahydrophthalic acid, or these anhydrides are mentioned. Among these, tetrahydrophthalic acid, succinic acid, or anhydrides thereof are preferable. These may be used alone or in combination of two or more.

By reacting the reaction product of the component (a ″) and the component (b ″) with a dibasic acid (anhydride) as the component (c ″), it is possible to easily adjust the solubility and to adhere to the substrate. Is preferable.
Examples of the tribasic acid (anhydride) (tricarboxylic acid and / or anhydride thereof) include trimellitic acid, hexahydrotrimellitic acid, and anhydrides thereof. 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 component (c ″), the molecular weight of the alkali-soluble resin (A ″) can be increased, branching can be introduced into the molecule, and the molecular weight and viscosity must be balanced. Can do. Moreover, the amount of acid groups introduced into the molecule can be increased, and a resin having a good balance of sensitivity, adhesion, and the like can be obtained.
As the component (c ″), it is particularly preferable to use a 4-basic acid (anhydride).
The addition rate of 4-basic acid (anhydride) is usually 10 to 100 mol%, preferably 20 to 100 mol%, based on the hydroxyl group produced when component (b ") is added to component (a"). More preferably, it is 30-100 mol%. If the addition rate of the (c ″) component tetrabasic acid (anhydride) is too small, the solubility of the alkali-soluble resin (A ″) may be insufficient or the adhesion to the substrate may be insufficient.

In addition, it is preferable to replace a part of the 4-basic acid (anhydride) described above with a dibasic acid (anhydride) from the viewpoint of adjusting the viscosity and solubility of the photosensitive colored resin composition.
When (c ″) a 4-basic acid (anhydride) and a 2-basic acid (anhydride) are used in combination, the molar ratio is 2 basic acid (anhydride): 4 basic acid (anhydride) = 99: 1 -20: 80 is preferable, and 80: 20-30: 70 is more preferable, and when the amount of 4-basic acid (anhydride) is less than this range, the film properties of the resulting coating film deteriorate. If the dibasic acid (anhydride) is too small, the viscosity of the resulting resin solution may increase and handling may be difficult.

In addition to the effects of improving adhesion to the substrate, easy adjustment of solubility, improvement of sensitivity and alkali resistance, etc., in order to achieve various balances such as molecular weight, viscosity, sensitivity, and adhesion, 4-basic acid is used. (Anhydride) and / or dibasic acid (anhydride) and tribasic acid (anhydride) are preferably used in combination.
In the case where a 4-basic acid (anhydride) and / or a 2-basic acid (anhydride) and a 3-basic acid (anhydride) are used in combination as the component (c ″), the amount of the 3-basic acid (anhydride) used is small. If the amount is too high, the effect is diminished and the alkali resistance may be lowered. Therefore, the amount of tribasic acid (anhydride) used is the amount of hydroxyl group produced when component (b ″) is added to component (a ″). On the other hand, it is usually about 5 to 70 mol%, preferably about 10 to 40 mol%.

The total addition rate of component (c ″) is usually 10 to 100 mol%, preferably 20 to 100 mol%, based on the hydroxyl group produced when component (b ″) is added to component (a ″). More preferably, it is 30 to 100 mol%. If the addition rate of the component (c ″) is too small, the solubility of the alkali-soluble resin (A ″) may be insufficient or the adhesion to the substrate may be insufficient. is there.
In addition, the component (c ″) is added with the component (b ″) to the component (a ″) in addition to reacting with the hydroxyl group generated when the component (b ″) is added to the component (a ″). When a polyhydric alcohol (d ″), which will be described later, is mixed therewith, it may be reacted with any hydroxyl group present in the mixture.

As a method of adding the component (c ″) after adding the component (b ″) to the component (a ″) or mixing a polyhydric alcohol (d ″) described later thereto, a known method is known. Can be used.
The reaction temperature is usually 80 to 130 ° C, preferably 90 to 125 ° C. When the reaction temperature exceeds 130 ° C., some of the unsaturated groups in the component (b ″) are polymerized, which may lead to a rapid increase in molecular weight. , (C ″) may remain.

(4) Polyhydric alcohol (d ″)
In the photosensitive colored resin composition of the present invention, the binder resin used in combination with the alkali-soluble resin (A) includes the reaction product of the aforementioned component (a ″) and component (b ″), and the polyhydric alcohol (d ″). (Hereinafter also referred to as “component (d ″)”) and the above-mentioned component (c ″) is reacted with (c ″) any hydroxyl group present in the mixture. It may be an alkali-soluble resin (A1 ″) obtained by subjecting the component to an addition reaction. The alkali-soluble resin (A1 ″) is usually a reaction obtained by adding the component (b ″) to the component (a ″). The product is obtained by mixing the component (c ″) and component (d ″) and heating. In this case, the mixing order of the component (c ″) and the component (d ″) is not particularly limited.

Examples of the component (d ″) include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. An alcohol is preferred.
By using the component (d ″), the molecular weight of the alkali-soluble resin (A1 ″) can be increased, branching can be introduced into the molecule, and a balance between the molecular weight and the viscosity can be achieved. Moreover, the rate of introduction of acid groups into the molecule can be increased, and an organic binder having a good balance of sensitivity and adhesion can be obtained.

When the amount of the component (d ″) used is too small, the effect is thin, and when it is too large, there is a possibility of thickening or gelation. Therefore, the amount of the component (a ″) and the component (b ″) is not adjusted. In general, it is about 0.01 to 0.5 times by weight, preferably about 0.02 to 0.2 times by weight.
(5) Acid value and molecular weight of alkali-soluble resins (A ″) and (A1 ″) The acid values of the alkali-soluble resins (A ″) and (A1 ″) thus obtained are usually 10 mgKOH / g or more, preferably Is 50 mg KOH / g or more. If the acid value is less than 10 mgKOH / g, developability may be insufficient. If the acid value is excessively high, there is a problem with the alkali resistance of the photosensitive colored resin composition (that is, the alkaline developer may cause roughening of the pattern surface or film loss). Is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.

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

By using the alkali-soluble resin (A) and the alkali-soluble resin (A ′, A1 ′, A ″, A1 ″) in combination, the linearity of the pattern is improved, and the development time and the taper angle are adjusted. Is obtained.
<Other binder resins (H)>
In the photosensitive colored resin composition of the present invention, alkali-soluble resins (A, A ′, A1 ′)
, A ″, A1 ″) may be replaced with another binder resin (H). That is, an alkali-soluble resin (A, A ′, A1 ′, A ″, A1 ″) and another binder resin may be used in combination.

  As long as the performance of the present invention is not impaired, other binder resins (H) that can be used in combination with alkali-soluble resins (A, A ′, A1 ′, A ″, A1 ″) are not limited, and are photosensitive colored resins for color filters. What is necessary is just to select from resin normally used for a composition. Examples thereof include binder resins described in JP 2007-271727 A, JP 2007-316620 A, JP 2007-334290 A, and the like.

