JP2013011845A - Photosensitive colored resin composition for color filter, color filter, liquid crystal display device, and organic electroluminescent display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive colored resin composition for a color filter, the composition having a high light-shielding property and high volume resistance and showing a good tapered shape.SOLUTION: The photosensitive colored resin composition for a color filter comprises an alkali-soluble resin, a photopolymerization initiator, a coloring material and a dispersant, in which the coloring material includes a black pigment and an organic color pigment excluding a black pigment, the content of the black pigment is 20 to 95 wt.% of the sum of the black pigment and the organic color pigment excluding a black pigment, and the alkali-soluble resin comprises an alkali-soluble resin (A-1) and/or an alkali-soluble resin (A-2). The alkali-soluble resin (A-1) is obtained by allowing a reaction product of a specified epoxy compound (a) and an unsaturated group-containing carboxylic acid to react with a polybasic acid and/or its anhydride. The alkali-soluble resin (A-2) is obtained by allowing a reaction product of an epoxy compound expressed by formula (1) and an unsaturated group-containing carboxylic acid to react with a polyhydric alcohol and a polybasic acid and/or its anhydride.

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, the present invention relates to a photosensitive colored resin composition for a color filter having high light shielding properties, high volume resistance, and good taper shape, and its use.

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 color filter usually has pixels of each color such as red, green, and blue, and a black matrix is usually formed between the pixels. The photosensitive colored resin composition used for black matrix image formation has been required to have characteristics such as sufficient light-shielding property, resolution, good adhesion to a substrate, and low development residue. Further, in recent years, it has been required as a performance of the black matrix that it corresponds to the panel system and has a high volume resistivity.

Patent Documents 1 and 2 describe increasing the resistance of a black matrix by using carbon black coated with a resin. However, the coated carbon black still has conductivity, and there remains a problem that the resistance value gradually decreases by increasing the concentration.
Patent Documents 3 and 4 describe a black matrix obtained by mixing carbon black and an organic coloring pigment. In these, it is preferable that the pigment concentration is high and the amount of organic coloring pigments is large. However, when the pigment concentration is not high, the taper angle cannot be sufficiently obtained.

  Patent Document 5 describes a resin containing an adamantyl group.

Japanese Patent Laid-Open No. 9-71733 JP-A-9-166869 JP 2007-249046 A JP 2009-074446 A JP 2008-287246 A

  An object of the present invention is to provide a photosensitive colored resin composition for a color filter having a high light-shielding property and volume resistance, and having a good taper shape, a color filter using the photosensitive colored resin composition, and using the same An object of the present invention is to provide a liquid crystal display device and an organic EL display.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a black pigment (C1) and an organic coloring pigment (C2) that is not a black pigment in a specific ratio and a specific alkali-soluble property having an adamantane structure. It discovered that the said subject could be solved by using resin (A-1) and / or alkali-soluble resin (A-2), and reached | attained this invention.
That is, the gist of the present invention is as follows.
[1] An alkali-soluble resin (A), a photopolymerization initiator (B), a color material (C), and a dispersant (D)
The coloring material (C) contains a black pigment (C1) and an organic coloring pigment (C2) that is not a black pigment, and the content of the black pigment (C1) is an organic coloring pigment that is not a black pigment (C1) and a black pigment (C1). 20 to 95% by weight of the sum of C2),
The photosensitive colored resin composition for a color filter, wherein the alkali-soluble resin (A) contains an alkali-soluble resin (A-1) and / or an alkali-soluble resin (A-2).

<Alkali-soluble resin (A-1)>
Alkali solubility obtained by reacting a reaction product of an epoxy compound (a) represented by the following general formula (1) with an unsaturated group-containing carboxylic acid (b) with a polybasic acid and / or its anhydride (c) Resin (A-1).
<Alkali-soluble resin (A-2)>
A reaction product of an epoxy compound (a) represented by the following general formula (1) and an unsaturated group-containing carboxylic acid (b) is converted into a polyhydric alcohol (d), a polybasic acid and / or an anhydride thereof (c). Alkali-soluble resin (A-2) obtained by reacting with.

[In the general formula (1), X represents a linking group represented by the following general formula (2a), (2b) or (3). However, one or more adamantane structures are included in the molecular structure. l 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), * indicates a binding site with the glycidyloxy group in the general formula (1). )]
[2] The photosensitive colored resin composition for color filters according to [1], wherein the black pigment (C1) is carbon black coated with a resin.
[3] The color filter photosensitivity according to [1] or [2], wherein the organic color pigment (C2) includes any one of the following (C2-1) to (C2-4): Colored resin composition.
(C2-1) C.I. I. A red pigment selected from CI Pigment Red 177, 209, 224, and 254.
(C2-2) C.I. I. Blue pigment that is Pigment Blue 15: 6.
(C2-3) C.I. I. A yellow pigment selected from CI Pigment Yellow 83, 138, 139, 150, and 180.
(C2-4) C.I. I. A purple pigment which is CI Pigment Violet 23.
[4] The content of the black pigment (C1) is 55 to 95% by weight of the sum of the black pigment (C1) and the organic coloring pigment (C2) that is not a black pigment [1] to [3 ] The photosensitive coloring resin composition for color filters in any one of these.
[5] The photosensitive colored resin composition for color filters according to any one of [1] to [4], wherein the dispersant (D) includes a polymer dispersant having a basic functional group.
[6] The photosensitive colored resin composition for a color filter according to any one of [1] to [5], wherein the photopolymerization initiator (B) includes oxime ester derivatives.
[7] A color filter having pixels or a black matrix formed on the substrate using the photosensitive colored resin composition according to any one of [1] to [6].
[8] A liquid crystal display device produced using the color filter according to [7].
[9] An organic EL display produced using the color filter according to [7].

