JP2013065000A - Photosensitive colored resin composition, color filter and liquid crystal display - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive colored resin composition that causes no surface defect in which unevenness occurs on the surface of a colored pattern, and has excellent productivity.SOLUTION: A photosensitive colored resin composition contains: (A) thiol compound represented by general formula (1); (B) alkali-soluble resin including (B) alkali-soluble resin and/or (B) alkali-soluble resin obtained by the reaction of a reactant of (a) epoxy compound represented by general formula (2a) and (b) α,β- unsaturated carboxylic acid, of (c) polybasic acid and/or the anhydride; (C) photoinitiator; (D) color material; and (E) photopolymerizable monomer.

Description

  The present invention relates to a photosensitive colored resin composition, a color filter, and a liquid crystal display device. Specifically, the present invention relates to a photosensitive colored resin composition that is less likely to cause development unevenness when forming a color filter and has excellent productivity. The present invention also relates to a cured product of this photosensitive colored resin composition 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 a pigment dispersion method, a photosensitive colored resin composition in which a binder resin, a photopolymerization initiator, a photopolymerizable monomer, etc. are added to a colored resin composition obtained by dispersing a pigment with a dispersant or the like. An object is coated on a glass substrate, dried, exposed using a mask, and developed to form a colored pattern, which is then heated to fix the pattern and form pixels. These steps are repeated for each color to form a color filter.

  Conventionally, photosensitive colored resin compositions having high sensitivity are used. However, even though conventional photosensitive colored resin compositions are highly sensitive, the surface of the colored pattern is often uneven. The surface defect which arises had the fault which cannot raise productivity.

  Accordingly, there has been a demand for a photosensitive colored resin composition that is free from surface defects that cause unevenness on the surface of the colored pattern and has excellent productivity.

  In addition, in the past, it is known to use a thiol compound and an alkali-soluble resin for the photosensitive colored resin composition (Patent Documents 1 to 7), but a thiol compound having a specific structure that solves the problems of the present invention. And a combination of an alkali-soluble resin having a specific structure is not known.

JP 2008-287246 A JP 2004-198542 A JP 2004-325733 A JP 2009-86563 A Japanese Patent No. 3641894 Japanese Patent No. 3641895 Japanese Patent No. 3641897

  The present invention provides a photosensitive colored resin composition that is free from surface defects that cause unevenness on the surface of a colored pattern and has excellent productivity, and a cured product, a color filter, and a liquid crystal display device using the same. This is the issue.

When the present inventors analyzed in detail the cause of unevenness on the surface of the colored pattern, it was found that the surface of the coating film was roughened during the development process, which appeared as unevenness.
As a result of intensive studies, the present inventors can suppress the roughness of the coating film surface in the development process by using a thiol compound having a specific structure and an alkali-soluble resin having a specific structure in combination, that is, The present inventors have found that the problem can be solved and have reached the present invention.

The first gist of the present invention is a composition containing a thiol compound (A), an alkali-soluble resin (B), a photopolymerization initiator (C), a coloring material (D), and a photopolymerizable monomer (E). The thiol compound (A) is represented by the following general formula (1), and the alkali-soluble resin (B) includes the following alkali-soluble resin (B ₁ ) and / or alkali-soluble resin (B ₂ ). A photosensitive colored resin composition.

[In the above general formula (1), m represents an integer from 0 to 4, and n represents an integer from 2 to 4. R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X represents an alkylene group having 1 to 8 carbon atoms which may have an ether bond and / or a branch when n is 2, and when n is 3, the following general formula (1a) or (1b When n is 4, it is represented by the following general formula (1c). ]

[In the general formula (1a), R ³ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a methylol group. ]

[In the general formula (1b), R ⁴ represents an alkylene group having 1 to 4 carbon atoms. ]

Alkali-soluble resin (B ₁ ); reaction product of epoxy compound (a) represented by the following general formula (2a) and α, β-unsaturated carboxylic acid (b), polybasic acid and / or anhydride thereof Alkali-soluble resin obtained by reacting product (c) Alkali-soluble resin (B ₂ ); epoxy compound (a) represented by the following general formula (2a) and α, β-unsaturated carboxylic acid (b) An alkali-soluble resin obtained by reacting a mixture of a reaction product with polyhydric alcohol (d) with a polybasic acid and / or anhydride (c) thereof

[In the general formula (2a), Y represents a linking group represented by the following general formula (2b) or (2c). However, the molecule contains one or more adamantane structures. p represents an integer of 2 or 3. ]

[In the above general formulas (2b) and (2c), R ^{5 to} R ⁸ and R ^{9 to} R ¹¹ each independently have an adamantyl group optionally having a substituent, a hydrogen atom, and a substituent. And an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted phenyl group. In the above general formulas (2b) and (2c), * represents a binding site with the glycidyloxy group in the general formula (2a). ]

  The second gist of the present invention resides in a cured product obtained by curing the photosensitive colored resin composition.

The third gist of the present invention resides in a color filter formed using the photosensitive colored resin composition.
The fourth gist of the present invention resides in a liquid crystal display device manufactured using the color filter.

  According to the photosensitive colored resin composition of the present invention, it is possible to form pixels in which the surface is not roughened in the development process. Therefore, according to the present invention, a color filter can be obtained with high productivity by using such a photosensitive colored resin composition.

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 or in the ink described later.
Moreover, in this invention, a weight average molecular weight means the weight average molecular weight (Mw) of polystyrene conversion 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]
The photosensitive colored resin composition of the present invention is
The thiol compound (A) represented by the general formula (1),
An alkali-soluble resin (B) comprising an alkali-soluble resin (B ₁ ) and / or an alkali-soluble resin (B ₂ ),
Photopolymerization initiator (C),
Color material (D),
And photopolymerizable monomer (E)
As an essential component, preferably further,
Dispersant (F)
As necessary, organic solvents, adhesion improvers, coatability improvers, current improvers, UV absorbers, antioxidants, silane coupling agents, surfactants, pigment derivatives, etc. Usually, each compounding component is used in a state dissolved or dispersed in an organic solvent.

<Thiol compound (A)>
The thiol compound (A) used in the present invention is represented by the following general formula (1).