In addition, as for other binder resin (H), all may be used individually by 1 type, or may be used in combination of 2 or more type.
<Photoinitiator (B)>
The photopolymerization initiator (B) is usually used as a mixture (photopolymerization initiator system) with an accelerator and an additive such as a sensitizing dye added as necessary. The photoinitiator system absorbs light directly,
Alternatively, it is a component having a function of generating a polymerization active radical by photosensitization to cause a decomposition reaction or a hydrogen abstraction reaction.

  Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197, and hexaarylbi compounds described in JP-A-2000-56118. Imidazole derivatives; N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives and N-phenylglycine described in JP-A-10-39503, N-aryl-α-amino acid salts, Radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime ester derivatives described in JP 2000-80068 A, JP 2006-36750 A, and the like. .

  Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny 1-yl), dicyclopentadienyl titanium di (2,6-difluorophen-1-yl), dicyclopentadienyl titanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclone) Pentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-difluoro-3- (pyro-1-yl) -phen-1-yl] and the like. Can be mentioned.

  Biimidazole derivatives include 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole. Dimer, 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxy) Phenyl) -4,5-diphenylimidazole dimer and the like.

  Examples of the halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′- Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2 -Trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

  Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -S-triazine and the like.

Examples of α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoe -To, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4 -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like It is.

  Moreover, as an oxime ester derivative, the following compounds etc. are mentioned, for example.

  Other benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether and benzoin isopropyl ether; anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone Benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, benzophenone derivatives such as 2-carboxybenzophenone; 2,2-dimethoxy-2-phenyl Acetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenol Nylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4′-methylthiophenyl) -2-morpholino-1 Acetophenone derivatives such as propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 Thioxanthone derivatives such as 1,4-diethylthioxanthone and 2,4-diisopropylthioxanthone; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; 9-phenylacridine, 9- (p- Methoxyph Acridine derivatives such as benzyl) acridine; phenazine derivatives such as 9,10-dimethylbenzphenazine; and anthrone derivatives such as benzanthrone.

Among these photopolymerization initiators, oxime ester derivatives are particularly preferable from the viewpoint of sensitivity.
These photopolymerization initiators and accelerators may be used alone or in combination.
Specific examples of the photopolymerization initiator component include dialkylacetophenone-based compounds described on pages 16 to 26 of "Fine Chemical" (March 1, 1991, vol. 20, No. 4). Benzoin, thioxanthone derivatives, and the like, as well as hexaarylbiimidazole series, S-trihalomethyltriazine series, and JP-A-4-221958 described in JP-A-58-403023 and JP-B-45-37377. And a combination of a titanocene and a xanthene dye, an addition-polymerizable ethylenic saturated double bond-containing compound having an amino group or a urethane group, and the like described in JP-A-4-219756. .

  If necessary, a sensitizing dye corresponding to the wavelength of the image exposure light source can be added to the photopolymerization initiator system component for the purpose of increasing the sensitivity. These sensitizing dyes include xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, and 3-ketocoumarin compounds described in Kaihei 3-239703 and 5-289335, pyromethene dyes described in JP-A-6-19240, and others, JP-A 47-2528, 54-155292, JP 45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-6988, JP-A-57-168088. No. 5, JP-A-5-107761, JP-A-5-210240, and JP-A-4-288818. Mention may be made of a dye or the like having a skeleton.

  Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone. Benzophenone compounds such as 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4,5 ] Benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylaminophenyl) Benzothiazole, 2- (p-di Tilaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, ( p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. P-dialkylaminophenyl group-containing compounds.

Of these, 4,4′-dialkylaminobenzophenone is most preferred.
A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.
<Coloring material (C)>
The color material (C) refers to a colorant for the photosensitive colored resin composition of the present invention. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like.

  As the pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. In addition to organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene, various inorganic pigments can be used. It is.

Hereinafter, specific examples of pigments that can be used in the present invention are shown by pigment numbers. Note that terms such as “CI Pigment Red 2” mentioned below mean a color index (CI).
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9,
12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 93,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6. Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.

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

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

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

  Moreover, when the photosensitive coloring resin composition of this invention is the photosensitive coloring resin composition for resin black matrices of a color filter, a black coloring material can be used as a coloring material (C). The black color material may be a single black color material or a mixture of red, green, blue, and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes.

  Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK 70: 100 (50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (The numbers in parentheses above mean the color index (CI)).

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

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

Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45 # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B
Made by Degussa: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, P
rintex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Colo Black S170
Cabot Corporation: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130 , VULCAN XC72R, ELFTEX-8 Colombian Made by Carbon: RAVEN11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30 RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000
As examples of other black pigments, titanium black, aniline black, iron oxide black pigments, and organic pigments of three colors of red, green, and blue can be mixed and used as black pigments.

In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, or the like can also be used as the pigment.
These various pigments can be used in combination. For example, in order to adjust chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.
These pigments are preferably used in a dispersed manner so that the average particle diameter is usually 1 μm, preferably 0.5 μm or less, more preferably 0.25 μm or less.

In the present invention, the average particle diameter of the pigment is a value obtained from the pigment particle diameter measured by dynamic light scattering DLS. For particle size measurement, a sufficiently diluted colored resin composition (usually diluted to a pigment concentration of about 0.005 to 0.2% by weight. However, if there is a concentration recommended by the measuring instrument, its concentration And measure at 25 ° C.
Examples of dyes that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

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

<A thiol compound (D) in which the carbon atom at the α-position to the mercapto group has at least one hydrocarbon group as a substituent and has two or more mercapto groups>
Examples of the accelerator constituting the photopolymerization initiator system component include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, and 2-mercaptobenzoxazole. And mercapto compounds having a heterocyclic ring such as 2-mercaptobenzimidazole or aliphatic polyfunctional mercapto compounds. In the present invention, in particular, the carbon atom at the α-position to the mercapto group is at least one carbon atom as a substituent. When a thiol compound having a hydrogen group and two or more mercapto groups was used, a photosensitive colored resin composition excellent in sensitivity, storage stability, and adhesion was obtained.

Examples of the hydrocarbon group possessed by the α-position carbon atom with respect to the mercapto group include an alkyl group having 1 to 3 carbon atoms, and specifically include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. More preferably, it is a methyl group or an ethyl group. The carbon atom at the α-position with respect to the mercapto group preferably has one hydrocarbon group.
Among the thiol compounds, a compound having a partial structure represented by the general formula (d-1) is preferable in terms of high reactivity.

(In General Formula (d-1), R ⁵¹ and R ⁵² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and a represents an integer of 0 to 4. However, R ⁵¹ And R ⁵² is hydrogen.)
R ⁵¹ and R ⁵² in the general formula (d-1) represent a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, An isopropyl group is exemplified, and a methyl group or an ethyl group is more preferable.
The thiol compound is preferably a carboxylic acid ester of a carboxylic acid represented by the general formula (d-2) and a polyfunctional alcohol.