  The photosensitive colored resin composition for a color filter of the present invention has high light shielding properties and volume resistance, and has a good taper shape.

It is typical sectional drawing which shows taper angle (theta). 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 a color filter of the present invention contains an alkali-soluble resin (A), a photopolymerization initiator (B), a color material (C), and a dispersant (D), and the color material (C) is The black pigment (C1) and the organic coloring pigment (C2) that is not a black pigment are contained, and the content of the black pigment (C1) is 20 to the sum of the black pigment (C1) and the organic coloring pigment (C2) that is not a black pigment. It is 95 weight%, and alkali-soluble resin (A) contains alkali-soluble resin (A-1) and / or alkali-soluble resin (A-2), It is characterized by the above-mentioned.

<Alkali-soluble resin (A-1)>
The alkali-soluble resin (A-1) is a polybasic acid and / or its anhydride ( An alkali-soluble resin obtained by reacting with c).

[In the general formula (1), X represents a linking group represented by the following general formula (2a), (2b) or (3). However, one or more adamantane structures are included in the molecular structure. l 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), * indicates a binding site with the glycidyloxy group in the general formula (1). )]
(1) Epoxy compound (a) represented by the general formula (1) First, a group in the epoxy compound (a) represented by the general formula (1) (hereinafter sometimes referred to as “component (a)”) X 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) each have an adamantane structure in the range of 2 to 4. 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 including an adamantyl structure which may have a substituent”. If it is, there is no restriction | limiting in particular other than that, For example, it is preferable that it is a coupling group represented by the following general formula (4) or (5).

[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) 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.

The molecular weight of X represented by the general formula (1) is preferably 200 or more and 1000 or less. If the molecular weight of X is less than 200, the chemical resistance tends to be inferior, and if it exceeds 1000, the sensitivity may be low.
Moreover, it is preferable that the epoxy equivalent of the epoxy compound (a) represented by General formula (1) is 210 or more, and it is more preferable that it is 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.

The epoxy compound (a) may be used alone or in combination of two or more.
A commercially available epoxy compound (a) 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 previously added 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. An epoxy which is added or is reacted at a temperature of 20 to 120 ° C. for 1 to 10 hours while X is a linking group represented by the general formula (2a) or (2b) in the general formula (1) 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. While reacting at a temperature of 20 to 120 ° C. for 1 to 10 hours, an epoxy compound (a) in which X in the general formula (1) is represented by the general formula (3) can be obtained.

  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, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure. The epihalohydrin may be 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) is also produced 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 do.

  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 “component (b)”) 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) acryloyloxyethylphthalic acid, 2- ( (Meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl maleic acid, 2- (meth) acryloyloxypropyl succinic acid, 2- (Meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropyltetrahydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meta ) Acryloyloxybutyl succinic acid, 2- (meth) acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutyl hydrophthalic acid, 2- (meth) acryloyloxybutyl phthalic acid, 2- (meth) (Meth) acryloyloxyalkyl esters of dibasic acids such as acryloyloxybutylmaleic acid; (meth) acrylic acid and lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, etc. Monomers added by adding (meth) acrylic acid dimer, etc.

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 component (a) with 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 ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, and benzyltriethylammonium chloride. Carboxylic acid can be added to the epoxy compound by reacting in an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours using 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 5% by weight, based on the reaction raw material mixture (the total of the components (a) and (b)). 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 component (b) to the epoxy group of the component (a) is usually 90 to 100 mol% with respect to the epoxy group. Since the remaining epoxy group tends to adversely affect storage stability, the component (b) is usually 0.8 to 1.5 equivalents, particularly 0.9 equivalents, relative to 1 equivalent of the epoxy group of the component (a). It is preferable to carry out the reaction at a ratio of ˜1.1 equivalents.
(3) Polybasic acid and / or anhydride (c)
As the polybasic acid and / or anhydride (c) (hereinafter, sometimes referred to as “component (c)” or “polybasic acid (anhydride)”), dibasic acid and / or anhydride thereof ( Hereinafter, referred to as “2 basic acid (anhydride)”, 3 basic acid and / or anhydride thereof (hereinafter referred to as “3 basic acid (anhydride)”), 4 basic acid and / or anhydride ( (Hereinafter referred to as “4-basic acid (anhydride)”).

  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 4-basic acid (anhydride) as the component (c), the molecular weight is increased by a crosslinking reaction. For this reason, there exist effects, such as an adhesive improvement to a board | substrate, adjustment of solubility, an improvement of a sensitivity or alkali tolerance, and it is preferable.

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. Of these, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, succinic acid or their anhydrides are preferred. These may be used alone or in combination of two or more.

By reacting a dibasic acid (anhydride) as the component (c) with the reaction product of the component (a) and the component (b), the solubility can be easily adjusted, and the adhesion to the substrate is improved. Therefore, it 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 can be balanced. . 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 tetrabasic acid (anhydride). In this case, 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 30 to 100 mol%. When the addition rate of the 4-basic acid (anhydride) as 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.
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.

  (C) When using together 4 basic acid (anhydride) and 2 basic acid (anhydride) as a component, the molar ratio is 2 basic acid (anhydride): 4 basic acid (anhydride) = 99: 1- 20:80 is preferable, and 80:20 to 30:70 is more preferable. If the amount of tetrabasic acid (anhydride) is less than this range, the film properties of the resulting coating film may be reduced. If the amount of dibasic acid (anhydride) is too small, the viscosity of the resulting resin solution will be low. May be difficult to handle.

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.
(C) When 4-basic acid (anhydride) and / or 2-basic acid (anhydride) and 3-basic acid (anhydride) are used in combination, the amount of tribasic acid (anhydride) used is too small. And the effect is low, and there is a possibility of reduced alkali resistance. Therefore, it is usually 5 to 70 mol%, preferably 10 to 40, based on the hydroxyl group produced when component (b) is added to component (a). About mol%.