[In the above general formula (1), m represents an integer from 0 to 4, and n represents an integer from 2 to 4. R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X represents an alkylene group having 1 to 8 carbon atoms which may have an ether bond and / or a branch when n is 2, and when n is 3, the following general formula (1a) or (1b When n is 4, it is represented by the following general formula (1c). ]

[In the general formula (1a), R ³ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a methylol group. ]

[In the general formula (1b), R ⁴ represents an alkylene group having 1 to 4 carbon atoms. ]

In the general formula (1), m is particularly preferably an integer of 0 to 2, and n is preferably an integer of 3 or 4. Moreover, as an alkyl group of R < ¹ > and R < ² >, a C1-C3 thing is preferable. At least one of R ¹ and R ² , for example, R ² is preferably a hydrogen atom, and in this case, R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

In the general formula (1a), ^{R 3} is preferably an alkyl group or a methylol group, having 1 to 3 carbon atoms. In the general formula (1b), R ⁴ is preferably an alkylene group having 2 to ⁴ carbon atoms.
The alkyl group of R ^{1 to} R ³ and the alkylene group of R ⁴ may be linear or branched.

  The thiol compound (A) is preferably an ester of a mercapto group-containing carboxylic acid represented by the following general formula (1d) and a polyfunctional alcohol.

[In the general formula (1d), R ¹ , R ² and m have the same meaning as in the general formula (1). ]

  Examples of the mercapto group-containing carboxylic acid represented by the general formula (1d) include 3-mercaptopropionic acid, 4-mercaptobutyric acid, 5-mercaptovaleric acid, 2-mercaptopropionic acid, 3-mercaptobutyric acid, 4-mercaptovalid. Examples include grass.

  As the polyfunctional alcohol, alkylene glycol (however, the alkylene group preferably has 2 to 8 carbon atoms, and the carbon chain thereof may be branched), diethylene glycol, glycerin, dipropylene glycol, trimethylolpropane, pentaerythritol. Can be exemplified.

  Specific examples of the thiol compound (A) used in the present invention include the following compounds.

Among the esters of the mercapto group-containing carboxylic acid represented by the general formula (1d) and the polyfunctional alcohol, examples of primary thiol compounds in which R ¹ and R ² are both hydrogen atoms include ethylene glycol bis (4 -Mercaptobutyrate), diethylene glycol bis (4-mercaptobutyrate), propanediol bis (4-mercaptobutyrate), butanediol bis (4-mercaptobutyrate), heptanediol bis (4-mercaptobutyrate), hexane Diol bis (4-mercaptobutyrate), octanediol bis (4-mercaptobutyrate), trimethylolpropane tris (4-mercaptobutyrate), pentaerythritol tetrakis (4-mercaptobutyrate), pentaerythritol tris (4- Mel Ptobutyrate), ethylene glycol bis (3-mercaptopropionate), diethylene glycol bis (3-mercaptopropionate), propanediol bis (3-mercaptopropionate), butanediol bis (3-mercaptopropionate), Hexanediol bis (3-mercaptopropionate), octanediol bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), penta Erythritol tris (3-mercaptopropionate), ethylene glycol bis (5-mercaptovalerate), diethylene glycol bis (5-mercaptovalerate), propanediol bis (5-mes Lucaptovalerate), butanediol bis (5-mercaptovalerate), hexanediol bis (5-mercaptovalerate), octanediol bis (5-mercaptovalerate), trimethylolpropane tris (5-mercaptovalerate) , Pentaerythritol tetrakis (5-mercaptovalerate), pentaerythritol tris (5-mercaptovalerate), 1,3,5-tris (4-mercaptobutyloxyethyl) -1,3,5-triazine-2,4 , 6 (1H, 3H, 5H) -trione.

As an example of a thiol compound in which at least one of R ¹ and R ² is an alkyl group among esters of a mercapto group-containing carboxylic acid represented by the general formula (1d) and a polyfunctional alcohol, ethylene glycol bis (3- Mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), propanediol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), heptanediol bis (3-mercaptobutyrate), hexanediol Bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris ( -Mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), propanediol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate) ), Hexanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate) ), Pentaerythritol tris (2-mercaptopropionate), ethylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), propanedio Bis (2-mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), heptanediol bis (2-mercaptoisobutyrate), hexanediol bis (2-mercaptoisobutyrate), octanediol bis ( 2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), pentaerythritol tris (2-mercaptoisobutyrate), diethylene glycol bis (4- Mercaptovalerate), propanediol bis (4-mercaptovalerate), butanediol bis (4-mercaptovalerate), heptanediol bis (4-mercaptovalerate), hexanediol bis ( -Mercaptovalerate), octanediol bis (4-mercaptovalerate), trimethylolpropane tris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercaptovalerate), pentaerythritol tris (4-mercaptovalerate) , Ethylene glycol bis (3-mercaptovalerate), diethylene glycol bis (3-mercaptovalerate), propanediol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), heptanediol bis (3- Mercaptovalerate), hexanediol bis (3-mercaptovalerate), octanediol bis (3-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), pe Taerythritol tetrakis (3-mercaptovalerate), pentaerythritol tris (3-mercaptovalerate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4 Examples include 6 (1H, 3H, 5H) -trione.

  Among these, ethylene glycol bis (4-mercaptobutyrate), diethylene glycol bis (4-mercaptobutyrate), propanediol bis (4-mercaptobutyrate), butanediol bis (4-mercaptobutyrate), Heptanediol bis (4-mercaptobutyrate), hexanediol bis (4-mercaptobutyrate), trimethylolpropane tris (4-mercaptobutyrate), pentaerythritol tetrakis (4-mercaptobutyrate), pentaerythritol tris (4 -Mercaptobutyrate), 1,3,5-tris (4-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, ethylene glycol bis (3 -Mercaptobuti ), Diethylene glycol bis (3-mercaptobutyrate), propanediol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), heptanediol bis (3-mercaptobutyrate), hexanediol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris ( 3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione.

  Particularly preferably, trimethylolpropane tris (4-mercaptobutyrate), pentaerythritol tetrakis (4-mercaptobutyrate), pentaerythritol tris (4-mercaptobutyrate), 1,3,5-tris (4-mercaptobutyl) Oxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), Pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione Can be mentioned.

  The thiol compound (A) is particularly preferably pentaerythritol tetrakis (3-mercaptobutyrate) represented by the following structural formula (3a) and pentaerythritol tetrakis (4-mercapto) represented by the following structural formula (3b). Butyrate) and trimethylolpropane tris (4-mercaptobutyrate) represented by the following structural formula (3c).