(In General Formula (d-1), R ⁵¹ and R ⁵² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and a represents an integer of 0 to 4. However, R ⁵¹ And R ⁵² is hydrogen.)
Examples of the mercapto group-containing carboxylic acid of the above formula (d-2) include 2-mercaptopropionic acid, 3-mercaptobutyric acid, 4-mercapto valerian and the like.

As the polyfunctional alcohol, alkylene glycol (wherein the alkylene group preferably has 2 to 10 carbon atoms, and the carbon chain thereof may be branched), diethylene glycol, glycerin, dipropylene glycol, trimethylolpropane, pentane. Examples include erythritol and dipentaerythritol.
Specific examples of the thiol compound used in the present invention include the following compounds.

Examples of the hydrocarbon dithiol include 2,5-hexanedithiol, 2,9-decanedithiol, 1,4-bis (1-mercaptoethyl) benzene, and the like.
As compounds containing an ester bond, di (1-mercaptoethyl ester) phthalate, di (2-mercaptopropyl ester) phthalate, di (3-mercaptobutyl ester) phthalate, di (3-mercaptoisobutyl ester) phthalate Can be exemplified.
As the carboxylic acid derivative of the general formula (d-2), ethylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3 -Mercaptobutyrate), nonanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate) , Dipentaerythritol hexakis (3-mercaptobutyrate), dipentaerythritol pentakis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), diethylene glycol Colebis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), nonanediol bis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), pentaerythritol tris (2-mercaptopropionate), dipentaerythritol hexakis (2-mercaptopropionate), dipentaerythritol Pentakis (2-mercaptopropionate), ethylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (
2-mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate), nonanediol bis (2-mercaptoisobutyrate), trimethylolpropane tris (2 -Mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), pentaerythritol tris (2-mercaptoisobutyrate), dipentaerythritol hexakis (2-mercaptoisobutyrate), dipentaerythritol pentakis (2
-Mercaptoisobutyrate), ethylene glycol bis (4-mercaptovalerate), diethylene glycol bis (4-mercaptovalerate), butanediol bis (4-mercaptovalerate), octanediol bis (4-mercaptovalerate), Nonanediol bis (4-mercaptovalerate), trimethylolpropane tris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercaptovalerate), pentaerythritol tris (4-mercaptovalerate), dipentaerythritol hexakis (4-mercaptovalerate), dipentaerythritol pentakis (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), diethylene glycol bis (3-mer Ptovalerate), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercaptovalerate), nonanediol bis (3-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), pentaerythritol Tetrakis (3-mercaptovalerate), pentaerythritol tris (3-mercaptovalerate), dipentaerythritol hexakis (3-mercaptovalerate), dipentaerythritol pentakis (3-mercaptovalerate), 1,3 Examples thereof include 5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione.

Among these, ethylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), tri Methylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptobutyrate), ethylene glycol bis ( 3-mercaptoisobutyrate), diethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), octanediol bis (3-mercap) Toisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), pentaerythritol tetrakis (3-mercaptoisobutyrate), dipentaerythritol hexakis (3-mercaptoisobutyrate) 1,3,5-tris (3-Mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione. More preferably, ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), penta Erythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethylolpropane tris (3-mercaptoisobutyrate), 1,3 , 5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione is desirable from the viewpoint of polymerization initiation ability and storage stability.

These thiol compounds can be used alone or in combination of two or more. Moreover, you may use together these thiol compounds and said other reaction accelerator.
Although the manufacturing method of a thiol compound (D) is not specifically limited, About the ester of mercapto group containing carboxylic acid and alcohol, the mercapto group containing carboxylic acid and alcohol shown by the formula (d-2) mentioned above Can be obtained by reacting with a compound according to a conventional method to form an ester. There is no restriction | limiting in particular about the conditions of ester reaction, It can select suitably from conventionally well-known reaction conditions.

<Dispersant (E)>
In the present invention, it is important to finely disperse the color material (C) and stabilize the dispersion state, so that it is important to ensure the stability of the quality. Therefore, it is preferable to include the dispersant (E).
As the dispersant (E), a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphate group; a sulfonate group; or a base thereof; primary, secondary, or tertiary A polymeric dispersant having a functional group such as a quaternary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine, is preferred. Among these, a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, pyrazine, or the like is particularly preferable.

  Examples of polymer dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants composed of amino group-containing monomers and macromonomers, and polyoxyethylene alkyl ethers. Examples thereof include a dispersant, a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, and an aliphatic modified polyester dispersant.

Specific examples of such a dispersant are trade names of EFKA (manufactured by EFKA Chemicals Beebuy (EFKA)), Disperbyk (manufactured by BYK Chemie), Disparon (manufactured by Enomoto Kasei), SOLPERSE (manufactured by Lubrizol) , KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (manufactured by Ajinomoto Co., Inc.) 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 1000 or more, and usually 100,000 or less, preferably 50,000 or less.
Among these, it is particularly preferable that the dispersant (E) contains a urethane polymer dispersant and / or an acrylic polymer dispersant having a functional group in terms of adhesion and linearity.
Examples of urethane and acrylic polymer dispersants include Disperbyk 160 to 166, 182 series (both urethane), Disperbyk 2000, 2001, etc. (both acrylic) (all manufactured by BYK Chemie).

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

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

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

Examples of the compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol and the like, and one terminal hydroxyl group of these compounds has a carbon number. Examples thereof include those alkoxylated with 1 to 25 alkyl groups and mixtures of two or more thereof.
Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of these is mentioned.

  Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

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

Examples of polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Is mentioned.
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 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.
A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described. Examples of the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Of these, the hydrogen atom of the amino group is preferred.

The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.
Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  In addition, when the tertiary amino group is a nitrogen-containing heterocyclic structure, examples of the nitrogen-containing heterocyclic ring include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzo N-containing hetero 5-membered ring such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, etc., nitrogen-containing hetero 6-membered ring such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring A ring is mentioned. Among these nitrogen-containing heterocycles, preferred are an imidazole ring or a triazole ring.

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

These may be used alone or in combination of two or more.
The preferred blending ratio of the raw materials for producing the urethane-based polymer dispersant is a number average molecular weight of 30 having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound.
0 to 10,000 compounds are 10 to 200 parts by weight, preferably 20 to 190 parts by weight, more preferably 30 to 180 parts by weight, and compounds having an active hydrogen and a tertiary amino group in the same molecule are 0.2 to 0.2 parts by weight. 25 parts by weight, preferably 0.3 to 24 parts by weight.

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

  In the above production, a urethanization reaction catalyst is usually used. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. 1 type, or 2 or more types, such as a secondary amine type | system | group, are mentioned.

  The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mgKOH / g. The amine value is a value obtained by neutralizing and titrating a basic amino group with an acid, and representing the acid value in mg of KOH. When the amine value is lower than the above range, the dispersing ability tends to be lowered, and when it exceeds the above range, the developability tends to be lowered.

