JP5707186B2 - Coloring composition for color filter, color filter, and color liquid crystal display element - Google Patents

Description

  The present invention relates to a coloring composition for a color filter, a color filter, and a color liquid crystal display element, and more specifically, a color used for a transmissive or reflective color liquid crystal display element, a color imaging tube element, an organic EL display element, and the like. The present invention relates to a colored composition used for forming a colored layer useful for a filter, a color filter including a colored layer formed using the colored composition, and a color liquid crystal display element including the color filter.

  In producing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. There is known a method (Patent Documents 1 and 2) for obtaining pixels of each color by irradiation (hereinafter referred to as “exposure”) and development. In addition, a method for obtaining pixels of each color by an ink jet method using a pigment-dispersed colored resin composition is also known (Patent Document 3).

  By the way, color liquid crystal display elements such as televisions and monitors are required to have high brightness and an expanded color reproduction area. Therefore, the color filters constituting the color liquid crystal display elements have recently been increasing in light transmittance. What has high color purity is required. In response to such a demand, use of a new pigment such as polyhalogenated zinc phthalocyanine has been proposed for green pixels (Patent Document 4).

JP-A-2-144502 JP-A-3-53201 JP 2000-310706 A JP 2007-284589 A

However, the conventional pigment-dispersed coloring composition has a limit in increasing the luminance and color purity of the green pixel. Against the background as described above, there is a strong demand for the development of a color filter coloring composition that can achieve higher brightness and higher color purity of the green pixel than the conventional pigment dispersion type coloring composition.
Therefore, the subject of this invention is providing the coloring composition for color filters which can implement | achieve the high brightness | luminance and high color purity of a green pixel exceeding the conventional pigment dispersion type coloring composition. Furthermore, the subject of this invention is providing the color liquid crystal display element which comprises a color filter provided with the green pixel formed using the said coloring composition, and the said color filter.

  In view of this situation, the present inventors have conducted extensive research and found that C.I. I. The present invention has been completed by finding that the above-mentioned problems can be solved by using Pigment Green 58 and a specific yellow dye.

That is, the present invention
(A) At least one selected from the group consisting of a compound represented by the following formula (1), a dimer formed from the compound, and a salt thereof (hereinafter collectively referred to as “specific yellow dye”) C.) and C.I. I. A colorant comprising CI Pigment Green 58;
(B) It provides the coloring composition for color filters characterized by containing the binder resin whose acid value is 85-300 mgKOH / g, and (C) polyfunctional monomer.

[In Formula (1),
Z represents a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxy group, a carboxyl group, a carbamoyl group, a sulfo group, a sulfamoyl group, and N. A phenyl group having one or two substituents selected from the group consisting of a substituted sulfamoyl group, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, carbon A naphthyl group having 1 to 3 substituents selected from the group consisting of an alkoxy group of formulas 1 to 8, a hydroxy group, a carboxyl group, a carbamoyl group, a sulfo group, a sulfamoyl group and an N-substituted sulfamoyl group. .
R ¹ represents a hydrogen atom, a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group or a trifluoromethyl group.
R ² represents a hydrogen atom, a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, a cyano group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, a sulfo group or an amino group.
R ³ is a hydrogen atom, an optionally substituted linear, branched or cyclic saturated hydrocarbon group having 1 to 10 carbon atoms, and an optionally substituted carbon atom having 6 to 30 carbon atoms. Aryl group, optionally substituted aralkyl group having 7 to 20 carbon atoms, optionally substituted heterocyclic group having 3 to 20 carbon atoms, cyano group, carbamoyl group, N-substituted A carbamoyl group, an optionally substituted alkyloxycarbonyl group having 2 to 20 carbon atoms, an optionally substituted aryloxycarbonyl group having 7 to 30 carbon atoms, and a substituent. An acyl group having 2 to 20 carbon atoms, an aliphatic sulfonyl group having 1 to 30 carbon atoms which may have a substituent, or an arylsulfonyl group having 6 to 30 carbon atoms which may have a substituent. Represent. ]

  The present invention also provides a color filter comprising a green pixel formed using the colored composition, and a color liquid crystal display device comprising the color filter.

If the coloring composition of the present invention is used, a color filter having green pixels with extremely high luminance and color purity can be obtained.
Therefore, the colored composition of the present invention is extremely suitable for the production of various color filters including color filters for color liquid crystal display elements, color filters for color separation of solid-state imaging elements, and color filters for organic EL display elements. Can be used for

Hereinafter, the present invention will be described in detail.
Color Filter Color Composition Hereinafter, the components of the color filter color composition of the present invention (hereinafter simply referred to as “color composition”) will be described.

-(A) Colorant-
The coloring composition of the present invention includes C.I. I. Pigment Green 58 and a specific yellow dye, that is, a compound represented by the above formula (1), a dimer formed from the compound, and at least one selected from the group consisting of salts thereof And C. I. Pigment Green 58 is brominated chlorinated zinc phthalocyanine.

  In formula (1), the hydrocarbon group having 1 to 12 carbon atoms in Z may be linear, branched or cyclic, but is preferably a saturated hydrocarbon group. The carbon number of the hydrocarbon group includes all the carbon numbers of the substituents, and the number is usually 1 to 12, preferably 2 to 11. Examples of the hydrocarbon group include an n-octyl group, a methylhexyl group (such as 1,5-dimethylhexyl group), an ethylhexyl group (such as 2-ethylhexyl group), a cyclooctyl group, and a methylcyclohexyl group (2, 2- A dimethylcyclohexyl group) and a cyclohexylalkyl group. The hydrogen atom contained in the hydrocarbon group may be substituted with an alkoxy group having 1 to 8 carbon atoms or a carboxyl group. Examples of the hydrocarbon group having a substituent include an alkoxypropyl group (such as 3- (2'-ethylhexyloxy) propyl group) and an 8-carboxyoctyl group.