  These thiol compounds can be used alone or in combination of two or more.

The method for producing the thiol compound (A) is not particularly limited, but for the ester of a mercapto group-containing carboxylic acid and an alcohol, the mercapto group-containing carboxylic acid represented by the above formula (1d) and the alcohol Can be obtained by reacting according to a conventional method to form an ester. There is no restriction | limiting in particular about the conditions of ester reaction, It can select suitably from conventionally well-known reaction conditions.

<Alkali-soluble resin (B)>
The alkali-soluble resin (B) contains the following alkali-soluble resin (B ₁ ) and / or alkali-soluble resin (B ₂ ) as an essential component.

Alkali-soluble resin (B ₁ ); reaction product of epoxy compound (a) represented by the following general formula (2a) and α, β-unsaturated carboxylic acid (b), polybasic acid and / or anhydride thereof Alkali-soluble resin obtained by reacting product (c) Alkali-soluble resin (B ₂ ); epoxy compound (a) represented by the following general formula (2a) and α, β-unsaturated carboxylic acid (b) An alkali-soluble resin obtained by reacting a mixture of a reaction product with polyhydric alcohol (d) with a polybasic acid and / or anhydride (c) thereof

[In the general formula (2a), Y represents a linking group represented by the following general formula (2b) or (2c). However, the molecule contains one or more adamantane structures. p represents an integer of 2 or 3. ]

[In the above general formulas (2b) and (2c), R ^{5 to} R ⁸ and R ^{9 to} R ¹¹ each independently have an adamantyl group optionally having a substituent, a hydrogen atom, and a substituent. And an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted phenyl group. In the above general formulas (2b) and (2c), * represents a binding site with the glycidyloxy group in the general formula (2a). ]

(1) Epoxy compound (a) represented by general formula (2a)
The linking group Y in the epoxy compound (a) represented by the general formula (2a) (hereinafter sometimes referred to as “component (a)”) is represented by the general formula (2b) or (2c), All have one or more adamantane structures, preferably 2 or more and 4 or less. When the adamantane structure in the epoxy compound (a) is small, the developer resistance tends to deteriorate and the resolution tends to be inferior. In particular, the epoxy compound (a) represented by the general formula (2a) is preferably represented by the following general formula (2d).

[In General Formula (2d), R ¹⁴ and R ¹⁵ are each independently an adamantyl group which may have a substituent, a hydrogen atom, or an optionally substituted C 1-12 carbon atom. An alkyl group or a phenyl group which may have a substituent is shown. The adamantyl group represented by the general formula (2d) may have a substituent. ]

In the general formulas (2b), (2c), and (2d), the alkyl group having 1 to 12 carbon atoms of R ^{5 to} R ¹¹ , R ¹⁴ , and R ¹⁵ is preferably an alkyl group having 1 to 10 carbon atoms. It is done.

  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.

Examples of the substituent that the phenyl group of R ^{5 to} R ¹¹ and R ^{14 to} R ^{15 in} the general formulas (2b), (2c), and (2d) may have include a halogen atom, a hydroxyl group, and a carbon number of 1 to Examples include 10 alkoxyl groups, alkenyl groups having 2 to 10 carbon atoms, phenyl groups, carboxyl groups, sulfanyl groups, phosphino groups, amino groups, and nitro groups.

In addition, the adamantyl group of R ^{5 to} R ¹¹ in the general formulas (2b) and (2c), the adamantyl group shown in the general formula (2d), and the adamantyl group of R ^{14 to} R ¹⁵ in the general formula (2d) Substituents that may be present include halogen atoms, hydroxyl groups, alkoxy groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, phenyl groups, carboxyl groups, sulfanyl groups, phosphino groups, amino groups, and nitro groups. Etc.

  The molecular weight of Y represented by the general formula (2a) is preferably 200 or more and 1000 or less. If the molecular weight of Y 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 (2a) 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 generated alkali-soluble resin (B) 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 by a known method from a phenol compound represented by the following general formula (2e) or (2f).

[R ^{5 to} R ¹¹ in the general formulas (2e) and (2f) have the same meanings as those in the general formulas (2b) and (2c), respectively. ]

  For example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to a dissolved mixture of a phenol compound represented by the general formula (2e) or (2f) and an excess of epihalohydrin such as epichlorohydrin or epibromohydrin. By adding in advance or reacting at a temperature of 20 to 120 ° C. for 1 to 10 hours while adding, Y in the general formula (2a) is a linking group represented by the general formula (2b) or (2c). An epoxy compound (a) 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 or trimethylbenzylammonium chloride is added as a catalyst to a dissolved mixture of the phenol compound represented by the general formulas (2e) and (2f) and epihalohydrin, A solid or aqueous solution of an alkali metal hydroxide is added to a halohydrin etherified product of a phenol compound represented by the general formulas (2e) and (2f) obtained by reacting at 50 to 150 ° C. for 1 to 5 hours, The epoxy compound (a) represented by the general formula (2a) can also be produced by a method of reacting again at a temperature of 20 to 120 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure).

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

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 5-100 with respect to the quantity of an epihalohydrin.
% By weight, preferably 10 to 90% by weight.

(2) α, β-unsaturated carboxylic acid (b)
Examples of the α, β-unsaturated carboxylic acid (b) (hereinafter sometimes referred to as “component (b)”) include unsaturated carboxylic acids having an ethylenically unsaturated group. Specific examples include ( (Meth) acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, cinnamic acid, α-position substituted with haloalkyl group, alkoxyl group, halogen atom, nitro group, or cyano group Monocarboxylic acids such as (meth) acrylic acid; 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl adipic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2 -(Meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethylmaleic 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 as the α, β-unsaturated carboxylic acid (b) 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%. Since the remaining epoxy group tends to adversely affect the storage stability, the component (b) is usually 0.8 to 1.5 equivalents, particularly 0.9 parts per 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 tetrabasic 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. Among these, tetrahydrophthalic acid, succinic acid, or anhydrides thereof are preferable. These may be used alone or in combination of two or more.

By reacting 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 component (c), the molecular weight of the alkali-soluble resin (B ₁ ) can be increased, branching can be introduced into the molecule, and the molecular weight and viscosity can be balanced. it can. 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 (B ₁ ) may be insufficient or the adhesion to the substrate may be insufficient.