In addition, when an isocyanate group remains in the polymer dispersant by the above reaction, it is preferable to further crush the isocyanate group with an alcohol or an amino compound because the stability of the product with time is increased.
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. If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor.

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

  Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acrylic acid. Tertiary amino groups such as unsaturated monomers having a carboxyl group such as leuoxyethyl hexahydrophthalic acid and acrylic acid dimer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof; Specific examples include unsaturated monomers having a quaternary ammonium base. 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, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, isobornyl (meth) acrylate, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohe N-substituted maleimides such as silmaleimide, N-phenylmaleimide, N-benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly-2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol Examples thereof include macromonomers, polypropylene glycol macromonomers, and macromonomers such as polycaprolactone macromonomers. These may be used alone or in combination of two or more.

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

The B block is composed of an unsaturated group-containing monomer that does not contain the above functional group. However, two or more types of monomers may be contained in one B block. It may be contained in any form of random copolymerization or block copolymerization in the block.
The AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below.

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

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

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

Whether the acrylic polymer dispersant used in the present invention is an AB block copolymer or a B-A-B block copolymer, the A block / B block ratio constituting the copolymer Is preferably 1/99 to 80/20, and more preferably 5/95 to 60/40 (weight ratio). Outside this range, it may not be possible to combine good heat resistance and dispersibility.
In addition, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and the BAB block copolymer according to the present invention is preferably 0.1 to 10 mmol, and outside this range. In some cases, good heat resistance and dispersibility cannot be combined.

Such a block copolymer usually contains an amino group produced in the production process, but its amine value is about 1 to 100 mgKOH / g.
Here, the amine value of the dispersant such as these block copolymers is expressed by the weight of KOH equivalent to the base amount per 1 g of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L HClO4 acetic acid solution using an automatic titrator equipped with a pH electrode. Using the inflection point of the titration pH curve as the end point of titration, the amine value is determined by the following formula.

Amine value [mgKOH / g] = (561 × V) / (W × S)
[However, W: Weighing amount of dispersant sample [g], V: Titration amount at the end of titration [mL], S: Solid content concentration [wt%] of the dispersant sample. ]
The acid value of the block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but is generally preferably low, and is usually 10 mg KOH / g or less, and its weight average molecular weight (Mw) ) Is preferably in the range of 1000 to 100,000. When the weight average molecular weight of the block copolymer is less than 1000, the dispersion stability tends to decrease, and when it exceeds 100,000, the developability and resolution tend to decrease.

Moreover, it is preferable to use a dispersing agent (E) together with the pigment derivative mentioned later from the point of a dispersion stability improvement.
<Photopolymerizable monomer (F)>
In the present invention, it is preferable to use a photopolymerizable monomer (F) (photopolymerizable compound) in view of sensitivity and the like.

  Examples of the photopolymerizable monomer (F) used in the present invention include compounds having at least one ethylenically unsaturated group in the molecule (hereinafter sometimes referred to as “ethylenic monomer”). . Specifically, for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, a carboxylic acid having one ethylenically unsaturated bond, a monoester of polyhydric or monohydric alcohol, etc. Can be mentioned.

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

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

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate and the like. Etc.
The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but representative examples include acrylic acid, phthalic acid, and Examples include condensates of ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

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

These may be used alone or in combination of two or more.
<Other compounding components of photosensitive colored resin composition>
In addition to the components described above, the photosensitive colored resin composition of the present invention includes an organic solvent, an adhesion improver, a coatability improver, a development improver, an ultraviolet absorber, an antioxidant, a silane coupling agent, and a surfactant. In addition, pigment derivatives and the like can be appropriately blended.

(1) Organic solvent The photosensitive colored resin composition of the present invention usually comprises an alkali-soluble resin (A), a photopolymerization initiator (B), a colorant (C), and various materials used as necessary. And used in a state dissolved or dispersed in an organic solvent.
As the organic solvent, it is preferable to select an organic solvent having a boiling point in the range of 100 to 300 ° C. More preferably, it is a solvent having a boiling point of 120 to 280 ° C.
Examples of such organic solvents include the following.

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-t-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 Monoe Ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-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, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
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 Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile:
Commercially available solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like.

These organic solvents may be used alone or in combination of two or more.
(1-1) Organic solvent when forming color filter pixels or black matrix by photolithography method When forming color filter pixels or black matrix by photolithography method, the organic solvent has a boiling point of 100 to 200. It is preferable to select the one in the range of ° C. (pressure of 101.25 [hPa]. Hereinafter, all the boiling points are the same). More preferably, it has a boiling point of 120 to 170 ° C.

Of the above organic solvents, glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension and the like, and relatively high solubility of the constituent components in the composition.
In addition, glycol alkyl ether acetates may be used alone or in combination with other organic solvents. As the organic solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability such as the viscosity of the colored resin composition obtained later tends to decrease. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by weight to 30% by weight, and more preferably 5% by weight to 20% by weight.

  It is also preferable to use an organic solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as “high boiling point solvent”). By using such a high boiling point solvent in combination, the colored resin composition becomes difficult to dry, but it has an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of a foreign matter defect due to precipitation or solidification of a color material or the like at the tip of the slit nozzle. Among these various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable because of such high effects.

  The content of the high boiling point solvent in the organic solvent is preferably 3% by weight to 50% by weight, more preferably 5% by weight to 40% by weight, and particularly preferably 5% by weight to 30% by weight. If the amount of the high boiling point solvent is too small, for example, a coloring material may precipitate and solidify at the tip of the slit nozzle to cause a foreign matter defect, and if it is too much, the drying temperature of the composition will be slowed down. There is a concern that the filter manufacturing process may cause problems such as tact defects in the vacuum drying process and pin marks of prebaking.

The high boiling point solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a high boiling point solvent having a boiling point of 150 ° C. or higher is not separately contained. It doesn't matter.
Preferred examples of the high boiling point solvent include diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.

(1-2) Organic solvent for forming color filter pixels by inkjet method When forming a color filter pixel by inkjet method, the organic solvent usually has a boiling point of 130 ° C to 300 ° C, preferably A temperature of 150 ° C. or higher and 280 ° C. or lower is appropriate. If the boiling point of the organic solvent is too low, the uniformity of the resulting coating film tends to be poor. Conversely, if the boiling point of the solvent is too high, the effect of inhibiting drying of the colored resin composition is high, as will be described later, but a large amount of residual solvent is present in the coating film even after heat firing, resulting in quality defects. In some cases, the drying time in vacuum drying or the like becomes longer, causing problems such as an increase in tact time.