The total addition rate of component (c) is usually 10 to 100 mol%, preferably 20 to 100 mol%, more preferably based on the hydroxyl group produced when component (b) is added to component (a). 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.
The reaction temperature for adding the component (c) is usually 80 to 130 ° C, preferably 90 to 125 ° C. When the reaction temperature exceeds 130 ° C., polymerization of a part of unsaturated groups in component (b) may occur, leading to a rapid increase in molecular weight. Moreover, if it is less than 80 degreeC, reaction does not advance smoothly but (c) component may remain | survive.

<Alkali-soluble resin (A-2)>
The alkali-soluble resin (A-2) is obtained by reacting a reaction product of the epoxy compound (a) represented by the general formula (1) with the unsaturated group-containing carboxylic acid (b), a polyhydric alcohol (d), and a polybasic compound. It is an alkali-soluble resin obtained by reacting with an acid and / or its anhydride (c).
The reaction product of the component (a) and the component (b), the component (c), the addition rate of the component (c), and the reaction conditions of the component (c) are the same as those of the alkali-soluble resin (A-1). is there.

(1) Polyhydric alcohol (d)
Examples of the polyhydric alcohol (d) (hereinafter sometimes referred to as “component (d)”) include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, 1,2,3- One or more polyhydric alcohols selected from propanetriol are preferred.

By using the component (d), it is possible to increase the molecular weight of the alkali-soluble resin (A1), introduce branching into the molecule, and balance the molecular weight and the viscosity. 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.
If the amount of the component (d) used is too small, the effect is thin, and if it is too large, there is a possibility of thickening or gelation. About 0.01 to 0.5 times by weight, preferably about 0.02 to 0.2 times by weight.
Although there is no restriction | limiting in the order which mixes (c) component and (d) component with the reaction material of (a) component and (b) component, Usually, the reaction material of (a) component and (b) component Further, the component (d) is further mixed, and the component (c) is added to any hydroxyl group present in the mixture.

<Acid value and molecular weight of alkali-soluble resins (A-1) and (A-2)>
The acid values of the alkali-soluble resins (A-1) and (A-2) thus obtained are usually 10 mgKOH / g or more, preferably 50 mgKOH / 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-1) and (A-2) is preferably 1,500 or more, and 2,000 or more. It is more preferable that 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.

<Other binder resins>
In the photosensitive colored resin composition of the present invention, a part of the alkali-soluble resin (A-1, A-2) may be replaced with another binder resin. That is, you may use together alkali-soluble resin (A-1, A-2) and another binder resin.
As long as the performance of the present invention is not impaired, there is no limitation on other binder resins that can be used in combination with the alkali-soluble resins (A-1, A-2), and the resins usually used for the photosensitive colored resin composition for color filters. Just choose. For example, it can be obtained by adding an α, β-unsaturated monocarboxylic acid to an epoxy resin or an α, β-unsaturated monocarboxylic acid ester having a carboxyl group at the ester portion, and further reacting with a polybasic acid anhydride. Resin etc. are mentioned.

  As an epoxy resin used as a raw material, for example, bisphenol A type epoxy resin (for example, “Epicoat 828”, “Epicoat 1001”, “Epicoat 1002”, “Epicoat 1004” manufactured by Yuka Shell Epoxy Co., Ltd.), bisphenol A type epoxy, etc. Epoxy obtained by reaction of alcoholic hydroxyl group of resin and epichlorohydrin (for example, “NER-1302” (epoxy equivalent 323, softening point 76 ° C.) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F-type resin (for example, oily shell epoxy) "Epicoat 807", "EP-4001", "EP-4002", "EP-4004 etc.") manufactured by the company, epoxy resin obtained by reaction of alcoholic hydroxyl group of bisphenol F type epoxy resin and epichlorohydrin (for example, Japan “NER-740” manufactured by Kayaku Co., Ltd. (Epoxy equivalent 350, softening point 66 ° C.), bisphenol S type epoxy resin, biphenyl glycidyl ether (eg “YX-4000” manufactured by Yuka Shell Epoxy), phenol novolac type epoxy resin (eg Nippon Kayaku) "EPPN-201", Yuka Shell Epoxy "EP-152", "EP-154", Dow Chemical "DEN-438"), (o, m, p-) cresol novolak Type epoxy resin (for example, “EOCN-102S”, “EOCN-1020”, “EOCN-104S” manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (for example, “TEPIC” manufactured by Nissan Chemical Co., Ltd.), trisphenol Methane type epoxy resin (for example, “EPPN-501”, “EPN-502”, “E” manufactured by Nippon Kayaku Co., Ltd.) PN-503 "), fluorene epoxy resin (for example, cardo epoxy resin" ESF-300 "manufactured by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy resin (" Celoxide 2021P "," Celoxide EHPE "manufactured by Daicel Chemical Industries, Ltd.) ), Epoxy resin obtained by glycidylation of phenol resin by reaction of dicyclopentadiene and phenol (for example, “XD-1000” manufactured by Nippon Kayaku Co., Ltd., “EXA-7200” manufactured by Dainippon Ink Co., Ltd., manufactured by Nippon Kayaku Co., Ltd.) "NC-3000", "NC-7300"), etc. can be preferably used.

<Photoinitiator (B)>
The photopolymerization initiator (B) is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. If necessary, an additive such as a sensitizing dye may be added and used.
Examples of the photopolymerization initiator include titanocene derivatives described in JP-A-59-152396 and JP-A-61-151197; biimidazole derivatives described in JP-A-2000-56118; Halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N- Radical activators such as aryl-α-amino acid esters, α-aminoalkylphenone derivatives; described in JP-A 2000-80068, JP-A 2006-36750, JP-A 2008-179611 Examples include oxime ester derivatives.