  In addition, it is preferable to replace a part of the 4-basic acid (anhydride) described above with a dibasic acid (anhydride) from the viewpoint of adjusting the viscosity and solubility of the photosensitive colored resin composition.

When (c) 4-basic acid (anhydride) and 2-basic acid (anhydride) are used in combination as components, the molar ratio is as follows: dibasic 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. Since the effect is thin and there is a possibility of reduced alkali resistance, the amount of tribasic acid (anhydride) used is usually relative to the hydroxyl group produced when component (b) is added to component (a). It is about 5-70 mol%, preferably about 10-40 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 (B ₁ ) may be insufficient, or the adhesion to the substrate may be insufficient.

In addition, (c) component adds (b) component to (a) component other than making it react with respect to the hydroxyl group produced | generated when (b) component is added to (a) component, and this is mentioned later When the polyhydric alcohol (d) to be mixed is mixed, it may be reacted with any hydroxyl group present in the mixture. The resin synthesized by this method is an alkali-soluble resin (B ₂ ).
As a method of adding the component (c) after adding the component (b) to the component (a) or mixing the polyhydric alcohol (d) described later thereto, a known method may be used. it can.
The reaction temperature 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.

(4) Polyhydric alcohol (d)
In the photosensitive colored resin composition of the present invention, the alkali-soluble resin (B) comprises a reaction product of the aforementioned component (a) and component (b), a polyhydric alcohol (d) (hereinafter referred to as “component (d)”). And the above-mentioned component (c) is allowed to react with the mixture, and the component (c) is added to any hydroxyl group present in the mixture. Resin (B ₂ ) may be included. The alkali-soluble resin (B ₂ ) is usually obtained by mixing the component (c) and the component (d) with a reaction product obtained by adding the component (b) to the component (a) and heating. In this case, the mixing order of the component (c) and the component (d) is not particularly limited.

Examples of the component (d) include one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. It is preferable that

By using the component (d), it is possible to increase the molecular weight of the alkali-soluble resin (B ₂ ), introduce branching into the molecule, and balance the molecular weight and 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.

When the amount of the component (d) used is too small, the effect is thin, and when it is too large, there is a possibility of thickening or gelation. Therefore, it is usually 0 with respect to the reaction product of the component (a) and the component (b). About 0.01 to 0.5 times by weight, preferably about 0.02 to 0.2 times by weight.

(5) an alkali-soluble resin _(B 1), _{(B 2)} acid value and molecular weight alkali-soluble resin thus obtained in _(B 1), the acid value of _{(B 2)} is usually 10 mgKOH / g or more, preferably Is 50 mg KOH / g or more. If the acid value is less than 10 mgKOH / g, developability may be insufficient. If the acid value is excessively high, there is a problem with the alkali resistance of the photosensitive colored resin composition (that is, the alkaline developer may cause roughening of the pattern surface or film loss). Is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less.

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

<Other resins>
In the photosensitive colored resin composition of the present invention, a part of the alkali-soluble resin (B) may be replaced with another binder resin such as another alkali-soluble resin (B ′). That is, for example, an alkali-soluble resin (B) and another alkali-soluble resin (B ′) may be used in combination.

Unless the performance of this invention is impaired, there is no restriction | limiting in other alkali-soluble resin (B ') which can be used together with alkali-soluble resin (B).
Examples of other alkali-soluble resins (B ′) include resins obtained by adding an α, β-unsaturated carboxylic acid to an epoxy resin and further reacting with a polybasic acid anhydride.

  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 resin 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) "Epicoat 807", "EP-4001", "EP-4002", "EP-4004 etc." manufactured by Epoxy Corporation), epoxy resins obtained by reaction of alcoholic hydroxyl groups of bisphenol F type epoxy resins with epichlorohydrin (for example, “NER-7” manufactured by Nippon Kayaku Co., Ltd. 06 ”(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” manufactured by Yakuhin, “EP-152”, “EP-154” manufactured by Yuka Shell Epoxy, “DEN-438” manufactured by Dow Chemical Co.), (o, m, p-) cresol Novolac-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.), Tris Phenolmethane type epoxy resin (for example, “EPPN-501”, “EPN-502” manufactured by Nippon Kayaku Co., Ltd., EPPN-503 "), fluorene epoxy resin (for example, cardo epoxy resin" ESF-300 "manufactured by Nippon Steel Chemical Co., Ltd.), cycloaliphatic 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. In addition, as for other alkali-soluble resin (B '), all may be used individually by 1 type, or may be used in combination of 2 or more type.

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

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

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

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

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

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

  Examples of the oxime ester derivatives include the following compounds (in the following, “Me” represents “methyl group”).

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

  Among these photopolymerization initiators, oxime ester derivatives (oxime ester compounds) are particularly preferable from the viewpoint of sensitivity.

  If necessary, the photopolymerization initiator can be mixed 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-diethyl Aminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, (p -Dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, (p-diethylaminophenyl) pyrimidine, etc. and p-dialkylaminophenyl group-containing compounds.
Of these, 4,4′-dialkylaminobenzophenone is most preferred.
A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.

<Coloring material (D)>
Coloring material (D) refers to the one coloring the photosensitive colored resin composition of the present invention. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like.

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

  Hereinafter, specific examples of pigments that can be used in the present invention are shown by pigment numbers. Note that terms such as “CI Pigment Red 2” mentioned below mean a color index (CI).

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

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

  Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Of these, C.I. I. And CI Pigment Green 7 and 36.

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

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

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

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

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

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

  Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, and titanium black.

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

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

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

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

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

  In order to increase the volume resistance value while increasing the carbon black content, carbon black coated with a resin may be used. For example, carbon black described in JP-A No. 09-73733 can be suitably used.

  As carbon black to be coated, the total content of Na and Ca is preferably 100 ppm or less. This is because the total content of Na and Ca in the carbon black coated with the resin is required to be 100 ppm or less. However, the above-mentioned content of the carbon black used for coating is more than 100 ppm. Even if it exceeds 100 ppm, it is possible to adopt a method of reducing it at the time of coating the resin. 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. Become.

  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 does not have a sufficient concentration feeling, and the film thickness of about 1 to 2 μm is light-shielding. This is because there is a risk of becoming scarce.