The vapor pressure of the organic solvent is usually 10 mmHg or less, preferably 5 mmHg or less, more preferably 1 mmHg or less, from the viewpoint of the uniformity of the resulting coating film.
In the production of color filters by the ink jet method, the ink emitted from the nozzle is very fine, from several to several tens of pL, so the organic solvent evaporates before landing on the periphery of the nozzle opening or in the pixel bank. There is a tendency to concentrate and dry. In order to avoid this, it is preferable 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, particularly preferably a boiling point of 220 ° C. or higher. The high boiling point solvent having a boiling point of 180 ° C. or higher is preferably 50% by weight or more, more preferably 70% by weight or more in the total organic solvent contained in the ink and / or color filter colored resin composition described later. Preferably, 90% by weight or more is most preferable. When the ratio of the high boiling point solvent having a boiling point of 180 ° C. or higher in the total organic solvent is less than 50% by weight, the effect of preventing evaporation of the solvent from the droplets may not be sufficiently exhibited.

  Preferred examples of the high boiling point solvent having a boiling point of 180 ° C. or higher include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, and 1,3-butylene glycol diacetate among the above-mentioned various solvents. 1,6-hexanol diacetate, triacetin and the like.

  Furthermore, it is also effective to partially contain an organic solvent having a boiling point lower than 180 ° C. in order to adjust the viscosity and the solid solubility of the ink and colored resin composition described later. As such an organic solvent, those having low viscosity, high solubility and low surface tension are preferable, and ethers, esters, ketones and the like are preferable. Of these, cyclohexanone, dipropylene glycol dimethyl ether, cyclohexanol acetate and the like are particularly preferable.

On the other hand, when the organic solvent contains alcohols, the ejection stability in the ink jet method may deteriorate. Therefore, the alcohol is preferably 20% by weight or less in the total organic solvent, more preferably 10% by weight or less, and particularly preferably 5% by weight or less.
(2) Silane coupling agent A silane coupling agent can be added to improve adhesion to the substrate. As the types of silane coupling agents, various types such as epoxy, (meth) acrylic, amino and the like can be used alone or in combination of two or more. Agents are preferred.

(3) Surfactant One or more surfactants such as anionic, cationic, nonionic and amphoteric surfactants can be used, but they may adversely affect various properties. It is preferable to use a nonionic surfactant from the viewpoint of low.
As such a surfactant, for example, those described in JP-A No. 2003-322716 are preferably used.

(4) Pigment derivatives As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketo Derivatives such as pyrrolopyrrole and dioxazine are listed, but quinophthalone is preferred.

Substituents of pigment derivatives include sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and complex groups. Examples thereof include those bonded via a ring group and the like, and a sulfonic acid group is preferable. Further, a plurality of these substituents may be substituted on one pigment skeleton. Specific examples of the pigment derivative include phthalocyanine sulfonic acid derivatives, quinophthalone sulfonic acid derivatives, anthraquinone sulfonic acid derivatives, quinacridone sulfonic acid derivatives, diketopyrrolopyrrole sulfonic acid derivatives, and dioxazine sulfonic acid derivatives. These may be used alone or in combination of two or more.

<Ingredient compounding amount in photosensitive colored resin composition>
The content of the alkali-soluble resin (A, A ′, A1 ′, A ″, A1 ″) is usually 5% by weight or more with respect to the total solid content of the photosensitive colored resin composition of the present invention, preferably It is 10% by weight or more, usually 85% by weight or less, preferably 80% by weight or less. If the content of the alkali-soluble resin (the total of A, A ′, A1 ′, A ″, A1 ″) is extremely small, the solubility of the unexposed portion in the developing solution is lowered, and development defects are likely to be induced. Conversely, if the content of the alkali-soluble resin (A, A ′, A1 ′, A ″, A1 ″) is too large, the permeability of the developer to the exposed area tends to increase, and the pixel sharpness And adhesion may be reduced.

  The blending ratio (weight ratio) of the alkali-soluble resin (A) and the alkali-soluble resin (A ′, A1 ′, A ″, A1 ″) is usually 9/1 to 1/9, preferably 8/2 to 2. / 8. When there is too much alkali-soluble resin (A), the linearity of the pattern tends to deteriorate, and when there is too much alkali-soluble resin (total of A ′, A1 ′, A ″, A1 ″), the sensitivity decreases. May occur.

In the present invention, the alkali-soluble resin (A) is selected from the group consisting of an alkali-soluble resin (A ′), an alkali-soluble resin (A1 ′), an alkali-soluble resin (A ″), and an alkali-soluble resin (A1 ″). Use one or more. Usually one is used together, but two or more may be used together.
As described above, in the present invention, a part of the alkali-soluble resin (A, A ′, A1 ′, A ″, A1 ″) may be replaced with another binder resin (H).

In this case, usually 20% by weight or less of the alkali-soluble resin (total of A, A ′, A1 ′, A ″, A1 ″) contained in the above-described proportion in the photosensitive colored resin composition of the present invention. , Preferably 10% by weight or less.
The content of the photopolymerization initiator (B) is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 0%, based on the total solid content of the photosensitive colored resin composition of the present invention. 0.7% or more, usually 30% by weight or less, preferably 20% by weight or less. When the content of the photopolymerization initiator (B) is too small, the sensitivity may be lowered. On the other hand, when the content is too large, the solubility of the unexposed portion in the developer is lowered and development failure is likely to be induced.

When using an accelerator with a photoinitiator (B), content of an accelerator is 0 weight% or more normally with respect to the total solid of the photosensitive coloring resin composition of this invention, Preferably it is 0.02 weight. %, Usually 10% by weight or less, preferably 5% by weight or less, and the accelerator is 0.1 to 50% by weight, particularly 0.1 to 10% by weight, based on the photopolymerization initiator (B). It is preferable to use in proportion.
When the blending ratio of the photopolymerization initiator component composed of the photopolymerization initiator (B) and the accelerator or the like is extremely low, the sensitivity to the exposure light may be lowered. The solubility in the liquid may be reduced, leading to poor development.

The blending ratio 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 in the photosensitive colored resin composition. Preferably it is 0 to 10% by weight.
Content of a color material (C) can be normally selected in the range of 1 to 70 weight% with respect to the total solid content in the photosensitive colored resin composition. In this range, 10 to 70% by weight is more preferable, and 20 to 60% by weight is particularly preferable. If the content of the color material (C) is too small, the film thickness with respect to the color density becomes too large, which may adversely affect the gap control and the like when forming a liquid crystal cell. Conversely, if the content of the color material (C) is too large, sufficient image forming properties may not be obtained.

  In the photosensitive colored resin composition, the amount of the alkali-soluble resin (A) with respect to the color material (C) is usually 20 to 500% by weight, preferably 30 to 300% by weight, more preferably 50 to 200% by weight. It is. If the content of the alkali-soluble resin (A) with respect to the color material (C) is too low, the solubility of the unexposed part in the developing solution is lowered, and it is easy to induce development failure. It becomes difficult to obtain.

  The content of the thiol compound (D) is usually 0.1% by weight or more, preferably 0.3% by weight or more, more preferably 0.5% by weight based on the total solid content of the photosensitive colored resin composition of the present invention. It is not less than the weight and is usually not more than 10% by weight, preferably not more than 5% by weight. When the content of the thiol compound (D) is too small, the sensitivity may be lowered. On the other hand, when the content is too large, the storage stability may be deteriorated.