Examples of the alkoxy group having 1 to 8 carbon atoms in Z include a methoxy group, an ethoxy group, an isopropoxy group, an n-propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. It is done.
Examples of the halogen atom in Z include a fluorine atom, a bromine atom, a chlorine atom and an iodine atom.

The N-substituted sulfamoyl group in Z is represented by —SO ₂ N (R ⁴ ) R ⁵ .
R ⁴ and R ⁵ are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or an aryl having 6 to 20 carbon atoms which may have a substituent. A group, an optionally substituted aralkyl group having 7 to 20 carbon atoms or an optionally substituted acyl group having 2 to 15 carbon atoms (provided that R ⁴ and R ⁵ are simultaneously It cannot be a hydrogen atom).
The saturated hydrocarbon group having 1 to 16 carbon atoms in R ⁴ and R ⁵ may be linear, branched or cyclic. The carbon number of the saturated hydrocarbon group does not include the carbon number of the substituent, and the number thereof is usually 1 to 16, preferably 6 to 10. Examples of the saturated hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a methylbutyl group (1,1,3,3). -Tetramethylbutyl group etc.), methylhexyl group (1,5-dimethylhexyl group etc.), ethylhexyl group (2-ethylhexyl group etc.), cyclopentyl group, cyclohexyl group, methylcyclohexyl group (2-methylcyclohexyl group etc.) and A cyclohexyl alkyl group etc. are mentioned. The hydrogen atom contained in the saturated hydrocarbon group may be substituted with an alkoxy group having 1 to 8 carbon atoms or a carboxyl group. Examples of the saturated hydrocarbon group having a substituent include a propoxypropyl group (such as 3- (isopropoxy) propyl group), a 2-carboxyethyl group, a 3-carboxypropyl group, and a 4-carboxybutyl group.

The aryl group having 6 to 20 carbon atoms in R ⁴ and R ⁵ may have a substituent such as an aliphatic hydrocarbon group or a hydroxy group. Carbon number of an aryl group contains all the carbon number of a substituent, and the number is 6-20 normally, Preferably it is 6-10. Examples of the aryl group include a phenyl group, and examples of the substituted aryl group include a carboxyphenyl group (such as a 2-carboxyphenyl group and a 2,4-dicarboxyphenyl group) and a hydroxyphenyl group (such as a 4-hydroxyphenyl group). ), Trifluoromethylphenyl group (such as 4-trifluoromethylphenyl group) and methoxyphenyl group (4-methoxyphenyl group).
The alkyl part of the aralkyl group having 7 to 20 carbon atoms in R ⁴ and R ⁵ may be either linear or branched. The carbon number of the aralkyl group is usually 7 to 20, preferably 7 to 10. Aralkyl includes benzyl group, phenylethyl group (2-phenylethyl group, 2- (4-hydroxyphenyl) ethyl group, etc.), phenylethylene group (2-phenylethylene group, etc.), phenylpropyl group (1-methyl- And phenylalkyl groups such as 3-phenylpropyl group and phenylbutyl group (3-amino-1-phenylbutyl group).
The acyl group having 2 to 15 carbon atoms in R ⁴ and R ⁵ may be unsubstituted or may have a substituent such as an aliphatic hydrocarbon group, an alkoxy group, or a carboxyl group. The carbon number of the acyl group includes all carbon atoms of the substituent, and the number is usually 2 to 15, preferably 6 to 10. As the acyl group, for example, acetyl group, benzoyl group, methoxybenzoyl group (p-methoxybenzoyl group etc.), carboxyacetyl group, 2-carboxypropionyl group, 3-carboxypropionyl group, 2-carboxybutyryl group, 3-carboxy Examples include butyryl group and 4-carboxybutyryl group.

  Z in the formula (1) is preferably a substituted phenyl group, and any of the above substituents can be selected, but a sulfo group and an N-substituted sulfamoyl group are preferred from the viewpoint of high solubility in a solvent. . In addition, the position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different.

R ¹ represents a hydrogen atom, a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group or a trifluoromethyl group. Especially, a C1-C10 hydrocarbon group which is linear, branched or cyclic is preferable.
The carbon number of the hydrocarbon group having 1 to 10 carbon atoms in R ¹ does not include the carbon number of the substituent. The carbon number is preferably 2 to 8, more preferably 2 to 4. The hydrocarbon group is preferably a saturated hydrocarbon group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopentyl group. And a cyclohexyl group.

R ² represents a hydrogen atom, a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, a cyano group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, a sulfo group or an amino group. Among these, a hydrocarbon group having 1 to 10 carbon atoms, a cyano group, a carbamoyl group or an amino group is preferable, and a cyano group is more preferable.

Examples of the N-substituted carbamoyl group for R ² include —CON (R ⁶ ) R ⁷ .
R ⁶ and R ⁷ are each independently a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 10 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. And a C 7-20 aralkyl group which may have a group or a substituent, or a C 2-10 acyl group which may have a substituent.
The explanation and specific examples of the saturated hydrocarbon group, aryl group, aralkyl group and acyl group for R ⁶ and R ⁷ are the same as those for R ⁴ and R ⁵ described above. However, the acyl group may have a halogen atom. Examples of the acyl group having a halogen atom include a bromobenzoyl group (such as a p-bromobenzoyl group).