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-difluoro-1-yl), dicyclopentadienyl titanium [2,6-difluoro-3-
(Pyro-1-yl) -phen-1-yl] and the like.

  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 Yl) acridine derivatives acridine like; 9,10-dimethyl-benz phenazine phenazine derivatives such as; anthrone derivatives such as benzanthrone etc. may be mentioned.
Among these photopolymerization initiators, oxime ester derivatives are particularly preferable from the viewpoint of sensitivity.

  If necessary, the photopolymerization initiator can be used in combination with a sensitizing dye according to the wavelength of the image exposure light source 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)>
Moreover, the color material (C) used for the photosensitive colored resin composition of the present invention contains a black pigment (C1) and an organic colored pigment (C2) that is not a black pigment. The color material (C) is preferably composed of a black pigment (C1) and an organic coloring pigment (C2) that is not a black pigment.
As the black pigment (C1), carbon black, titanium black, acetylene black, lamp black, bone black, aniline black, cyanine black, iron oxide black pigment, graphite and the like can be used.
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, OIL
9B, OIL11B, OIL30B, OIL31B Degussa: Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, ColorBlack, ColorBlack4 W1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

Cabot Corporation: Monarch120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130 , VULCAN XC72R, ELFTEX-8
Made by Colombian Carbon: Raven11, Raven14, Raven15, Raven16, Raven22, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10 , RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000
In the present invention, it is effective to use carbon black coated with a resin in order to increase the volume resistance value. For example, carbon black described in JP-A No. 09-71733 can be suitably used.

  As carbon black to be coated, the total content of Na and Ca is preferably 100 ppm or less. Carbon black is usually raw material oil or combustion oil (or gas) at the time of production, reaction stop water or granulated water, Na mixed from furnace materials of the reactor, Ca, K, Mg, Al, Fe, etc. Is contained in the order of percent. Of these, Na and Ca are generally contained in a few hundred ppm or more, but if many of these are present, they penetrate into the transparent electrode (ITO) and other electrodes, causing electrical shorts. This is because there is a case.

  As a method for reducing the content of ash containing Na and Ca, carefully selected raw oil, fuel oil (or gas), and reaction stop water for producing carbon black with as little content as possible. And a method of reducing the addition amount of the alkaline substance for adjusting the structure as much as possible. As another method, there is a method in which Na or Ca is dissolved and removed by washing carbon black produced from a furnace with water or hydrochloric acid.

Specifically, after carbon black is mixed and dispersed in water, hydrochloric acid or hydrogen peroxide solution, when a solvent that is hardly soluble in water is added, the carbon black moves to the solvent side and completely separates from water. Most of Na and Ca present in carbon black are dissolved and removed in water and acid. In order to reduce the total amount of Na and Ca to 100 ppm or less, there may be a case where a carbon black production process alone or a water or acid dissolution method alone with carefully selected raw materials may be possible. The total amount of Na and Ca can be easily made 100 ppm or less.

  The resin-coated carbon black is preferably so-called acidic carbon black having a pH of 6 or less. Such carbon black is suitable because it has a small dispersed diameter (agglomerated diameter) in water, and can cover even fine units. Further, the resin-coated carbon black preferably has a particle diameter of 40 nm or less and a dibutyl phthalate (DBP) absorption of 140 ml / 100 g or less. If the particle size is larger than 40 nm and the DBP absorption is larger than 140 ml / 100 g, the dispersibility when made into a paste is excellent, but the coating film may not have sufficient density, and the film thickness is about 1 to 2 μm. It is because there is a possibility that it may become scarce.

  The method for preparing the carbon black coated with the resin is not particularly limited. For example, after appropriately adjusting the blending amount of the carbon black and the resin, After mixing and stirring the resin solution obtained by mixing the resin and a solvent such as cyclohexanone, toluene, xylene, and the like, and the suspension obtained by mixing carbon black and water, the carbon black and water are separated, 1. A method in which water is removed and the composition obtained by heating and kneading is formed into a sheet, pulverized and then dried; A method of mixing and stirring the resin solution and suspension prepared in the same manner as above to granulate carbon black and the resin, separating the obtained granular material, and heating to remove the remaining solvent and water; 3. Dissolve carboxylic acid such as maleic acid and fumaric acid in the above-mentioned solvent, add carbon black, mix and dry, remove the solvent to obtain carboxylic acid-impregnated carbon black, and then add resin to it. 3. dry blending method; Reactive group-containing monomer components constituting the resin to be coated and water are stirred at a high speed to prepare a suspension. After polymerization, the suspension is cooled to obtain a reactive group-containing resin from the polymer suspension. A method of adding black and kneading, reacting carbon black with a reactive group (grafting carbon black), cooling and pulverizing, and the like can be employed.

The type of resin used to coat carbon black is not particularly limited, but synthetic resins are common, and resins with benzene nuclei in the structure function more as amphoteric active surfactants. Is preferable from the viewpoint of dispersibility and dispersion stability.
Specific synthetic resins include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyphtal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene. Thermoplastic resins such as oxide, polysulfone, polyparaphenylene terephthalamide, polyamide imide, polyimide, polyamino bismaleimide, polyether sulfone, polyphenylene sulfone, polyarylate, polyether ether ketone, can be used.

  The coating amount of the resin on the carbon black is preferably 1 to 30% by weight with respect to the total amount of the carbon black and the resin. When the coating amount of the resin with respect to carbon black is less than 1% by weight, there is a possibility that only dispersibility and dispersion stability similar to those of untreated carbon black can be obtained. On the other hand, if it exceeds 30% by weight, the adhesiveness between the resins is strong, and it becomes a dumpling-like lump, which may prevent the dispersion from proceeding.