  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, a low surface reflectance, and a thin film thickness can be achieved at a low cost. This is presumably because the dispersibility and dispersion stability of carbon black was significantly improved compared to the resin and solvent that make up the black matrix liquid. As a result, it is difficult to disperse to 0.1 μm or less, and even if dispersed, the stability is poor and the aggregation increases with time.) It is also presumed that by coating the carbon black surface with a resin, Ca and Na can be contained in the carbon black.

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

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

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

  These pigments are preferably used in a dispersed manner so that the average particle diameter is usually 1 μm, preferably 0.5 μm or less, more preferably 0.25 μm or less.

  In the present invention, the average particle diameter of the pigment is a value obtained from the pigment particle diameter measured by dynamic light scattering DLS. For particle size measurement, a sufficiently diluted colored resin composition (usually diluted to a pigment concentration of about 0.005 to 0.2% by weight. However, if there is a concentration recommended by the measuring instrument, its concentration And measure at 25 ° C.

  Examples of dyes that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

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

  Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 etc. are mentioned.

  Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

<Photopolymerizable monomer (E)>
In the present invention, a photopolymerizable monomer (E) (photopolymerizable compound) is further used to increase 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.

  Among these, it is preferable to use an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid as the photopolymerizable monomer (E). In particular, pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate are preferable, and among them, pentaerythritol tetraacrylate is preferable.

  These photopolymerizable monomers (E) may be used alone or in combination of two or more, but the ratio of pentaerythritol tetraacrylate in the total photopolymerizable monomer (E) is 40 to 40%. It is preferable to use pentaerythritol tetraacrylate so as to be 100% by weight, particularly 50 to 100% by weight, from the viewpoint of further improving the effect of suppressing surface roughness in the development step.

<Dispersant (F)>
In the present invention, since it is important to finely disperse the coloring material (D) and stabilize the dispersion state, it is preferable to include the dispersing agent (F).

  As the dispersant (F), a polymer dispersant having a functional group is preferable, and further, from the viewpoint of dispersion stability, a carboxyl group; a phosphate group; a sulfonate group; or a base thereof; primary, secondary, or tertiary A polymeric dispersant having a functional group such as a quaternary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine, is preferred. Of these, basic polymer dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine, etc. are particularly preferred. .

  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 BASF), Disperbyk (manufactured by Big Chemie), disparon (manufactured by Enomoto Kasei), SOLPERSE (manufactured by Lubrizol), KP (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 (F) 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 and acrylic polymer dispersants include Disperbyk 160 to 166, 182 series (both urethane), Disperbyk 2000, 2001, etc. (both acrylic) (all manufactured by BYK Chemie).

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

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

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

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

  Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of these is mentioned.

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

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

  Examples of polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Is mentioned.

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

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

A compound having an active hydrogen and a tertiary amino group in the same molecule used in the present invention will be described. Examples of the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Of these, the hydrogen atom of the amino group is preferred.
The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.

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

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

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

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

  The preferred blending ratio of the raw materials for producing the urethane-based polymer dispersant is 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, and if it exceeds 200,000, the solubility is lowered and the dispersibility is poor, and at the same time, it becomes difficult to control the reaction.

  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. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida Inoue Shohei, Synthetic Organic Chemistry, 43, 300 (1985), DYSogoh, WRHertler et al, Macromolecules, 20, 1473 (1987), etc. can be employed.

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

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

  Such a block copolymer usually contains an amino group produced in the production process, but its amine value is about 1 to 100 mgKOH / g.

Here, the amine value of the dispersant such as these block copolymers is expressed by the weight of KOH equivalent to the base amount per 1 g of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
Disperse 0.5-1.5 g of the dispersant sample in a 100 mL beaker and dissolve with 50 mL of acetic acid. This solution is neutralized with a 0.1 mol / L 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. ]

  The acid value of the block copolymer depends on the presence and type of the acid group that is the basis of the acid value, but is generally preferably low, and is usually 10 mg KOH / g or less, and its weight average molecular weight (Mw) ) Is preferably in the range of 1000 to 100,000. When the weight average molecular weight of the block copolymer is less than 1000, the dispersion stability tends to decrease, and when it exceeds 100,000, the developability and resolution tend to decrease.

  Moreover, it is preferable to use a dispersing agent (F) together with the pigment derivative mentioned later from the point of a dispersion stability improvement.

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

(1) Organic solvent The photosensitive colored resin composition of the present invention usually comprises a thiol compound (A), an alkali-soluble resin (B), a photopolymerization initiator (C), a colorant (D), a photopolymerizable monomer ( E), a dispersant (F) used as necessary, and other various materials are used in a state of being dissolved or dispersed in an organic solvent.
As the organic solvent, it is preferable to select an organic solvent having a boiling point in the range of 100 to 300 ° C. More preferably, it is a solvent having a boiling point of 120 to 280 ° C.

  Examples of such organic solvents include the following.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol Monoe Ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;

Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones;

Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile:

  Commercially available solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like.

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

(1-1) Organic solvent when forming color filter pixels or black matrix by photolithography method When forming color filter pixels or black matrix by photolithography method, the organic solvent has a boiling point of 100 to 200. It is preferable to select the one in the range of ° C. (pressure of 101.25 [hPa]. Hereinafter, all the boiling points are the same). More preferably, it has a boiling point of 120 to 170 ° C.
Of the above organic solvents, glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension and the like, and relatively high solubility of the constituent components in the composition.

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

  It is also preferable to use an organic solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as “high boiling point solvent”). By using such a high boiling point solvent in combination, the colored resin composition becomes difficult to dry, but it has an effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. That is, for example, there is an effect of preventing the occurrence of a foreign matter defect due to precipitation 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.

(1-2) Organic solvent for forming color filter pixels by inkjet method When forming a color filter pixel by inkjet method, the organic solvent has a boiling point of usually 130 ° C to 300 ° C, preferably A temperature of 150 ° C. or higher and 280 ° C. or lower is appropriate. If the boiling point of the organic solvent is too low, the uniformity of the resulting coating film tends to be poor. Conversely, if the boiling point of the solvent is too high, the effect of inhibiting drying of the colored resin composition is high, as will be described later, but a large amount of residual solvent is present in the coating film even after heat firing, resulting in quality defects. In some cases, the drying time in vacuum drying or the like becomes longer, causing problems such as an increase in tact time.
The vapor pressure of the organic solvent is usually 10 mmHg or less, preferably 5 mmHg or less, more preferably 1 mmHg or less, from the viewpoint of the uniformity of the resulting coating film.

