JP5581566B2 - Colored curable composition - Google Patents

Description

  The present invention relates to a colored curable composition.

  Colored curable compositions are used for the production of color filters used in display devices such as liquid crystal display panels, electroluminescence, and plasma display panels.

In this colored curable composition, it is known to use a pigment or a dye as a colorant.
Among these, colored curable compositions using pigments generally have high light resistance and heat resistance, but the light transmittance of the color filter is reduced due to the pigment particles. There is a problem that the contrast is lowered (see Patent Document 1).
Further, a colored curable composition using a dye has a feature that the color filter has a high contrast because there is no light scattering by the pigment particles, but there is a problem that the light resistance and heat resistance are low. (See Patent Documents 2 and 3).

  Accordingly, various studies have been made to improve the light resistance and heat resistance of colored curable compositions using dyes. Among them, phthalocyanine dyes having a specific structure and pyridone azo having a specific structure are used for green colored curable compositions. It has been proposed to use a dye in combination (see Patent Document 4).

JP 2000-352610 A, page 2, right column, lines 24-30 JP 2004-157455 A3 page 42 line 4 page 8 line JP 2004-246105 A2 page 35 line 3 page 3 line JP 2006-71822 A

However, even with the invention described in Patent Document 4, the present inventors still have room for improvement in heat resistance, and the resulting color filter has insufficient solvent resistance. I found out.
An object of the present invention is to provide a new colored curable composition that is excellent in heat resistance and solvent resistance, and that can form a color filter that does not deteriorate contrast and light resistance.

  As a result of intensive studies to find a colored curable composition that can solve the above-described problems, the present inventors include a phthalocyanine dye having a specific structure different from the phthalocyanine dye conventionally known as a colorant. The present inventors have found that a colored curable composition can solve the above problems, and have completed the present invention.

  That is, the present invention is a colored curable composition containing (A) a colorant and (B) a polymerizable compound, wherein (A) the colorant contains a dye represented by the formula (1). A colored curable composition is provided.

[In Formula (1), M represents a metal-free, a metal, and a metal oxide.
A ^{1 to} A ¹⁶ each independently represent a hydrogen atom, a halogen atom, or a substituent selected from the group of substituents represented by formulas (2) to (5). Provided ^{that at} 1-8 of A 1 ^{to A 16} represents a substituent selected from the group of substituents represented by the formula (2) to (5).

(In formulas (2) to (5), G ^{1 to} G ⁴ each independently represents an oxygen atom, a sulfur atom, or N (R ¹⁴ ) —.
R ¹⁴ represents a hydrogen atom or a linear or branched saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms.
R ^{11 to} R ¹³ each independently represent a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a linear or branched saturated aliphatic hydrocarbon having 1 to 8 carbon atoms. Represents a group.
J ^{1 to} J ³ each independently represent a halogen atom, a linear or branched saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, or an alkoxyl group having 1 to 4 carbon atoms.
L represents a halogen atom, a linear or branched saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms or an alkoxyl group having 1 to 4 carbon atoms.
e1, g1 and i1 are each independently an integer of 1 to 5.
e2, g2 and i2 are each independently an integer of 0 to 5;
However, the sum of e1 and e2, the sum of g1 and g2, and the sum of i1 and i2 are integers of 5 or less.
f and h are each independently an integer of 1 to 6.
j is an integer of 1 or 2]

  The present invention also provides a color filter produced by a photolithographic method or an inkjet method using the colored curable composition, and a liquid crystal display device using the color filter. is there.

  When the colored curable composition of the present invention is used, a color filter that is excellent in heat resistance and solvent resistance and does not deteriorate light resistance and contrast can be produced.

  The colored curable composition of this invention contains the pigment | dye represented by Formula (1) as (A) a coloring agent.

[In formula (1), M represents a metal-free, a metal, or a metal oxide.
A ^{1 to} A ¹⁶ each independently represent a hydrogen atom, a halogen atom, or a substituent selected from the group of substituents represented by formulas (2) to (5). Provided ^{that at} 1-8 of A 1 ^{to A 16} represents a substituent selected from the group of substituents represented by the formula (2) to (5).