  The carbon black coated with the resin in this manner can be used as a black matrix shading material according to a conventional method, and a color filter having this black matrix as a constituent element can be prepared by a conventional method. When such carbon black is used, a black matrix having a high light shielding rate and a low surface reflectance can be achieved at a low cost.

As the organic coloring pigment (C2) that is not a black pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment can be used. As the structure, organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene can be used.
Specific examples of pigments that can be used in the present invention are shown by pigment numbers below. Note that terms such as “CI Pigment Red 2” described below mean a color index (CI).

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

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

Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 , 174,175,176,180,181,182,183,184,185,188,189,190,191,191: 1,192,193,194,195,196,197,198,199,2
00, 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.

The organic coloring pigment (C2) preferably contains any one of the following (C2-1) to (C2-4) from the viewpoints of volume resistance, light shielding properties, and dispersibility.
(C2-1) C.I. I. A red pigment selected from CI Pigment Red 177, 209, 224, and 254.
(C2-2) C.I. I. Blue pigment that is Pigment Blue 15: 6.
(C2-3) C.I. I. A yellow pigment selected from CI Pigment Yellow 83, 138, 139, 150, and 180.
(C2-4) C.I. I. A purple pigment which is CI Pigment Violet 23.

The pigments (C1) and (C2) are preferably dispersed and used so that the average particle size 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.

<Dispersant (D)>
In the present invention, it is important to finely disperse the coloring material (C) and stabilize the dispersion state, so that it is important to ensure the stability of the quality. Therefore, it is preferable that the dispersing agent (D) is included.
As the dispersant (D), 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 nitrogen-containing heterocycle-containing group 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 nitrogen-containing heterocycle-containing group such as pyridine, pyrimidine or pyrazine is particularly preferable. In the present invention, the “... ring-containing group” is usually a monovalent group obtained by removing one hydrogen atom from the “... ring”. It may be a polyvalent group obtained by removing two or more hydrogen atoms from the group.

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 include 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 (D) contains a urethane-based polymer dispersant and / or an acrylic-based polymer dispersant having a functional group in terms of adhesion and linearity.
Examples of urethane-based and acrylic polymer dispersants include Disperbyk 160 to 167, 182 series (both are urethane-based), Disperbyk 2000, 2001, etc. (both are acrylic-based) (all manufactured by Big Chemie).

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

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

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

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

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

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

Examples of the polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of the polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated poly. Examples include isoprene glycol.
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 10 compounds having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. -200 parts by weight, preferably 20-190 parts by weight, more preferably 30-180 parts by weight, 0.2-25 parts by weight of a compound having an active hydrogen and a tertiary amino group in the same molecule, preferably 0.3 -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 class amine system, 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 copolymer, a graft copolymer, or a block copolymer with an unsaturated group-containing monomer having no functional group. These copolymers can be produced by a known method.

  Examples of the unsaturated group-containing monomer having a functional group include (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acrylic acid. Tertiary amino groups such as unsaturated monomers having a carboxyl group such as leuoxyethyl hexahydrophthalic acid and acrylic acid dimer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and quaternized products thereof; Specific examples include unsaturated monomers having a quaternary ammonium base. 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. Aid
a, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), DYSogoh, WRHertler et al, Macromolecules, 20, 1473 (1987) The known methods described 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 HClO ₄ 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. ]
Further, 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 lower, 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.
Further, from the viewpoint of improving dispersion stability, the dispersant (D) may be used in combination with a pigment derivative described later.

<Photopolymerizable monomer (E)>
In the present invention, it is preferable to use a photopolymerizable monomer (E) (photopolymerizable compound) in terms of sensitivity and the like.
Examples of the photopolymerizable monomer (E) 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.
Further, (meth) acryloyloxyethyl phosphate, bis [(meth) acryloyloxyethyl] phosphate, (meth) acryloyloxyethylene glycol phosphate and the like can also be used.

<Other compounding components of photosensitive colored resin composition>
In addition to the above-mentioned components, the photosensitive colored resin composition of the present invention includes an organic solvent, a silane coupling agent, a surfactant, a thiol compound, an adhesion improver, a coating improver, a development improver, an ultraviolet absorber, An antioxidant, a pigment derivative, etc. can be mix | blended suitably.

(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.
When a pixel or black matrix of a color filter is formed by photolithography, the boiling point of the organic solvent is 100 to 200 ° C. (under a pressure of 101.25 [hPa]. Hereinafter, all of the boiling points are the same). It is preferable to select one. 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 and solidification of a coloring material 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.

(2) Silane coupling agent In order to improve the adhesion to the substrate, a silane coupling agent can be added. As the type of the silane coupling agent, various types such as epoxy-based, (meth) acrylic-based, and amino-based ones can be used alone or in admixture of two or more.
Preferred silane coupling agents include, for example, (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. 3
-Epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and ureidosilanes such as 3-ureidopropyltriethoxysilane, 3 -Isocyanate silanes such as isocyanate propyltriethoxysilane are mentioned, and particularly preferably, epoxy silane silane coupling agents are used.

(3) Surfactant As the surfactant, for example, various types such as anionic, cationic, nonionic, and amphoteric surfactants can be used. Among these, nonionic surfactants are preferably used because they are less likely to adversely affect various properties, and among them, fluorine-based and silicon-based surfactants are effective in terms of coatability.

Examples of such surfactants include TSF4460 (manufactured by GE Toshiba Silicone), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by BYK Chemie), and KP340 (Shin-Etsu Silicone). F-470, F-475, F-478, F-559 (Dainippon Ink & Chemicals), SH7PA (Toray Silicone), DS-401 (Daikin), L-77 Nippon Unicar), FC4430 (
Sumitomo 3M).
In addition, 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and a ratio.

(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.