  The content of the dispersant (E) is usually 50% by weight or less, preferably 30% by weight or less, usually 1% by weight or more, preferably 3% by weight or more in the solid content of the photosensitive colored resin composition. Further, the content of the dispersant (D) is usually 5% by weight or more, particularly 10% by weight or more, and usually 200% by weight or less, particularly 80% by weight or less with respect to the coloring material (C). preferable. If the content of the dispersant (E) is too small, sufficient dispersibility may not be obtained. If the content is too large, the ratio of other components is relatively reduced, resulting in a decrease in color density, sensitivity, film formability, and the like. Tend to.

In particular, as the dispersant (E), it is preferable to use a polymer dispersant and a pigment derivative in combination. In this case, the blending ratio of the pigment derivative is based on the total solid content of the photosensitive colored resin composition of the present invention. Thus, it is usually 1% by weight or more, usually 10% by weight or less, preferably 5% by weight or less.
When using a photopolymerizable monomer (F), the content is 90 weight% or less normally with respect to the total solid of the photosensitive coloring resin composition, Preferably it is 80 weight% or less. When there is too much content of a photopolymerizable monomer (E), the permeability of the developing solution to an exposed part will become high and it may become difficult to obtain a favorable image. In addition, the minimum of content of a photopolymerizable monomer (F) is 1 weight% or more normally, Preferably it is 5 weight% or more.

  When using surfactant, the content is 0.001 to 10 weight% normally with respect to the total solid in a photosensitive colored resin composition, Preferably it is 0.005-1 weight%, More preferably, it is 0.00. 01 to 0.5% by weight, most preferably 0.03 to 0.3% by weight. If the surfactant content is less than the above range, the smoothness and uniformity of the coating film may not be expressed. If the content is too high, the smoothness and uniformity of the coating film may not be expressed, and other characteristics deteriorate. There is a case.

The photosensitive colored resin composition of the present invention is prepared using the above-mentioned 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 “resist”) is produced according to a conventional method.

  Usually, it is preferable to disperse the color material (C) in advance using a paint conditioner, a sand grinder, 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 resist coating characteristics are improved. Moreover, when a black color material is used as a color material (C), it contributes to the improvement of a light-shielding capability.

  The dispersion treatment is usually performed by using a coloring material (C), an organic solvent, and, if necessary, a dispersing agent (E), an alkali-soluble resin (A, A ′, A1 ′, A ″, A1 ″) and / or other It is preferable to carry out in a system in which part or all of the binder resin (H) is used in combination. (Hereinafter, the mixture subjected 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 dispersant (E), the obtained ink and This is preferable since the thickening of the resist over time is suppressed (excellent dispersion stability).

In addition, when a dispersion treatment is performed on a liquid containing all components to be blended in the colored resin composition, a highly reactive component may be modified due to heat generated during the dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing the above-described components.
When the color material (C) is dispersed with a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. In the dispersion treatment conditions, the temperature is usually from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the liquid and the size of the dispersion treatment apparatus. The standard of dispersion is to control the gloss of the ink so that the 20-degree specular gloss (JIS Z8741) of the resist is in the range of 100 to 200. When the glossiness of the resist is low, the dispersion treatment is not sufficient, and rough pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, resolution, and the like. . Further, when the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so that the dispersion stability tends to be impaired.

Next, the ink obtained by the dispersion treatment and the other components contained in the resist are mixed to obtain a uniform solution. In the resist manufacturing process, fine dust is often mixed in the liquid, and thus the obtained resist is preferably filtered 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 according to its production method.

(1) Transparent substrate (support)
The transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, epoxy resins, unsaturated polyester resins, and poly (meth). Examples thereof include thermosetting resin sheets such as acrylic resins, and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance.

For transparent substrates and black matrix forming substrates, to improve surface properties such as adhesion, corona discharge treatment, ozone treatment, silane coupling agents, thin film formation treatment of various resins such as urethane resins, etc. May be performed.
The thickness of the transparent substrate is usually 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is 0.01-10 micrometers normally, Preferably it is the range of 0.05-5 micrometers.

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

The black matrix is formed on a transparent substrate using a light-shielding metal thin film or a photosensitive colored resin composition for resin black matrix. As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide and chromium nitride, nickel and tungsten alloy, etc. are used, and these may be laminated in a plurality of layers.
These metal light shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape with a positive photoresist, ceric ammonium nitrate, perchloric acid and / or nitric acid are added to chromium. Other materials are etched using an etching solution according to the material, and finally a positive photoresist is stripped with a special stripping agent to form a black matrix. be able to.

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

  When using the photosensitive colored resin composition for resin black matrix, the black matrix is formed using the photosensitive colored resin composition of the present invention containing a black coloring material. For example, black color material such as carbon black, graphite, iron black, aniline black, cyanine black, titanium black or the like, or red, green, blue or the like appropriately selected from inorganic or organic pigments and dyes A black matrix can be formed in the same manner as described below for forming a red, green, and blue pixel image using a photosensitive colored resin composition containing a black color material by mixing.

(3) Pixel formation
(3-1) Application of photosensitive colored resin composition After applying and drying a photosensitive colored resin composition containing a color material of one of red, green and blue on a transparent substrate provided with a black matrix. Then, a photomask is overlaid on the coating film, and a pixel image is formed through image exposure, development, and heat curing or photocuring as necessary through this photomask to form a colored layer. A color filter image can be formed by performing this operation for each of the three colored photosensitive colored resin compositions of red, green, and blue.

  The photosensitive colored resin composition for color filters can be applied by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, a spray coating method, or the like. In particular, the die coating method significantly reduces the amount of coating solution used, and has no influence from mist adhering to the spin coating method. To preferred.

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

(3-2) Drying of the coating film The drying of the coating film after applying the photosensitive colored resin composition to the substrate is preferably performed by a drying method using a hot plate, IR oven, or convection oven. Drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected in a range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably 50 to 130 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes.

The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, when the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.
(3-3) Exposure Image exposure is performed by overlaying a negative mask pattern on the coating film of the photosensitive colored resin composition and irradiating a UV or visible light source through this mask pattern. At this time, if necessary, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

(3-4) Development The color filter according to the present invention contains an organic solvent or a surfactant and an alkaline compound after image-exposing the coating film of the photosensitive colored resin composition with the above-mentioned light source. An image can be formed on a substrate by development using an aqueous solution. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.

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

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

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent may be used alone or in combination with an aqueous solution.
There are no particular limitations on the conditions for the development treatment, and the development temperature is usually in the range of 10 to 50 ° C.
The developing method can be any method such as an immersion developing method, a spray developing method, a brush developing method, and an ultrasonic developing method.

(3-5) Thermosetting treatment The color filter substrate after development is subjected to thermosetting treatment. The thermosetting treatment conditions at this time are selected such that the temperature is in the range of 100 to 280 ° C, preferably 150 to 250 ° C, and the time is in the range of 5 to 60 minutes. Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black, red, green, and blue to form a color filter. Note that the order of patterning the four colors is not limited to the order described above.