In formulas (2) to (5), G ^{1 to} G ⁴ each independently represent an oxygen atom, a sulfur atom or an N (R ¹⁴ ) — group.
R ¹⁴ represents a hydrogen atom or a linear or branched saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms.
R ^{11 to} R ¹³ each independently represent a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or a linear or branched saturated aliphatic hydrocarbon having 1 to 8 carbon atoms. Represents a group.
J ^{1 to} J ³ each independently represent a halogen atom, a linear or branched saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, or an alkoxyl group having 1 to 4 carbon atoms.
L represents a halogen atom, a linear or branched saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms or an alkoxyl group having 1 to 4 carbon atoms.
e1, g1 and i1 are each independently an integer of 1 to 5.
e2, g2 and i2 are each independently an integer of 0 to 5;
However, the sum of e1 and e2, the sum of g1 and g2, and the sum of i1 and i2 are integers of 5 or less.
f and h are each independently an integer of 1 to 6.
j is an integer of 1 or 2. ]

Examples of the metal in M include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, and Fe, and preferably Zn, Cu, Ni, and Co. .
Examples of the metal oxide in M include VO and TiO.
The metal-free in M represents one in which one hydrogen atom is bonded to each of two nitrogen atoms that should be coordinated to a metal or metal oxide.

Examples of the halogen atom in A ^{1 to} A ¹⁶ include a fluorine atom, a chlorine atom, and a bromine atom.

Examples of the aryl group having 6 to 20 carbon atoms which may have a substituent in R ^{11 to} R ¹³ include an aryl group which may have a substituent such as a saturated aliphatic hydrocarbon group or a hydroxyl group. It is done. Examples of the aryl group include a phenyl group, a hydroxyphenyl group (such as 4-hydroxyphenyl group), and a trifluoromethylphenyl group (such as 4-trifluoromethylphenyl group).
Examples of the saturated aliphatic hydrocarbon group as the substituent 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, and a tert-butyl group. .

Examples of the linear or branched saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms in R ^{11 to} R ¹³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Examples thereof include a tert-butyl group, a linear or branched pentyl group, a linear or branched hexyl group, a linear or branched heptyl group, and a linear or branched octyl group. Includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.

The halogen atom in J ¹ through J ^3, a fluorine atom, a chlorine atom, a bromine atom and the like, preferably a fluorine atom.

Examples of the linear or branched saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms in J ^{1 to} J ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, A tert-butyl group is mentioned.

Examples of the alkoxyl group having 1 to 4 carbon atoms in J ^{1 to} J ³ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.

Examples of the halogen atom, linear or branched saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, and alkoxyl group having 1 to 4 carbon atoms in L are the same as those exemplified above for J ^{1 to} J ^3. Things.

In formula (2), G1 represents an oxygen atom, a sulfur atom or an N (R ¹⁴ ) — group, preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom.
e1 is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably an integer of 1 or 2.
e2 is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably an integer of 0 or 1.

  Examples of the substituent represented by the formula (2) include groups represented by the formulas (2-1) to (2-26), preferably (2-1) to (2-7), ( 2-9) to (2-11), (2-13) to (2-18), (2-20) to (2-22), (2-24) and (2-25) And more preferably (2-1) to (2-7), (2-9), (2-11), (2-13) to (2-15), (2-17) and And a group represented by (2-21).

In formula (3), G2 represents an oxygen atom, a sulfur atom or an N (R ¹⁴ ) — group, preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom.
f is an integer of 1 to 6, preferably an integer of 1 to 3, and more preferably an integer of 1 or 2.
g1 is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably an integer of 1 or 2.
g2 is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably an integer of 0 or 1.

  Examples of the substituent represented by the formula (3) include groups represented by (3-1) to (3-19), and preferably (3-1) to (3-3), (3 -6), (3-8), (3-10), (3-11), (3-12), (3-14), (3-15) and groups represented by (3-17) More preferably, groups represented by (3-1) to (3-3), (3-6), (3-10), (3-12) and (3-14) are exemplified. .