Examples of the linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms for R ² include the same groups as the hydrocarbon groups for R ¹ described above.
As the amino group in R ² , an aliphatic amino group, an arylamino group, an acylamino group, a carbamoylamino group, a sulfamoylamino group, an aliphatic oxycarbonylamino group, an aryloxycarbonylamino group, an aliphatic sulfonylamino group, or , Arylsulfonylamino group and the like, each of which may further have a substituent.

R ³ is a hydrogen atom, a linear, branched or cyclic saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and a carbon number 6 to 30 which may have a substituent. Aryl group, optionally substituted aralkyl group having 7 to 20 carbon atoms, optionally substituted heterocyclic group having 3 to 20 carbon atoms, cyano group, carbamoyl group, N-substituted A carbamoyl group, an optionally substituted alkyloxycarbonyl group having 2 to 20 carbon atoms, an optionally substituted aryloxycarbonyl group having 7 to 30 carbon atoms, and a substituent. An acyl group having 2 to 20 carbon atoms, an aliphatic sulfonyl group having 1 to 30 carbon atoms which may have a substituent, or an arylsulfonyl group having 6 to 30 carbon atoms which may have a substituent. Represent.

Examples of the saturated hydrocarbon group for R ³ include the same groups as the hydrocarbon groups for R ¹ described above.
The carbon number of the aryl group in R ³ includes the carbon number of the substituent, and the number is usually 6 to 30, preferably 6 to 20, and more preferably 6 to 16. Specific examples of the aryl group include a phenyl group, and the substituted aryl group includes a 4-nitrophenyl group, 2-nitrophenyl group, 2-chlorophenyl group, 2,4-dichlorophenyl group, 2,4- Examples include dimethylphenyl group, 2-methylphenyl group, 4-methoxyphenyl group, 2-methoxyphenyl group, 2-methoxycarbonyl-4-nitrophenyl group and the like.
The aralkyl group in R ³ may be either linear or branched, and the carbon number of the aralkyl group does not include the carbon number of the substituent, and the number is preferably 7 to 10. Specific examples of aralkyl include phenylalkyl groups such as benzyl group, phenylpropyl group and phenylbutyl group. Specific examples of substituted aralkyl groups include 1-methyl-3-phenylpropyl group, 3-amino- Examples thereof include 1-phenylbutyl group.

The heterocyclic group having 3 to 20 carbon atoms in R ³ may be saturated or unsaturated. The carbon number of the heterocyclic group includes the carbon number of the substituent, and the number is preferably 3 to 20, more preferably 5 to 15. Specific examples of the heterocyclic group include pyrazole group, 1,2,4-triazole group, isothiazole group, benzoisothiazole group, thiazole group, benzothiazole group, oxazole group and 1,2,4-thiadiazole group. Etc. The heterocyclic group may further have a substituent.
The N-substituted carbamoyl group for R ³ is the same as the N-substituted carbamoyl group described above for R ² .
The alkyloxycarbonyl group for R ³ may be unsubstituted or substituted, or may be cyclic. As carbon number of an alkyloxycarbonyl group, it is 2-20 normally, Preferably it is 2-16, More preferably, it is 2-10. Examples of the alkyloxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group.

The aryloxycarbonyl group for R ³ may be unsubstituted or may have a substituent. The carbon number of the aryloxycarbonyl group includes the carbon number of the substituent, and the number is usually 7 to 30, preferably 7 to 20, and more preferably 7 to 16. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group and a 4-methylphenoxycarbonyl group.
The acyl group for R ³ may be an aliphatic carbonyl group or an arylcarbonyl group, may be saturated or unsaturated, may be cyclic, and may further have a substituent. Good. The carbon number of the acyl group includes all of the carbon atoms of the substituent, and the number thereof is usually 2 to 20, preferably 2 to 15, and more preferably 2 to 10. Examples of the acyl group include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, and benzoyl group.
The aliphatic sulfonyl group for R ³ may be saturated, unsaturated, or cyclic. The number of carbon atoms of the aliphatic sulfonyl group includes the number of carbon atoms of the substituent, and the number thereof is usually 1 to 30, preferably 1 to 20, and more preferably 1 to 16. Examples of the aliphatic sulfonyl group include a methanesulfonyl group, a butanesulfonyl group, a methoxymethanesulfonyl group, a methoxyethanesulfonyl group, and an ethoxyethanesulfonyl group.
The arylsulfonyl group in R ³ may have a substituent, and the number of carbons of the arylsulfonyl group includes the number of carbons of the substituent, and the number is usually 6 to 30, preferably 6 It is -20, More preferably, it is 6-18. Examples of the arylsulfonyl group include benzenesulfonyl and toluenesulfonyl groups.

R ³ is preferably a linear or branched unsubstituted saturated hydrocarbon group having 2 to 10 carbon atoms, particularly preferably 2 to 8 carbon atoms, from the viewpoint of high solubility in a solvent.

Examples of the substituent of the saturated hydrocarbon group in R ^{2 to} R ⁷ include a hydroxy group, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an alkylthio group, a sulfo group, a carboxyl group, and an acyl group. These substituents may further have a substituent.
Although the specific example of the suitable compound represented by Formula (1) in this invention is shown to the following Tables 1-6, the compound of this invention is not limited to these.

  Among the compounds represented by the above formula (1), particularly preferred compounds include compounds represented by the formulas (1-1) to (1-13).