(5) Thiols Thiols can be added for higher sensitivity and improved adhesion to the substrate.
Types of thiols include hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate , Butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, Ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), trimethylolpropane tris 3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate) Rate), trimethylolpropane tris (3-mercaptoisobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like, and various of 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) is usually 5% by weight or more, preferably 10% by weight or more, and usually 85% by weight or less, preferably based on the total solid content of the photosensitive colored resin composition of the present invention. Is 80% by weight or less. When the content of the alkali-soluble resin (A) is remarkably small, the solubility of the unexposed portion in the developer is lowered, and it becomes easy to induce development failure. On the contrary, when there is too much content of alkali-soluble resin (A), the permeability of the developing solution to an exposure part will become high, and the sharpness and adhesiveness of a pixel will deteriorate.

As described above, in the present invention, a part of the alkali-soluble resin (A) may be replaced with another binder resin.
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 15 to 60% by weight is particularly preferable. When the content of the color material (C) is too small, sufficient light shielding properties cannot be obtained. Conversely, if the content of the color material (C) is too large, sufficient image forming properties may not be obtained.

The proportion of the black pigment (C1) in the total colorant amount (C) is 20% by weight or more, preferably 35% by weight or more, and more preferably 55% by weight or more. Moreover, it is 95 weight% or less, Preferably it is 80 weight% or less, More preferably, it is 70 weight% or less. If the proportion of the black pigment (C1) is too small, sufficient light shielding properties may not be obtained. On the other hand, if the amount is too large, the volume resistance is lowered, which may affect the display performance of the panel.

  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 dispersant (D) 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 based on the color material (C). preferable. If the content of the dispersant (D) is too small, sufficient dispersibility may not be obtained. If the content is too large, the proportion of other components is relatively reduced, resulting in a decrease in color density, sensitivity, film formability, and the like. Tend to.

  When using a photopolymerizable monomer (E), 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 (E) is 1 weight% or more normally, Preferably it is 5 weight% or more.

When silane coupling is used, the content is usually 0.01% by weight or more, preferably 0.1% by weight, usually 5% by weight or less, based on the total solid content in the photosensitive colored resin composition. Preferably it is 3 weight% or less. If the amount is less than the above range, sufficient substrate adhesion cannot be obtained, while if it is too large, the storage stability may be deteriorated.
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 exhibited. There is a case.

The blending ratio of the pigment derivative is usually 0% by weight or more, preferably 1% by weight or more, and usually 10% by weight or less, preferably 5% by weight or less, based on the total solid content of the photosensitive colored resin composition of the present invention. It is preferable to do.
The content of the thiol compound is usually 0.1% by weight or more, preferably 0.3% by weight or more, more preferably 0.5% by weight or more based on the total solid content of the photosensitive colored resin composition of the present invention. The amount is usually 10% by weight or less, preferably 5% by weight or less. When the content of the thiol compound 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 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.

In the dispersion treatment, a color material (C), an organic solvent, and, if necessary, a dispersant (D) and an alkali-soluble resin (A) and / or a part of or another binder resin are used in combination. It is preferable to carry out. (Hereinafter, the mixture used for 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 (D), 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 materials 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 The color filter of the present invention can be produced by providing a black matrix on a transparent substrate and usually forming red, green, and blue pixel images, 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, red, green,
For blue, coating, heat drying, image exposure, development and heat on the resin black matrix forming surface formed on the transparent substrate or on the metal black matrix forming surface formed using a chromium compound or other light shielding metal material Each of the curing processes is performed to form a pixel image of each color.

The black matrix is formed on a transparent substrate using a light-shielding metal thin film or a photosensitive colored resin composition for 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 by a positive photoresist, ceric ammonium nitrate, perchloric acid and / or nitric acid are added to chromium. Other materials are etched using an etchant according to the material, and finally a positive photoresist is stripped with a dedicated stripper to form a black matrix. be able to.

  In this case, first, a thin film of the metal or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Next, after forming a coating film of the 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, and a black color by mixing red, green, blue, etc. as appropriate selected from organic pigments Using the photosensitive colored resin composition containing the material, a black matrix can be formed in the same manner as in the following red, green and blue pixel images.

(3) Formation of pixels (3-1) Application of photosensitive colored resin composition A photosensitive colored resin composition containing a color material of one color of red, green and blue on a transparent substrate provided with a black matrix. After coating and drying, a photomask is overlaid on the coating film, and a pixel image is formed through image exposure, development, and thermal 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 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, an IR oven, or a convection oven. Drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like.
The drying time is usually selected in a range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably 50 to 130 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes.
The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, when the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.

(3-3) Exposure Image exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive colored resin composition and irradiating an ultraviolet or visible light source through the mask pattern. At this time, if necessary, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. 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 made of the photosensitive colored resin composition with the light source described above. 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.
The development processing conditions are not particularly limited, and the development temperature is usually in the range of 10 to 50 ° C., in particular 15 to 45 ° C., particularly preferably 20 to 40 ° C., and the development methods are immersion development, spray development, brush Any of a developing method, an ultrasonic developing method and the like can be used.

(3-5) Thermosetting treatment The color filter substrate after development is subjected to thermosetting treatment. In this case, the thermosetting treatment conditions are such that the temperature is selected in the range of 100 to 280 ° C, preferably in the range of 150 to 250 ° C, and the time is selected in the range of 5 to 60 minutes. Through these series of steps, the 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 In this state, the color filter forms a transparent electrode such as ITO on the image and is used as a part of components such as a color display and a liquid crystal display device. 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. 2, first, a pattern (that is, the pixel 20 and adjacent) formed on the transparent support substrate 10 by the colored resin composition 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.

[Characteristics of black matrix]
<Taper angle>
The taper angle θ is an angle θ formed between the substrate 1 and the black matrix 2 as shown in FIG. Japanese Patent Application Laid-Open No. 2004-295084 describes that the smaller the in-plane step, the better the panel performance. However, if it is too small, fluctuations in the line width before and after firing become large, so 20 degrees or more is preferable.
The taper angle of the resin black matrix is measured by the method shown in the Examples section described later.