  In the production of color filters by the ink jet method, the ink emitted from the nozzle is very fine, from several to several tens of pL, so the organic solvent evaporates before landing on the periphery of the nozzle opening or in the pixel bank. There is a tendency to concentrate and dry. In order to avoid this, it is preferable that the organic solvent contained in the colored resin composition has a higher boiling point. Specifically, the colored resin composition preferably contains a solvent having a boiling point of 180 ° C. or higher. More preferably, the colored resin composition contains an organic solvent having a boiling point of 200 ° C. or higher, particularly preferably a boiling point of 220 ° C. or higher. The high boiling point solvent having a boiling point of 180 ° C. or higher is preferably 50% by weight or more, more preferably 70% by weight or more in the total organic solvent contained in the ink and / or color filter colored resin composition described later. Preferably, 90% by weight or more is most preferable. When the ratio of the high boiling point solvent having a boiling point of 180 ° C. or higher in the total organic solvent is less than 50% by weight, the effect of preventing evaporation of the solvent from the droplets may not be sufficiently exhibited.

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

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

  On the other hand, when the organic solvent contains alcohols, the ejection stability in the ink jet method may deteriorate. Therefore, the alcohol is preferably 20% by weight or less in the total organic solvent, more preferably 10% by weight or less, and particularly preferably 5% by weight or less.

(2) Adhesion improver An adhesion improver may be included in order to improve adhesion to the substrate. As the adhesion improver, a silane coupling agent, a phosphoric acid group-containing compound and the like are preferable.

  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. Epoxyglycans such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and ureidosilanes such as 3-ureidopropyltriethoxysilane, Although isocyanate silanes, such as 3-isocyanate propyl triethoxysilane, are mentioned, Especially preferably, the silane coupling agent of epoxy silanes is mentioned.

  As the phosphoric acid group-containing compound, (meth) acryloyloxy group-containing phosphates are preferable, and those represented by the following general formulas (5a), (5b), and (5c) are preferable.

[In the above general formulas (5a), (5b) and (5c), R ⁵¹ represents a hydrogen atom or a methyl group, p and p ′ are integers of 1 to 10, and q is 1, 2 or 3. ]

(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 Co., Ltd.), FC4430 (Sumitomo 3M Co., Ltd.) and the like.

  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.

<Ingredient compounding amount in photosensitive colored resin composition>
The content of the thiol compound (A) is usually 0.1% by weight or more, preferably 0.3% by weight or more, more preferably 0.5% by weight based on the total solid content of the photosensitive colored resin composition of the present invention. It is not less than the weight and is usually not more than 10% by weight, preferably not more than 5% by weight. If the content of the thiol compound (A) is too small, the effect of suppressing the roughness of the pattern surface in the development process may not be sufficiently obtained. On the other hand, if the content is too large, the storage stability may be deteriorated.

  The content of the alkali-soluble resin (B) 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 (B) is remarkably small, the solubility of the unexposed portion in the developer is lowered, and it becomes easy to induce development failure. On the other hand, when the content of the alkali-soluble resin (B) is too large, the permeability of the developer into the exposed area tends to be high, and the sharpness and adhesion of the pixel may be lowered.

As described above, in the present invention, a part of the alkali-soluble resin (B) may be replaced with another binder resin such as another alkali-soluble resin (B ′).
In this case, in the photosensitive colored resin composition of the present invention, the alkali-soluble resin (B) contained in the above proportion is usually replaced by 70% by weight or less, preferably 50% by weight or less. The ratio of the other binder resin to the total of the soluble resin (B) and other binder resin such as other alkali-soluble resin (B ′) is 70% by weight or less, preferably 50% by weight or less. It uses together with soluble resin (B).

  The content of the photopolymerization initiator (C) 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 (C) 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 (C), 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 (C). It is preferable to use in proportion.

  If the blending ratio of the photopolymerization initiator component composed of the photopolymerization initiator (C) and the accelerator 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 coloring material (D) can be normally selected in the range of 1 to 70 weight% with respect to the total solid content in the photosensitive colored resin composition. In this range, 10 to 70% by weight is more preferable, and 20 to 60% by weight is particularly preferable. If the content of the color material (D) is too small, the film thickness with respect to the color density becomes too large, which may adversely affect the gap control during liquid crystal cell formation. Conversely, if the content of the color material (D) is too large, sufficient image formability may not be obtained.

  In the photosensitive colored resin composition, the amount of the alkali-soluble resin (B) with respect to the color material (D) 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 (B) with respect to the color material (D) is too low, the solubility of the unexposed portion in the developing solution is lowered, and it is easy to induce development failure. It becomes difficult to obtain.

  The content of the photopolymerizable monomer (E) is usually 90% by weight or less, preferably 80% by weight or less, based on the total solid content of the photosensitive colored resin composition. When 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 with respect to the total solid of a photosensitive coloring resin composition, Preferably it is 5 weight% or more.

  The content of the dispersant (F) 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 (F) is usually 5% by weight or more, particularly 10% by weight or more, and usually 200% by weight or less, particularly 80% by weight or less with respect to the coloring material (D). preferable. If the content of the dispersant (F) 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.

  In particular, as the dispersant (F), it is preferable to use a polymer dispersant and a pigment derivative in combination. In this case, the blending ratio of the pigment derivative is based on the total solid content of the photosensitive colored resin composition of the present invention. Thus, it is usually 1% by weight or more, usually 10% by weight or less, preferably 5% by weight or less.

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

  The photosensitive colored resin composition of the present invention is prepared using the above-mentioned organic solvent so that the solid content concentration is usually 5 to 50% by weight, preferably 10 to 30% by weight. .

<Method for producing photosensitive colored resin composition>
The photosensitive colored resin composition of the present invention (hereinafter sometimes referred to as “resist”) is produced according to a conventional method.
Usually, it is preferable to disperse the color material (D) 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 (D) 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 (D), it contributes to the improvement of a light-shielding capability.