In the dimer formed from the compound represented by the formula (1) and a salt thereof, two compounds represented by the formula (1) may be bonded at an arbitrary position to form a dimer. . Examples of the dimer include a compound represented by the formula (1-a) and a compound represented by the formula (1-b).

(In formula (1-a) and formula (1-b), R ¹ , R ³ and Z represent the same meaning as described above. R ′ ¹ represents R ¹ , R ′ ³ represents R ³ and Z ′. and Z is .R ^{'' 3} and X represent the same meanings, respectively, each independently, an alkylene group or ^-R 8 having 1 to 12 carbon atoms _{^{- (O-R 8) m}} - represents .R ⁸ each a Independently, an alkylene group having 1 to 12 carbon atoms, m represents a number of 1 to 8. Z ₁ and Z ₂ each independently have a divalent carbon number of 6 to 14 which may have a substituent. Represents an aromatic hydrocarbon group.)

Examples of the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenylene group and a naphthylene group, and a phenylene group is preferable.
As a substituent of a bivalent C6-C14 aromatic hydrocarbon group, a halogen atom, a C1-C8 alkyl group, a C1-C8 alkoxy group, a nitro group, a sulfo group, a sulfamoyl group, and N -Substituted sulfamoyl groups and the like can be mentioned.
As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom, a chlorine atom, or a bromine atom is preferable.
Examples of the alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group. An alkyl group having 1 to 4 carbon atoms is preferable, an alkyl group having 1 to 2 carbon atoms is more preferable, and a methyl group is particularly preferable.
Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group and hexyloxy group. An alkoxy group having 1 to 4 carbon atoms is preferable, an alkoxy group having 1 to 2 carbon atoms is more preferable, and a methoxy group is particularly preferable.
As the N-substituted sulfamoyl group, a —SO ₂ NH (R ⁴ ) R ⁵ group is preferable. R ⁴ and R ⁵ represent the same meaning as described above.
Examples of the alkylene group having 1 to 12 carbon atoms of R ″ ³ , R ⁸ and X include, for example, a methylene group, an ethylene group, an n-propylene group, an isopropylene group, an n-butylene group, an isobutylene group, and a sec-butylene group. Tert-butylene group, methylbutylene group (1,1,3,3-tetramethylbutylene group etc.), methylhexylene group (1-methylhexylene group, 1,5-dimethylhexylene group etc.) and ethyl A xylene group (2-ethylhexylene group etc.) etc. can be illustrated. Preferably it is a C1-C4 alkylene group. X of ^{-R 8 - (O-R 8} ) m - as preferably ^{R 8} is an alkylene group, m is 1 to 4, more preferably ^{R 8} is an ethylene group, m is 2. Specific examples include compounds represented by formula (1-14) to formula (1-17).

  Examples of the compound represented by the formula (1) and a dimer salt formed from the compound include organic amine salts such as ammonium salt, ethanolamine salt, and alkylamine salt, lithium salt, sodium salt, potassium salt, and the like. Examples include alkali metal salts.

  The method for producing the specific yellow dye is not particularly limited, and a conventionally known method can be appropriately used. For example, as is well known in the dye field, it can be produced by coupling a diazonium salt and a pyridone.

  The coloring composition of the present invention contains C.I. I. In addition to Pigment Green 58 and the specific yellow dye, another colorant can be further contained. Other colorants are not particularly limited, and any of pigments, dyes and natural pigments can be used. From the viewpoint of obtaining green pixels with high luminance and color purity, organic pigments and organic dyes can be used. Is preferred.

  As the organic pigment, compounds classified as pigments in the color index (CI; issued by The Society of Dyer's and Colorists), that is, the following color index (CI) names are given. You can list what you have.

C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211;
C. I. Pigment green 7, C.I. I. Pigment Green 36.

  Moreover, as an organic dye, what has the following color index (CI) name can be mentioned, for example.

C. I. Acid Yellow 11, C.I. I. Direct Yellow 12, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Azo dyes such as Moldant Yellow 5;
C. I. Anthraquinone dyes such as Acid Green 25;
C. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Quinoline dyes such as Disperse Yellow 64;
C. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Nitro dyes such as Disperse Yellow 42.

  In the present invention, other colorants can be used alone or in admixture of two or more.

  In the present invention, C.I. I. It is preferable to use the pigment green 58 and other pigments used as necessary by refining primary particles by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.

  In the present invention, C.I. I. The content ratio of Pigment Green 58 is preferably 1 to 90% by mass, particularly preferably 5 to 70% by mass in the total colorant, and the content ratio of the specific yellow dye is preferably 10 to 99% in the total colorant. It is 30 mass%, Most preferably, it is 30-95 mass%.

  (A) The content rate of a coloring agent is 5-70 mass% normally in the solid content of a coloring composition from the point which forms the pixel excellent in a brightness | luminance and color purity, Preferably it is 5-60 mass%. Here, solid content is components other than the solvent mentioned later.

  In the present invention, C.I. I. Pigment Green 58 and other pigments used as necessary can be used by dispersing them in a coloring composition together with a dispersing agent and / or a dispersing aid. Examples of the dispersant include appropriate cationic, anionic, and nonionic dispersants. Examples of the dispersion aid include pigment derivatives. The contents of the dispersant and the dispersion aid can be appropriately determined within a range that does not impair the object of the present invention.

-(B) Binder resin-
The binder resin (B) in the present invention is not particularly limited as long as the acid value is 85 to 300 mgKOH / g. When the acid value is less than 85 mgKOH / g, the thermal stability of the specific yellow dye is lowered. On the other hand, when it exceeds 300 mgKOH / g, the specific yellow dye is likely to be eluted during alkali development. In the present invention, examples of the acidic functional group that expresses an acid value include a carboxyl group, a phenolic hydroxyl group, an imido acid group (—CO—NH—CO—), a sulfo group, a sulfino group, and a sulfeno group. Among them, a carboxyl group is preferable from the viewpoint of solubility in a solvent described later.