(3-6) Formation of transparent electrode The color filter is used as a part of components such as color displays and liquid crystal display devices by forming transparent electrodes such as ITO on the image as it is. In order to enhance the property and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed.

[Liquid Crystal Display]
The liquid crystal display device of the present invention is manufactured using the above-described color filter of the present invention.
A liquid crystal display device usually forms an alignment film on a color filter, spreads spacers on the alignment film, and then bonds to a counter substrate to form a liquid crystal cell, injects liquid crystal into the formed liquid crystal cell, Complete by connecting to the counter electrode. As the alignment film, a resin film such as polyimide is suitable. For the formation of the alignment film, a gravure printing method and / or a flexographic printing method is usually employed, and the thickness of the alignment film is several tens of nm. After the alignment film is cured by thermal baking, it is surface-treated by irradiation with ultraviolet rays or a rubbing cloth to be processed into a surface state in which the tilt of the liquid crystal can be adjusted.

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

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

The type of liquid crystal is not particularly limited, and is a conventionally known liquid crystal such as an aromatic, aliphatic, or polycyclic compound, and may be any of lyotropic liquid crystal, thermotropic liquid crystal, and the like. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like are known, but any of them may be used.
[Organic EL display]
The organic EL display of the present invention is produced using the color filter of the present invention.

  When an organic EL display is produced using the color filter of the present invention, for example, as shown in FIG. A color filter in which a resin black matrix (not shown) provided between the pixels 20 is formed is manufactured, and the organic light-emitting body 500 is formed on the color filter via the organic protective layer 30 and the inorganic oxide film 40. By laminating, the organic EL element 100 can be manufactured. In addition, at least one of the pixel 20 and the resin black matrix is produced using the photosensitive colored resin composition of the present invention. As a method for laminating the organic light emitter 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 sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. A method described in, for example, “Organic EL display” (Ohm, Inc., August 20, 2004, light emission, Shizushi Tokito, Chiba Adachi, Hideyuki Murata) using the organic EL element 100 manufactured in this manner, etc. Thus, an organic EL display can be produced.

  The color filter of the present invention can be applied to both passive drive type organic EL displays and active drive type organic EL displays.

Next, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
<Synthesis Example 1: Synthesis of alkali-soluble resin (I)>
“NC3000H” manufactured by Nippon Kayaku Co., Ltd. (in the general formula (1-a), R ⁴¹ = H, epoxy equivalent 288, softening point 69 ° C.) 400 parts by weight, acrylic acid 102 parts by weight, p-methoxyphenol 0 .3 parts by weight, 5 parts by weight of triphenylphosphine, and 264 parts by weight of propylene glycol monomethyl ether acetate were charged in a reaction vessel and stirred at 95 ° C. until the acid value was 3 mgKOH / g or less. It took 9 hours for the acid value to reach the target (acid value 2.2 mgKOH / g). Subsequently, 151 parts by weight of tetrahydrophthalic anhydride was further added and reacted at 95 ° C. for 4 hours. An alkali-soluble resin (I) solution having an acid value of 102 mgKOH / g and a polystyrene-reduced weight average molecular weight (Mw) of 3900 measured by GPC Got.

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

  40 g of an epoxy compound (epoxy equivalent 231) represented by the above structural formula, 12.7 g of acrylic acid, 47.8 g of methoxybutyl acetate, 1.00 g of triphenylphosphine, and 0.025 g of paramethoxyphenol were mixed with a thermometer, a stirrer, The mixture was placed in a flask equipped with a condenser and allowed to react at 90 ° C. with stirring until the acid value was 5 mgKOH / g or less. The reaction took 15 hours to obtain an epoxy acrylate solution.

25 parts of the above epoxy acrylate solution, 0.76 parts by weight of trimethylolpropane (TMP), 3.7 parts by weight of biphenyltetracarboxylic dianhydride (BPDA), and 3.9 parts by weight of tetrahydrophthalic anhydride (THPA) Was put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.
When the resin solution becomes transparent, it is diluted with methoxybutyl acetate, prepared to have a solid content of 50% by weight, and an alkali-soluble resin having an acid value of 131 mgKOH / g and a polystyrene-reduced weight average molecular weight (Mw) of 3000 measured by GPC (II) was obtained.

In addition, this alkali-soluble resin (II) is the “alkali-soluble resin (A
1 ') ".
<Synthesis Example 3: Synthesis of alkali-soluble resin (III)>

  50 g of epoxy compound having the above structure (epoxy equivalent 264), 13.65 g of acrylic acid, 60.5 g of methoxybutyl acetate, 0.936 g of triphenylphosphine, and 0.032 g of paramethoxyphenol were attached to a thermometer, a stirrer and a cooling pipe. The reaction was continued at 90 ° C. with stirring until the acid value was 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, 0.76 parts by weight of trimethylolpropane (TMP), 3.3 parts by weight of biphenyltetracarboxylic dianhydride (BPDA), 3.5 parts by weight of tetrahydrophthalic anhydride (THPA) Was put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.
When the resin solution becomes transparent, it is diluted with methoxybutyl acetate, prepared to have a solid content of 50% by weight, an acid value of 131 mg KOH / g, and an alkali-soluble resin having a polystyrene equivalent weight average molecular weight (Mw) of 2600 measured by GPC (III) was obtained.

The alkali-soluble resin (III) is an “alkali-soluble resin (A
1 ")".
<Synthesis Example 4: Preparation of ink>
Carbon black for color (“MA-8” manufactured by Mitsubishi Chemical Co., Ltd., average particle size 24 μm, DBP oil absorption 58 ml / 100 g), propylene glycol monomethyl ether acetate (PGMEA) and urethane polymer dispersant Disperbyk-182 "(manufactured by Big Chemie) was added so that the dispersant was in a proportion of 10 parts by weight as a solid content and the solid content concentration was 30% by weight. The total weight of the dispersion was 181 g.

  This was thoroughly stirred with a stirrer and premixed. Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 6 hours. As the beads, 0.5 mmφ zirconia beads were used, and the same weight as the dispersion was added. After the completion of dispersion (20-degree specular gloss in JIS Z8741 was 170), beads and dispersion were separated by a filter to prepare ink 1.

[Examples 1-6 and Comparative Examples 1-3]
(1) Preparation of resist (photosensitive coloring resin composition) Using ink 1 prepared in Synthesis Example 4, each component was added so that the ratio in the solid content was the mixing ratio in Table 1, and the solid content was further increased. An organic solvent was added so as to be 20% by weight, and the mixture was stirred and dissolved with a stirrer to prepare a black resist.