  In the dispersion treatment, a color material (D), an organic solvent, and, if necessary, a dispersant (F), and a system in which a part or all of the alkali-soluble resin (B) and / or other binder resin are used in combination. It is preferable to carry out. (Hereinafter, the mixture subjected to the dispersion treatment and the composition obtained by the treatment may be referred to as “ink”.) In particular, when a polymer dispersant is used as the dispersant (F), 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,
Due to the heat generated during the dispersion process, highly reactive components may be denatured. Therefore, it is preferable to perform the dispersion treatment in a system containing the above-described components.

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

  The black matrix is formed on a transparent substrate using a light-shielding metal thin film or a photosensitive colored resin composition for resin black matrix. As the light-shielding metal material, chromium compounds such as metal chromium, chromium oxide and chromium nitride, nickel and tungsten alloy, etc. are used, and these may be laminated in a plurality of layers.

  These metal light shielding films are generally formed by a sputtering method, and after forming a desired pattern in a film shape with a positive photoresist, ceric ammonium nitrate, perchloric acid and / or nitric acid are added to chromium. Other materials are etched using an etching solution according to the material, and finally a positive photoresist is stripped with a special stripping agent to form a black matrix. be able to.

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

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

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

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

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

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

  The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate. However, when the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature.

(3-3) Exposure Image exposure is performed by overlaying a negative mask pattern on the coating film of the photosensitive colored resin composition and irradiating a UV or visible light source through this mask pattern. At this time, if necessary, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film in order to prevent a decrease in sensitivity of the photopolymerizable layer due to oxygen. The light source used for said image exposure is not specifically limited. Examples of the light source include a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, and a fluorescent lamp, an argon ion laser, a YAG laser, Examples include an excimer laser, a nitrogen laser, a helium cadmium laser, and a laser light source such as a semiconductor laser. An optical filter can also be used when used by irradiating light of a specific wavelength.

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

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

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

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

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

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

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

[Liquid Crystal Display]
The liquid crystal display device of the present invention is manufactured using the above-described color filter of the present invention.

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

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

  The gap for bonding to the counter substrate varies depending on the use of the liquid crystal display device, but is usually selected in the range of 2 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]
An organic EL display can be 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. 1, 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.

  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 1-1: Synthesis of alkali-soluble resin (BI)>

  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 became transparent, it was diluted with methoxybutyl acetate and prepared to have a solid content of 50% by weight. The acid value was 131 mgKOH / g, and the polystyrene-soluble weight average molecular weight (Mw) of 2600 was measured with GPC. Resin (BI) was obtained.
The alkali-soluble resin (BI) corresponds to the “alkali-soluble resin (B ₂ )” in the present invention.

<Synthesis Example 1-2: Synthesis of alkali-soluble resin (B-II)>

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

  25 parts of the above epoxy acrylate solution, 0.76 parts by weight of trimethylolpropane (TMP), 3.7 parts by weight of biphenyltetracarboxylic dianhydride (BPDA), and 3.9 parts by weight of tetrahydrophthalic anhydride (THPA) Was put into a flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature was slowly raised to 105 ° C. while stirring to react.

  When the resin solution becomes transparent, it is diluted with methoxybutyl acetate, prepared to have a solid content of 50% by weight, an acid value of 131 mg KOH / g, an alkali having a polystyrene equivalent weight average molecular weight (Mw) of 3000 measured by GPC A soluble resin (B-II) was obtained.

<Synthesis Example 2: Preparation of coated carbon black>
Carbon black was produced by a normal oil furnace method. However, ethylene bottom oil with a small amount of Na, Ca, S 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.

<Synthesis Example 3: Preparation of coated carbon black ink (DI)>
To 20 parts by weight of the coated carbon black prepared in Synthesis Example 2, 4.5 parts by weight of EFKA4046 (manufactured by BASF) as a dispersant and 1 part by weight of S12000 (manufactured by Lubrizol) as a pigment derivative are added, and the solid content concentration Of propylene glycol monomethyl ether acetate (PGMEA) was added so as to be 25% by weight.
This was sufficiently stirred with a stirrer and premixed. Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 6 hours. As the beads, 0.5 mmφ zirconia beads were used, and the same weight as the dispersion was added. After the completion of dispersion, the beads and the dispersion were separated by a filter to prepare ink (DI).

<Synthesis Example 4: Synthesis of Photopolymerization Initiator (CI)>
<Diketone body>
Ethylcarbazole (5 g, 25.61 mmol) and o-toluoyl chloride (4.15 g, 26.89 mmol) are dissolved in 50 ml of dichloromethane, cooled to 2 ° C. with an ice-water bath and stirred, and then added with AlCl ₃ (3. 41 g, 25.61 mmol) was added. The mixture was further stirred at that temperature for 3 hours. To the reaction solution, a 15 ml dichloromethane solution of crotonoyl chloride (2.81 g, 26.89 mmol) was added, AlCl ₃ (4.1 g, 30.73 mmol) was added, and the mixture was further stirred for 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 white solid (9.13 g).

<Oxime body>
A diketone body (2.74 g, 7.19 mmol), NH ₂ OH · HCl (1.09 g, 15.81 mmol), and sodium acetate (1.23 g, 15.08 mmol) were mixed with 30 ml of isopropanol, and heated under reflux for 3 hours. did.
After completion of the reaction, the reaction mixture was concentrated, 50 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 2.77 g of a solid. This was purified by column chromatography to obtain 2.04 g of an oxime pale yellow solid.

<Oxime ester body>
The oxime (2.00 g, 4.65 mmol) and acetyl chloride (1.30 g, 16.5 mmol) were added to 30 ml of dichloromethane, and ice-cooled to 2 ° C., and triethylamine (1.72 g, 17.0 mmol) was added dropwise. The reaction was continued 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 10 ml of saturated aqueous sodium hydrogen carbonate solution and twice with 10 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 a photopolymerization initiator (CI) as 1.29 g of a pale yellow solid. )

The measured value and structural formula in ¹ H-NMR of the obtained photopolymerization initiator (CI) are shown below.
¹ H NMR (CDCl ₃ ): σ 1.21 (d, 3H), 1.51 (t, 3H), 1.87 (s, 3H), 2.24 (s, 3H), 2.34 (s, 3H), 2.38 (s, 3H), 3.22-3.38 (m, 2H), 4.44 (q, 2H), 4.91 (bs, 1H), 7.29-7.50. (M, 6H), 7.99 (dd, 1H), 8.11 (dd, 1H), 8.50 (d, 1H), 8.58 (d, 1H)

[Examples 1-8 and Comparative Examples 1-3]
(1) Preparation of resist (photosensitive coloring resin composition) Using the ink (D-1) prepared in Synthesis Example 3, each component was added so that the ratio in the solid content was the following ratio as the solid content. Further, an organic solvent (propylene glycol monomethyl ether acetate (PGMEA)) was added so that the solid content concentration was 14.5% by weight, and the mixture was stirred and dissolved with a stirrer to prepare a black resist.