  Examples of the polymer having a carboxyl group include, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-140654, JP-A-7-207211, and JP-A-8-259876. JP-A-09-325494, JP-A-10-31308, JP-A-10-300902, JP-A-11-140144, JP-A-11-174224, JP-A-11-231523, Examples include polymers disclosed in Kaihei 11-258415, JP-A 2000-56118, JP-A 2002-296778, JP-A 2004-101728, JP-A 2008-181095, and the like. it can.

  In the present invention, the lower limit of the acid value of the (B) binder resin is more preferably 100 mgKOH / g or more from the viewpoint that the thermal stability of the specific yellow dye can be enhanced. On the other hand, the upper limit of the acid value of the (B) binder resin is more preferably 270 mgKOH / g or less from the viewpoint that the elution of the specific yellow dye during alkali development can be further suppressed. Here, the “acid value” is the number of mg of KOH required to neutralize 1 g of the resin, and specifically, it is measured by the method described in the examples below. Moreover, in this invention, the acid value of binder resin means the acid value as the whole binder resin. That is, even when a plurality of types of binder resins having different acid values are used, it means an acid value measured in a mixed state.

  The (B) binder resin in the present invention has a polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) measured by GPC (elution solvent: tetrahydrofuran), usually 1,000 to 100,000, preferably 3, 000 to 50,000. If Mw is too small, the remaining film rate of the resulting film may be reduced, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. On the other hand, if Mw is too large, resolution may be reduced. The pattern shape may be damaged.

  In addition, the ratio (Mw / Mn) of Mw of (B) binder resin in the present invention to the number average molecular weight (hereinafter referred to as “Mn”) in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) is preferably It is 1.0-5.0, More preferably, it is 1.0-3.0.

In this invention, (B) binder resin can be used individually or in mixture of 2 or more types.
In this invention, content of (B) binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts.

-(C) polyfunctional monomer-
The (C) polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds, and is a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups. It is preferable. Examples of such compounds include polyfunctional (meth) acrylates obtained by reacting aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, and alkylene oxide-modified polyfunctional compounds. Functional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting hydroxyl-containing (meth) acrylate and polyfunctional isocyanate, carboxyl group obtained by reacting hydroxyl-containing (meth) acrylate and acid anhydride The polyfunctional (meth) acrylate etc. which have can be mentioned.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of trivalent or higher aliphatic polyhydroxy compounds. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol dihydrate. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include ethylene oxide of bisphenol A and / or propylene oxide modified di (meth) acrylate, ethylene oxide of isocyanuric acid and / or propylene oxide modified tri (meth) acrylate, tri Ethylene oxide and / or propylene oxide modified tri (meth) acrylate of methylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of pentaerythritol, ethylene oxide and / or propylene oxide modified tetra (meth) acrylate of pentaerythritol , Ethylene oxide and / or propylene oxide modified penta (meth) acrylate of dipentaerythritol, And ethylene oxide pentaerythritol and / or propylene oxide-modified hexa (meth) acrylate.

In the present invention, the polyfunctional monomer (C) can be used alone or in admixture of two or more.
Content of (C) polyfunctional monomer in this invention is 5-500 mass parts normally with respect to 100 mass parts of (B) binder resin, Preferably it is 20-300 mass parts.

-(D) Photopolymerization initiator-
The coloring composition of the present invention can be provided with radiation sensitivity by incorporating a photopolymerization initiator. The term “radiation” as used herein means a substance including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.
The photopolymerization initiator (D) used in the present invention has an activity capable of initiating polymerization of the polyfunctional monomer (C) by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. A compound that generates seeds.

Such a photopolymerization initiator is not particularly limited, and for example, a known photoradical generator can be used. For example, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, Examples thereof include diazo compounds and imide sulfonate compounds.
The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

  Among preferred photopolymerization initiators in the present invention, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

  Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′. -Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, Examples thereof include 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, hydrogen donors can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

  In this invention, when using photoinitiators other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

In the present invention, the photopolymerization initiator (D) can be used alone or in admixture of two or more.
In the present invention, the content of the (D) photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass with respect to 100 parts by mass of the (C) polyfunctional monomer. . In this case, if the content of the photopolymerization initiator is too small, curing by exposure may be insufficient. On the other hand, if the content is too large, the formed colored layer tends to be detached from the substrate during development.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Examples include inhibitors, residue improvers such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid.

-Solvent-
The colored composition of the present invention is usually prepared as a liquid composition by blending a solvent. As the solvent in the present invention, the above-mentioned components (A) to (C) constituting the colored composition and other components optionally added are dispersed or dissolved, and do not react with these components and have appropriate volatility. As long as it has, it can be appropriately selected and used.

As such a solvent, for example,
(Poly) alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether;
(Poly) alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate;
Ketones such as methyl ethyl ketone, methyl n-amyl ketone, and cyclohexanone;
Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate;
(Cyclo) alkyl esters such as ethyl acetate, butyl acetate, cyclohexyl acetate and the like can be mentioned.

In this invention, a solvent can be used individually or in mixture of 2 or more types.
The content of the solvent in the present invention is such that the total concentration of each component excluding the solvent of the composition is usually 5 to 50% by mass from the viewpoint of the coating property and stability of the resulting colored composition. The quantity which becomes 10-40 mass% is preferable.