<Formulation>
Ink 1 prepared in Synthesis Example 4
Each alkali-soluble resin solution prepared in Synthesis Examples 1 to 3 Photopolymerizable monomer: Dipentaerythritol hexaacrylate (DPHA)
Photopolymerization initiator: “CGI242” manufactured by Ciba Specialty Chemicals Co., Ltd. Oxime ester compound represented by the following structural formula

Thiol compound: “Karenz MT PE1” (pentaerythritol tetrakis (3-mercaptobutyrate)) manufactured by Showa Denko KK
Organic solvent: PGMEA
(2) Evaluation of resist The black resist prepared in (1) was applied to a glass substrate with a spin coater and dried on a hot plate at 80 ° C. for 1 minute. The film thickness of the resist after drying was measured with a stylus type film thickness meter (“α-step” manufactured by Tencor), and it was 1 μm. Next, this sample was image-exposed through a mask while changing the exposure amount with a high-pressure mercury lamp. Then, a resist pattern was obtained by spray development using a KOH aqueous solution with a concentration of 0.1% by weight at a temperature of 23 ° C.

The sensitivity, resolution and linearity of the formed resist pattern were evaluated according to the following criteria, and the results are shown in Table 2.
1. Sensitivity A mask pattern having a dimension of 20 μm was displayed with an appropriate exposure (mJ / cm ² ) that can be formed according to the dimension. That is, a resist with a small exposure amount is highly sensitive because an image can be formed with a low exposure amount.

2. Resolution The minimum resist pattern dimension that can be resolved at an exposure amount that faithfully reproduces a mask pattern with a dimension of 20 μm was observed with a microscope at a magnification of 200 times.
Minimum pattern dimension is 10μm or less: ◎
Minimum pattern dimension is more than 10μm and 15μm or less: ○
Minimum pattern dimension exceeds 15 μm: ×
3. Linearity The shape of fine black pixels at an exposure amount that faithfully reproduces a mask pattern with a dimension of 20 μm was observed with a microscope at a magnification of 1000 times.

Excellent edge linearity: ◎
Edge linearity is relatively good: ○
Some protrusions or irregularities on the edge: △
Edges with a lot of protrusions and irregularities: ×

  From Table 2, it can be seen that according to the present invention, a photosensitive colored resin composition having high sensitivity and excellent resolution and linearity is provided.

DESCRIPTION OF SYMBOLS 10 Transparent support substrate 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode 51 Hole injection layer 52 Hole transport layer 53 Light emitting layer 54 Electron injection layer 55 Cathode 100 Organic EL element 500 Organic light emitter

Claims (10)

1 or more selected from the group consisting of alkali-soluble resin (A), alkali-soluble resin (A ′), alkali-soluble resin (A1 ′), alkali-soluble resin (A ″), and alkali-soluble resin (A1 ″) A photopolymerization initiator (B), a coloring material (C), and two or more mercapto groups, and a carbon atom at the α-position to the mercapto group has at least one hydrocarbon group as a substituent. A photosensitive colored resin composition for a color filter, which comprises a thiol compound (D) having a colorant.
<Alkali-soluble resin (A)>
The reaction product of the epoxy resin (a) represented by the following general formula (1-a) and the unsaturated group-containing carboxylic acid (b) is further reacted with a polybasic acid and / or its anhydride (c). An alkali-soluble resin (A) obtained in this way.

[In the said general formula (1-a), n shows an average value and shows the number of 0-10. R ⁴¹ represents any of 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, and a biphenyl group. A plurality of R ⁴¹ present in one molecule may be the same or different. G represents a glycidyl group. ]
<Alkali-soluble resin (A ')>
An epoxy compound (a ′) represented by the following general formula (1-a ′), an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group at the ester moiety ( An alkali-soluble resin (A ′) obtained by reacting a reaction product with b ′) with a polybasic acid and / or its anhydride (c ′).

[In the general 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 represents an alkylene group. x and y each independently represents an integer of 0 or more. ]
<Alkali-soluble resin (A1 ′)>
The epoxy compound (a ′) represented by the above general formula (1-a ′) and an α, β-unsaturated monocarboxylic acid and / or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group at the ester moiety ( An alkali-soluble resin (A1 ′) obtained by reacting a mixture of a reaction product with b ′) and a polyhydric alcohol (d ′) with a polybasic acid and / or its anhydride (c ′).
<Alkali-soluble resin (A ")>
A reaction product of an epoxy compound (a ″) represented by the following general formula (1-a ″) and an unsaturated group-containing carboxylic acid (b ″) is reacted with a polybasic acid and / or its anhydride (c ″). Alkali-soluble resin (A ") obtained by making it.

[In the above general formula (1-a ″), X represents a linking group represented by the following general formula (2a), (2b) or (3), provided that one or more adamantane structures are present in the molecular structure. 1 represents an integer of 2 or 3.

(In the above general formulas (2a) and (2b), R ^{1 to} R ⁴ and R ^{13 to} R ¹⁵ each independently have an adamantyl group, a hydrogen atom, and a substituent which may have a substituent. An optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted phenyl group is shown.
In the general formula (3), R ^{5 to} R ¹² may each independently have a hydrogen atom, an alkyl group having 1 to 12 carbon atoms that may have a substituent, or a substituent. Represents a phenyl group; Y represents a divalent linking group containing an adamantane structure, which may have a substituent.
In the general formulas (2a), (2b), and (3), * represents a binding site with the glycidyloxy group in the general formula (1-a ″).
<Alkali-soluble resin (A1 ")>
A mixture of a reaction product of the epoxy compound (a ″) represented by the general formula (1-a ″) and the unsaturated group-containing carboxylic acid (b ″) and a polyhydric alcohol (d ″) is converted into a polybasic acid. And / or an alkali-soluble resin (A1 ″) obtained by reacting with the anhydride (c ″) thereof.   The photosensitive colored resin composition for a color filter according to claim 1, further comprising a dispersant (E).   Furthermore, the photosensitive colored resin composition for color filters of Claim 1 or 2 containing a photopolymerizable monomer (F).   The photosensitive colored resin composition for color filters according to any one of claims 1 to 3, wherein the photopolymerization initiator (B) contains oxime ester derivatives.   The photosensitive coloring resin for color filters according to any one of claims 1 to 4, wherein the content of the coloring material (C) is 20 to 60% by weight in the total solid content of the photosensitive coloring resin composition. Composition.   The photosensitive coloring resin composition for color filters as described in any one of Claims 1 thru | or 5 in which a color material (C) contains a black color material. The photosensitive colored resin composition for a color filter according to any one of claims 1 to 6, wherein the thiol compound (D) is a thiol compound including a partial structure represented by the following general formula (d-1).

(In General Formula (d-1), R ⁵¹ and R ⁵² each independently represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, and a represents an integer of 0 to 4. However, R ⁵¹ And R ⁵² is hydrogen.)   The color filter which has a pixel or black matrix formed using the photosensitive coloring resin composition as described in any one of Claims 1 thru | or 7 on a transparent substrate.   A liquid crystal display device produced using the color filter according to claim 8. An organic EL display produced using the color filter according to claim 8.

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