<Formulation>
Ink prepared in Synthesis Example 3 (D-I): 61.2% by weight
Alkali-soluble resins (BI) and (B-II) prepared in Synthesis Examples 1-1 and 1-2:
Amounts listed in Table 1 Photopolymerizable monomer: Amounts listed in Table 1 EI: Dipentaerythritol hexaacrylate E-II: Pentaerythritol tetraacrylate Photopolymerization initiator (CI) synthesized in Synthesis Example 4: 5.3% by weight
Adhesion improver (PM-21 (Nippon Kayaku Co., Ltd.)): 0.5% by weight
Surfactant (F-475 (manufactured by Dainippon Ink and Chemicals)): 0.1% by weight
Thiol compound: Amount described in Table 1 AI: Pentaerythritol tetrakis (4-mercaptobutyrate)
A-II: Trimethylolpropane tris (4-mercaptobutyrate)
A-III: 1,4-butanediol bis (4′-mercaptobutyrate)
A-IV: “Karenzu MT” manufactured by Showa Denko
PE1 "(pentaerythritol tetrakis (3-mercaptobutyrate))
AV: “Karenz MT NR1” (1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) manufactured by Showa Denko KK -Trion)
A-VI: “Karenzu MT” manufactured by Showa Denko
BD1 "(1,4-butanediol bis (3'-mercaptobutyrate))
A-VII: 1,6-hexanedithiol

(2) Evaluation of resist
The black resist prepared in (1) was applied to a glass substrate with a spin coater and dried on a hot plate at 80 ° C. for 2.5 minutes. The film thickness of the resist after drying was measured with a stylus-type film thickness meter (“α-step” manufactured by Tencor), and it was 1.7 μm. Next, this sample was image-exposed with a high-pressure mercury lamp through a mask at an exposure amount of 50 mJ. Then, a resist pattern was obtained by spray development using a KOH aqueous solution having a concentration of 0.05% by weight at a temperature of 23 ° C.
The surface roughness Sa [nm] of the resist pattern before and after development is measured by a non-contact surface / layer cross-sectional shape measurement system (“Vert Scan” manufactured by Ryoka System Co., Ltd.) Was evaluated by the difference between Sa after development and before development: ΔSa. The results are shown in Table 1.

From Table 1, according to the photosensitive colored resin composition of the present invention, a difference ΔSa between the surface roughness Sa after development and before development is small, that is, a pixel in which the surface is not roughened in the development process can be formed. I understand that I can do it.
On the other hand, Comparative Example 1 containing no thiol compound (A), Comparative Example 2 using a thiol compound other than the thiol compound (A) defined in the present invention, an alkali-soluble resin (B defined in the present invention) In Comparative Example 3 using an alkali-soluble resin other than (), the difference ΔSa between the surface roughness Sa after development and before development is large.

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

Claims (9)

A composition containing a thiol compound (A), an alkali-soluble resin (B), a photopolymerization initiator (C), a coloring material (D), and a photopolymerizable monomer (E),
The thiol compound (A) is represented by the following general formula (1),
The photosensitive colored resin composition, wherein the alkali-soluble resin (B) contains the following alkali-soluble resin (B ₁ ) and / or alkali-soluble resin (B ₂ ).

[In the above general formula (1), m represents an integer from 0 to 4, and n represents an integer from 2 to 4. R ¹ and R ² each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. X represents an alkylene group having 1 to 8 carbon atoms which may have an ether bond and / or a branch when n is 2, and when n is 3, the following general formula (1a) or (1b When n is 4, it is represented by the following general formula (1c). ]

[In the general formula (1a), R ³ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a methylol group. ]

[In the general formula (1b), R ⁴ represents an alkylene group having 1 to 4 carbon atoms. ]

Alkali-soluble resin (B ₁ ); reaction product of epoxy compound (a) represented by the following general formula (2a) and α, β-unsaturated carboxylic acid (b), polybasic acid and / or anhydride thereof Alkali-soluble resin obtained by reacting product (c) Alkali-soluble resin (B ₂ ); epoxy compound (a) represented by the following general formula (2a) and α, β-unsaturated carboxylic acid (b) An alkali-soluble resin obtained by reacting a mixture of a reaction product with polyhydric alcohol (d) with a polybasic acid and / or anhydride (c) thereof

[In the general formula (2a), Y represents a linking group represented by the following general formula (2b) or (2c). However, the molecule contains one or more adamantane structures. p represents an integer of 2 or 3. ]

[In the above general formulas (2b) and (2c), R ^{5 to} R ⁸ and R ^{9 to} R ¹¹ each independently have an adamantyl group optionally having a substituent, a hydrogen atom, and a substituent. And an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted phenyl group. In the above general formulas (2b) and (2c), * represents a binding site with the glycidyloxy group in the general formula (2a). ] Thiol compounds (A), in formula (1), n represents an integer of 3 or 4, and R ² is a hydrogen atom, a photosensitive colored resin composition of claim 1. The photosensitive coloring resin composition of Claim 2 whose thiol compound (A) is a compound represented by either of following structural formula (3a), (3b), and (3c).

  The photosensitive colored resin according to any one of claims 1 to 3, wherein the photopolymerizable monomer (E) contains pentaerythritol tetraacrylate in a ratio of 40 to 100% by weight in the total photopolymerizable monomer (E). Composition.   The photosensitive coloring resin composition in any one of Claims 1 thru | or 4 whose photoinitiator (C) is an oxime ester type compound.   Furthermore, the photosensitive colored resin composition in any one of Claim 1 thru | or 5 containing a basic polymer dispersing agent.   Hardened | cured material formed by hardening the photosensitive colored resin composition in any one of Claims 1 thru | or 6.   A color filter formed using the photosensitive colored resin composition according to claim 1.   A liquid crystal display device produced using the color filter according to claim 8.

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