Color filter and manufacturing method thereof The color filter of the present invention comprises a green pixel formed from the colored composition of the present invention.
As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, after applying a liquid composition of the colored radiation-sensitive composition of the present invention on this substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which green pixel patterns are arranged in a predetermined arrangement.
Then, using the liquid composition of each colored radiation-sensitive composition of red or blue, the liquid composition is applied, pre-baked, exposed, developed and post-baked in the same manner as described above, and the red pixel array and Blue pixel arrays are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  The black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method. And can be formed in the same manner as in the case of forming the pixel.

Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

When applying the liquid composition of the colored radiation-sensitive composition to the substrate, an appropriate application method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method is used. Can be adopted.
Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pass. Moreover, the conditions of heat drying are 70-110 degreeC normally for about 1 to 10 minutes.
The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm as the film thickness after drying.

Examples of radiation light sources used in forming pixels and / or black matrices include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, and low pressure mercury lamps. Examples of the light source include a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. Radiation having a wavelength in the range of 190 to 450 nm is preferable.
Exposure of the radiation is generally preferred 10~10,000J / m ^2.

Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.
The post-baking conditions are usually 180 to 280 ° C. and about 10 to 60 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.

As a second method for producing a color filter, a method for obtaining pixels of each color by an ink jet method, which is disclosed in JP-A-7-318723, JP-A-2000-310706, and the like, is also known. In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, for example, a liquid composition of a green coloring composition containing a specific yellow dye is discharged into the formed partition wall by an ink jet apparatus, and then prebaked to evaporate the solvent. Next, this coating film is exposed as necessary and then cured by post-baking to form a green pixel pattern.
Next, a red pixel pattern and a blue pixel pattern are sequentially formed on the same substrate using a liquid composition of each colored composition of red or blue in the same manner as described above. Thereby, a color filter in which pixel patterns of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.
In addition, the partition has not only a light shielding function but also a function for preventing the color composition of each color discharged in the section from being mixed, so that the film is a film compared to the black matrix used in the first method described above. Thick. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.
The color filter of the present invention thus obtained is excellent in various characteristics, and thus is extremely useful for a color liquid crystal surface element, a color image pickup tube element, an organic EL display element and the like.

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
The color liquid crystal display element of the present invention can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. In addition, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure that is opposed to each other. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

  The color liquid crystal display element of the present invention may include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light using a red LED, a green LED, and a blue LED having independent spectra, a white LED that obtains white light by mixing colors by combining the red LED, the green LED, and the blue LED, White LED that obtains white light by color mixing by combining blue LED, red LED and green phosphor, White LED that obtains white light by color mixing by combining blue LED, red light emitting phosphor and green light emitting phosphor, Blue LED and YAG system White LED that obtains white light by mixing phosphors, white LED that obtains white light by mixing blue LED, orange light emitting phosphor and green light emitting phosphor, UV LED, red light emitting phosphor, green light emitting phosphor and blue A white LED that obtains white light by mixing colors by combining light emitting phosphors can be exemplified.

  The color liquid crystal display element of the present invention includes a TN (twisted nematic) type, a STN (super twisted nematic) type, an IPS (in-plane switching) type, a VA (vertical aligned type) type, and an OCB (optically conjugated type). An appropriate liquid crystal mode can be applied.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Synthesis of specific yellow dye>
Synthesis example 1
(Synthesis of azo dye intermediate (a))

  After sufficiently stirring 37.0 parts by mass of sulfanilic acid together with 150 parts by mass of water and 32 parts by mass of concentrated hydrochloric acid, diazotization at 5 to 10 ° C. using 25 parts by mass of 4N sodium nitrite, followed by 1-ethyl-1, To 42 parts by mass of 2-dihydro-6-hydroxy-4-methyl-2-oxo-3-pyridinecarbonitrile, 370 parts by mass of water was added, and a solution prepared to pH 8 with 2N sodium hydroxide was added to the coupling component. The temperature was kept at a temperature of ℃ or less and added. The pH is adjusted to 5.0 with sodium hydroxide to complete the coupling reaction. After the reaction is completed, salting out is performed using 100 parts by mass of sodium chloride, and the precipitated product is filtered off and dried to obtain an azo dye intermediate ( 60.4 mass parts (78 mol% with respect to sulfanilic acid) was obtained for a).

(Synthesis of sulfonic acid chloride (b))

  While 35 parts by mass of the azo dye intermediate (a) was suspended in a mixed solvent of 15.6 parts by mass of dimethylformamide and 215.5 parts by mass of acetonitrile under ice-cooling, thionyl chloride was added dropwise. . After a while, the temperature was raised to 40 ° C. and further stirred for 4 hours. Thereafter, the suspension was poured into 525 parts by mass of water with stirring, and further stirred for 10 minutes. The resulting precipitate was collected by filtration and vacuum dried at 60 ° C. for several hours to obtain 29.2 parts by mass (80 mol% with respect to the azo dye intermediate) of the sulfonic acid chloride (b).

(Synthesis of specific yellow dye)

  29.2 parts by mass of the sulfonic acid chloride (b) was suspended in chloroform under ice-cooling, and a mixed solution of 14.9 parts by mass of 2-ethylhexylamine and 38.9 parts by mass of triethylamine was slowly added dropwise. After warming to room temperature and stirring for 10 minutes, the reaction solution was concentrated. The concentrate was dissolved in 150 parts by mass of acetone, poured into 600 parts by mass of 1M hydrochloric acid, and the resulting precipitate was collected by filtration. This precipitate was dissolved in 400 parts by mass of methanol under heating and refluxing, and slowly cooled to room temperature. The resulting precipitate was collected by filtration and then vacuum-dried at 60 ° C. for several hours to obtain 28.4 parts by mass of specific yellow dye (78 mol% based on the sulfonate chloride).