<Volume resistivity>
The volume resistivity required for the resin black matrix varies depending on the panel design, but is preferably 1 × 10 ¹⁰ Ω · cm or more, more preferably 1 × 10 ¹² Ω · cm or more. The volume resistivity of the resin black matrix is measured by the method shown in the Examples section described later.

<Light shielding>
The optical density required for the light shielding property of the resin black matrix varies depending on the panel design, but is usually 3 or more. If it is less than 3, the light transmitted through the resin black matrix adversely affects the contrast and chromaticity. The higher the optical density of the resin black matrix, the better. The upper limit is not particularly limited, but it is usually 6 or less. The light-shielding property of the resin black matrix is measured by the method shown in the Examples section below.

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)>

  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 (I) was obtained.
This alkali-soluble resin (I) corresponds to “alkali-soluble resin (A-2)” in the present invention.

<Synthesis Example 2: Synthesis of alkali-soluble resin (II)>
“XD1000” manufactured by Nippon Kayaku Co., Ltd. (polyglycidyl ether of dicyclopentadiene / phenol polymer, epoxy equivalent 252) 300 parts by weight, 87 parts by weight of acrylic acid, 0.2 parts by weight of p-methoxyphenol, triphenylphosphine 5 parts by weight and 255 parts by weight of propylene glycol monomethyl ether acetate were charged into a reaction vessel and stirred at 100 ° C. until the acid value became 3.0 mg-KOH / g. . Next, 145 parts by weight of tetrahydrophthalic anhydride was further added and reacted at 120 ° C. for 4 hours. The solid content was 50% by weight, the acid value was 100 mg-KOH / g, and the polystyrene equivalent weight average molecular weight (Mw) of 2600 An alkali-soluble resin (II) was obtained.

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

  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 by weight 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 condenser, 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 equivalent weight average molecular weight (Mw) of 3000 measured by GPC (III) was obtained.

<Synthesis of Dispersant-1>
50 parts by weight of polyethyleneimine having a molecular weight of about 5000 and 40 parts by weight of polycaprolactone with n = 5 were mixed with 300 parts by weight of propylene glycol monomethyl ether acetate and stirred at 150 ° C. for 3 hours in a nitrogen atmosphere. MW of the obtained Dispersant-1 was 9000.

<Creation Example-1: Creation of coated carbon black>
Carbon black was produced by a normal oil furnace method. However, ethylene bottom oil was used as the raw material oil, and coke oven gas was used for combustion. Furthermore, pure water treated with an ion exchange resin was used as the reaction stop water. 540 g of the obtained carbon black was stirred at 5,000 to 6,000 rpm for 30 minutes together with 14500 g of pure water using a homomixer to obtain a slurry. The slurry was transferred to a container with a screw type stirrer, and 600 g of toluene in which 60 g of epoxy resin “Epicoat 828” (manufactured by Japan Epoxy Resin) was dissolved was added little by little while mixing at about 1,000 rpm. In about 15 minutes, the entire amount of carbon black dispersed in water was transferred to the toluene side, and became particles of about 1 mm.
Next, after draining with a 60 mesh wire net, it was put into a vacuum dryer and dried at 70 ° C. for 7 hours to completely remove toluene and water.

<Preparation of pigment dispersion liquids 1-2>
Each light-shielding component, dispersant, dispersion aid, and solvent described in Table 1 were mixed at the stated weight ratio. After mixing, each was filled in a stainless steel container with zirconia beads (average particle size 0.5 mmφ) of 3 times the total weight, and dispersed in a paint shaker for 6 hours. After the completion of dispersion, beads and dispersion were separated by a filter to prepare pigment dispersions 1 and 2.

* 1: Coated carbon black prepared in Preparation Example-1 * 2: BYK161 manufactured by Big Chemie
* 3: Lubrizol * 4: Propylene glycol monomethyl ether acetate

<Synthesis of Photopolymerization Initiator- (I)>
<Diketone body>
Ethylcarbazole (5 g, 25.61 mmol) and o-naphthoyl chloride (5.13 g, 26.89 mmol) are dissolved in 30 ml of dichloromethane, cooled to 2 ° C. with an ice-water bath and stirred, and then AlCl ₃ (3. 41 g, 25.61 mmol) was added. After further stirring at room temperature for 3 hours, a 15 ml dichloromethane solution of crotonoyl chloride (2.81 g, 26.89 mmol) was added to the reaction solution, and AlCl ₃ (4.1 g, 30.73 mmol) was added.
And stirred for another 1 hour 30 minutes. The reaction solution was poured into 200 ml of ice water, 200 ml of dichloromethane was added, and the organic layer was separated. The collected organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure to obtain a diketone body as a white solid (10 g).

<Oxime body>
Diketone (3.00 g, 7.19 mmol), NH ₂ OH · HCl (1.09 g, 1
5.81 mmol) and sodium acetate (1.23 g, 15.08 mmol) were mixed with 30 ml of isopropanol and refluxed for 3 hours.
After completion of the reaction, the reaction mixture was concentrated, 30 ml of ethyl acetate was added to the resulting residue, washed with 30 ml of saturated aqueous sodium hydrogen carbonate solution and 30 ml of saturated brine, and dried over anhydrous magnesium sulfate. After filtration, the organic layer was concentrated under reduced pressure to obtain 3.01 g of a solid. This was purified by column chromatography to obtain 2.22 g of an oxime compound as a pale yellow solid.