<Preparation of pigment dispersion>
Preparation Example 1
As a coloring agent, C.I. I. 15 parts by mass of Pigment Green 58, 12.5 parts by mass of BYK-LPN21116 (produced by BYK) as a dispersant (solid content concentration = 40% by mass), and 72.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent The pigment dispersion (A-1) was prepared by using a bead mill.

Preparation Example 2
As a coloring agent, C.I. I. 15 parts by weight of Pigment Yellow 150, 12.5 parts by weight of BYK-LPN21116 (produced by BYK) as a dispersant (solid content concentration = 40% by weight), and 72.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent Then, it was processed by a bead mill to prepare a pigment dispersion (A-2).

Preparation Example 3
As a coloring agent, C.I. I. 15 parts by mass of Pigment Green 36, 12.5 parts by mass of BYK-LPN21116 (produced by BYK) as a dispersant (solid content concentration = 40% by mass), and 72.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent Then, it was processed by a bead mill to prepare a pigment dispersion (A-3).

<Preparation of dye solution>
Preparation Example 4
10 parts by mass of the specific yellow dye obtained in Synthesis Example 1 as a colorant and 90 parts by mass of cyclohexanenone as a solvent were mixed to prepare a dye solution A.

<(B) Synthesis of binder resin>
Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 15 parts by mass of styrene, 25 parts by mass of butyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, N-phenylmaleimide A mixed solution of 25 parts by mass and 2,2′-azobis (2,4-dimethylvaleronitrile) 6 parts by mass was added dropwise over 1 hour, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C. and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin was Mw = 10,500 and Mn = 5,500. This binder resin is referred to as “binder resin (B1)”.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 16 parts by mass of methacrylic acid, 15 parts by mass of styrene, 29 parts by mass of butyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, N-phenylmaleimide A mixed solution of 25 parts by mass and 2,2′-azobis (2,4-dimethylvaleronitrile) 6 parts by mass was added dropwise over 1 hour, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C. and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin was Mw = 10,300 and Mn = 5,200. This binder resin is referred to as “binder resin (B2)”.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of cyclohexanone, 40 parts by mass of methacrylic acid, 15 parts by mass of styrene, 10 parts by mass of butyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate, 25 parts by mass of N-phenylmaleimide, And a mixed solution of 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added dropwise over 1 hour, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C. and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin was Mw = 11,000 and Mn = 5,600. This binder resin is referred to as “binder resin (B3)”.

Synthesis example 5
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of cyclohexanone, 46 parts by mass of methacrylic acid, 15 parts by mass of styrene, 4 parts by mass of butyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate, 25 parts by mass of N-phenylmaleimide, And a mixed solution of 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added dropwise over 1 hour, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C. and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin was Mw = 10,000 and Mn = 5,100. This binder resin is referred to as “binder resin (B4)”.

Synthesis Example 6
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 12 parts by mass of methacrylic acid, 15 parts by mass of styrene, 33 parts by mass of butyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, N-phenylmaleimide A mixed solution of 25 parts by mass and 2,2′-azobis (2,4-dimethylvaleronitrile) 6 parts by mass was added dropwise over 1 hour, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C. and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin was Mw = 10,700 and Mn = 5,500. This binder resin is referred to as “binder resin (B5)”.

<(B) Measurement of acid value of binder resin>
The acid value of the binder resin obtained in each of the above synthesis examples was measured as follows. Table 1 shows the measurement results.
0.5 g of the binder resin solution was precisely weighed to a unit of 1 mg and separated into a glass container. After diluting to 50 mL with cyclohexanone, phenolphthalein was added, titrated with 0.1N ethanolic potassium hydroxide aqueous solution, and the point colored pink was the end point. Similarly, a blank test was performed. The acid value (unit: mgKOH / g) was calculated from the binder resin and the drop amount of 0.1N ethanolic potassium hydroxide aqueous solution in the blank test.

<Preparation of colored radiation-sensitive composition>
Preparation Example 5
32.7 parts by mass of the pigment dispersion (A-1), 21.0 parts by mass of the dye solution A obtained in Preparation Example 4 above, 12.2 parts by mass of the binder resin (B1) solution as a binder resin, polyfunctionality Dipentaerythritol hexaacrylate 6.0 parts by mass as a monomer, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Ciba Specialty Chemicals) as a photopolymerization initiator A colored composition (CR1) having a solid content of 20% by mass was prepared by mixing 1.3 parts by mass of trade name, IRGACURE 369), and propylene glycol monomethyl ether acetate as a solvent.

Preparation Example 6
A colored composition (CR2) having a solid concentration of 20% by mass was prepared in the same manner as in Example 1 except that the binder resin (B2) was used instead of the binder resin (B1).

Preparation Example 7
A colored composition (CR3) having a solid content concentration of 20% by mass was prepared in the same manner as in Example 1 except that the binder resin (B3) was used instead of the binder resin (B1).

Preparation Example 8
A colored composition (CR4) having a solid content concentration of 20% by mass was prepared in the same manner as in Example 1 except that the binder resin (B4) was used instead of the binder resin (B1).

Comparative Preparation Example 1
28.0 parts by mass of the pigment dispersion (A-1), 18.7 parts by mass of the pigment dispersion (A-2), 11.4 parts by mass of the binder resin (B1) solution as a binder resin, and as a polyfunctional monomer 5.6 parts by mass of dipentaerythritol hexaacrylate, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (manufactured by Ciba Specialty Chemicals, Inc.) as a photopolymerization initiator Name IRGACURE 369) 1.3 parts by mass and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a colored composition (CR5) having a solid content concentration of 20% by mass.

Comparative Preparation Example 2
31.7 parts by mass of the pigment dispersion (A-3), 22.4 parts by mass of the dye solution A obtained in Preparation Example 4 above, 12.2 parts by mass of the binder resin (B1) solution as the binder resin, multifunctional 6.8 parts by mass of dipentaerythritol hexaacrylate as a monomer and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (Ciba Specialty Chemicals) as a photopolymerization initiator A colored composition (CR6) having a solid content of 20% by mass was prepared by mixing 1.3 parts by mass of trade name, IRGACURE 369), and propylene glycol monomethyl ether acetate as a solvent.

Comparative Preparation Example 3
A colored composition (CR7) having a solid content concentration of 20% by mass was prepared in the same manner as in Example 1 except that the binder resin (B5) was used instead of the binder resin (B1).

Example 1
The coloring composition (CR1) was applied on a glass substrate using a spin coater, and then pre-baked on an 80 ° C. hot plate for 10 minutes to form a coating film. Three coating films having different film thicknesses were formed by the same operation while changing the rotation speed of the spin coater.
Next, after cooling these substrates to room temperature, a high-pressure mercury lamp is used, and a radiation containing each wavelength of 365 nm, 405 nm, and 436 nm is applied to each coating film without using a photomask at an exposure dose of 2,000 J / m ² . And exposed. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230 ° C. for 30 minutes to form a cured film for evaluation.

  The three cured films obtained were measured for chromaticity coordinate values (x, y) in the CIE color system using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) with a C light source and a 2-degree field of view. . Moreover, the film thickness of the obtained cured film was measured using the alpha step IQ made from KLA-Tencor. From the measurement results, the chromaticity coordinate value x, the stimulus value (Y), and the film thickness at the chromaticity coordinate value y = 0.590 were obtained. The evaluation results are shown in Table 1. The larger the stimulus value (Y), the higher the light transmittance (brightness), and the thinner the film thickness, the higher the coloring power.

Further, the substrate on which the cured film is formed is sandwiched between two deflecting plates, and the front side deflecting plate is rotated while irradiating with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side, and the luminance meter LS-100 (Minolta The maximum value and the minimum value of the transmitted light intensity were measured. And about each cured film, the value which remove | divided the maximum value by the minimum value was made into the contrast ratio. From the measurement result, the contrast ratio at the chromaticity coordinate value y = 0.590 was determined. The evaluation results are shown in Table 1.

Examples 2 to 4 and Comparative Examples 1 to 3
Evaluation was performed in the same manner as in Example 1 except that the colored compositions (CR2) to (CR7) were used instead of the colored composition (CR1). The evaluation results are shown in Table 2.

  In Table 7, “G58” means C.I. I. Pigment Green 58, “G36” is C.I. I. Pigment Green 36, “Y150” is C.I. I. Pigment Yellow 150 means each.

Claims (5)

(A) at least one selected from the group consisting of a compound represented by the following formula (1), a dimer formed from the compound and a salt thereof; I. A colorant comprising CI Pigment Green 58;
(B) A colored resin composition for color filters, comprising a binder resin having an acid value of 104 to 300 mgKOH / g, and (C) a polyfunctional monomer.

[In Formula (1),
Z represents a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxy group, a carboxyl group, a carbamoyl group, a sulfo group, a sulfamoyl group, and N. A phenyl group having one or two substituents selected from the group consisting of a substituted sulfamoyl group, a halogen atom, an optionally substituted hydrocarbon group having 1 to 12 carbon atoms, carbon A naphthyl group having 1 to 3 substituents selected from the group consisting of an alkoxy group of formulas 1 to 8, a hydroxy group, a carboxyl group, a carbamoyl group, a sulfo group, a sulfamoyl group and an N-substituted sulfamoyl group. .
R ¹ represents a hydrogen atom, a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group or a trifluoromethyl group.
R ² represents a hydrogen atom, a linear, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms, a cyano group, a sulfamoyl group, a sulfo group or an amino group.
R ³ is a hydrogen atom, an optionally substituted linear, branched or cyclic saturated hydrocarbon group having 1 to 10 carbon atoms, and an optionally substituted carbon atom having 6 to 30 carbon atoms. Aryl group, optionally substituted aralkyl group having 7 to 20 carbon atoms, optionally substituted heterocyclic group having 3 to 20 carbon atoms, cyano group, carbamoyl group, N-substituted A carbamoyl group, an optionally substituted alkyloxycarbonyl group having 2 to 20 carbon atoms, an optionally substituted aryloxycarbonyl group having 7 to 30 carbon atoms, and a substituent. An acyl group having 2 to 20 carbon atoms, an aliphatic sulfonyl group having 1 to 30 carbon atoms which may have a substituent, or an arylsulfonyl group having 6 to 30 carbon atoms which may have a substituent. Represent. ] (B) the acid value of the binder resin is 104 ~270mgKOH / g, a color filter coloring composition according to claim 1.   The coloring composition for a color filter according to claim 1 or 2, further comprising (D) a photopolymerization initiator.   The color filter provided with the green pixel formed using the coloring composition for color filters of any one of Claims 1-3.   A color liquid crystal display device comprising the color filter according to claim 4.