<Oxime ester body>
The oxime form (2.22 g, 4.77 mmol) and acetyl chloride (1.34 g, 17.0 mmol) were added to 20 ml of dichloromethane, and the mixture was ice-cooled and triethylamine (1.77).
g, 17.5 mmol) was added dropwise and reacted for 1 hour. After confirming disappearance of the raw material by thin layer chromatography, water was added to stop the reaction. The reaction solution was washed twice with 5 ml of saturated aqueous sodium hydrogen carbonate solution and twice with 5 ml of saturated brine, and dried over anhydrous sodium sulfate. After filtration, the organic layer was concentrated under reduced pressure, and the resulting residue was purified by column chromatography (ethyl acetate / hexane = 2/1) to give 0.79 g of a light yellow solid photopolymerization initiator- (I). Got.

[Examples 1-7 and Comparative Examples 1-4]
(1) Preparation of resist (photosensitive coloring resin composition) Resins (I) to (III) synthesized in Synthesis Examples, Pigment dispersions 1 to 2, Photopolymerization initiator (I),
Using a photopolymerizable compound, a surfactant, and a solvent, each component is added so that the ratio in the solid content is the mixing ratio in Table 2, and an organic solvent is added so that the solid content is 20% by weight, A black resist was prepared by stirring and dissolving with a stirrer.

(2) Evaluation of resist The black resist prepared in (1) was applied to a glass substrate with a spin coater and dried at 90 ° C. for 1 minute on a hot plate. 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. Then, it baked at 230 degreeC for 30 minutes. When the film thickness of the resist after baking was measured with a stylus type film thickness meter (“α-step” manufactured by Tencor), it was 2.0 μm.

[Measurement of taper angle]
The cross-sectional shape of the resin black matrix line of the glass substrate (pattern 1) obtained as described above is observed with a scanning electron microscope (SEM, “S-4500” manufactured by Hitachi, Ltd.), and is in contact with the glass substrate. The taper angle of the part was measured. The results are shown in Table 2.
[Light shielding]
The black resist prepared in (1) was applied to a glass substrate with a spin coater and dried on a hot plate at 90 ° C. for 1 minute. After baking at 230 ° C. for 30 minutes, the resist film thickness was measured with a stylus-type film thickness meter, and the light shielding property was measured with a transmission densitometer Gretag Macbeth D200-II.

[Volume resistivity]
A substrate having a resin black matrix formed on the entire surface was produced in the same manner as described above on a glass substrate having a chromium vapor deposition film. Using the chromium film of this sample as a main electrode, a gold counter electrode was formed on a resin black matrix by vapor deposition. Using an ultrahigh resistance ammeter (R8340A manufactured by Advantest Corporation), the current value when the applied voltage was 1 V DC was measured and determined. The results are shown in Table 2.

* 1: Photopolymerizable compound: Dipentaerythritol hexaacrylate (DPHA)
* 2: Surfactant: “F475” manufactured by DIC
* 3: Propylene glycol monomethyl ether acetate It can be seen from Table 2 that the present invention provides a photosensitive colored resin composition having high resistance, high light-shielding properties, and maintaining a good taper angle.

DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Black matrix 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 (9)

Containing an alkali-soluble resin (A), a photopolymerization initiator (B), a coloring material (C), a dispersant (D),
The coloring material (C) contains a black pigment (C1) and an organic coloring pigment (C2) that is not a black pigment, and the content of the black pigment (C1) is an organic coloring pigment that is not a black pigment (C1) and a black pigment (C1). 20 to 95% by weight of the sum of C2),
The photosensitive colored resin composition for a color filter, wherein the alkali-soluble resin (A) contains an alkali-soluble resin (A-1) and / or an alkali-soluble resin (A-2).
<Alkali-soluble resin (A-1)>
Alkali solubility obtained by reacting a reaction product of an epoxy compound (a) represented by the following general formula (1) with an unsaturated group-containing carboxylic acid (b) with a polybasic acid and / or its anhydride (c) Resin (A-1).
<Alkali-soluble resin (A-2)>
A reaction product of an epoxy compound (a) represented by the following general formula (1) and an unsaturated group-containing carboxylic acid (b) is converted into a polyhydric alcohol (d), a polybasic acid and / or an anhydride thereof (c). Alkali-soluble resin (A-2) obtained by reacting with.

[In the general formula (1), X represents a linking group represented by the following general formula (2a), (2b) or (3). However, one or more adamantane structures are included in the molecular structure. l 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), * indicates a binding site with the glycidyloxy group in the general formula (1). )]   The photosensitive colored resin composition for a color filter according to claim 1, wherein the black pigment (C1) is carbon black coated with a resin. The organic colored pigment (C2) contains any one of the following (C2-1) to (C2-4), and the photosensitive colored resin composition for a color filter according to claim 1 or 2.
(C2-1) C.I. I. A red pigment selected from CI Pigment Red 177, 209, 224, and 254.
(C2-2) C.I. I. Blue pigment that is Pigment Blue 15: 6.
(C2-3) C.I. I. A yellow pigment selected from CI Pigment Yellow 83, 138, 139, 150, and 180.
(C2-4) C.I. I. A purple pigment which is CI Pigment Violet 23.   The content of the black pigment (C1) is 55 to 95% by weight of the sum of the black pigment (C1) and the organic coloring pigment (C2) that is not a black pigment, according to any one of claims 1 to 3. The photosensitive coloring resin composition for color filters as described in the item.   The photosensitive coloring resin composition for color filters according to any one of claims 1 to 4, wherein the dispersant (D) contains a polymer dispersant having a basic functional group.   6. The photosensitive colored resin composition for a color filter according to any one of claims 1 to 5, wherein the photopolymerization initiator (B) contains oxime ester derivatives.   A color filter having a pixel or black matrix formed using the photosensitive colored resin composition according to any one of claims 1 to 6 on a substrate.   A liquid crystal display device produced using the color filter according to claim 7.   An organic EL display produced using the color filter according to claim 7.

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