In Formula (4), G3 represents an oxygen atom, a sulfur atom or an N (R ¹⁴ ) — group, preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom.
h is an integer of 1 to 6, preferably an integer of 1 to 3, and more preferably an integer of 1 or 2.
i1 is an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably an integer of 1 or 2.
i2 is an integer of 0-4, preferably an integer of 0-2, more preferably an integer of 0 or 1.

  Examples of the substituent represented by the formula (4) include groups represented by (4-1) to (4-19), preferably (4-1) to (4-4), (4 -7), (4-8), (4-10), (4-13), (4-14) and groups represented by (4-16), more preferably (4-1) ) To (4-3), (4-7), (4-10) and groups represented by (4-14).

In formula (5), G4 represents an oxygen atom, a sulfur atom or an N (R ¹⁴ ) — group, preferably an oxygen atom or a sulfur atom, more preferably an oxygen atom.
In formula (5), j is an integer of 1 or 2, and is preferably 1.

  Examples of the substituent represented by the formula (5) include groups represented by (5-1) to (5-18), preferably (5-1) to (5-6) and (5 -8) to (5-16), and more preferably (5-1) to (5-6), (5-10), (5-11), (5-13). ) And groups represented by (5-16).

  Examples of the dye represented by the formula (1) include dyes represented by (1-1) to (1-33), preferably (1-1) to (1-5), (1-7). ) To (1-11), (1-13), (1-14), (1-16), (1-18), (1-19), (1-22) to (1-24), Examples thereof include dyes represented by (1-27) to (1-31) and (1-33), and more preferably (1-1) to (1-3), (1-7), (1- 8), (1-10), (1-13), (1-14), (1-18), (1-22), (1-24), (1-28) and (1-29) The pigment | dye represented by these is mentioned.

Content of the pigment | dye represented by Formula (1) in the colored curable composition of this invention is a mass fraction with respect to solid content of a colored curable composition, Preferably it is 15-65 mass%, More preferably Is 20 to 60% by mass, particularly preferably 25 to 60% by mass.
When the content of the pigment is in the above range, the color density when the color filter is obtained is sufficient, and a necessary amount of the polymerizable compound can be contained in the composition, so that the solvent resistance tends to be improved. This is preferable.
Here, in this specification, solid content means the total amount of the component except the solvent contained in a colored curable composition.

  In the colored curable composition of the present invention, the (A) colorant is at least one selected from the group consisting of barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cyanine dyes. Species dyes can be included.

  Although it does not specifically limit as said barbituric acid azo dye, Although a well-known substance can be used, Preferably the barbituric acid azo dye represented by Formula (7) is used.

Wherein (7), ^{T 1} and ^{T 2} each independently represent an oxygen atom or a sulfur atom.
R ^{31 to} R ³⁴ are each independently a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted by a hydroxyl group, or 1 carbon atom. A saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted by an alkoxyl group having 8 to 8 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with a thioalkoxyl group having 1 to 8 carbon atoms, An aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 2 to 10 carbon atoms is represented.
R ^{35 to} R ⁴² are each independently a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted by a halogen atom, An alkoxyl group having 1 to 8 carbon atoms, a carboxyl group, a sulfo group, a sulfamoyl group or an N-substituted sulfamoyl group is represented. ]

T ¹ and T ² each independently represent an oxygen atom or a sulfur atom, and may be the same or different, but are preferably the same.

The saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ^{31 to} R ³⁴ may be linear, branched or cyclic. Carbon number of a C1-C10 saturated aliphatic hydrocarbon group becomes like this. Preferably it is 2-8, More preferably, it is 3-6. Examples of the saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and ethylhexyl. Groups (such as 2-ethylhexyl group), cyclopentyl group, cyclohexyl group, cyclohexylalkyl group and the like.
In addition, as described above, the saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms is a hydroxyl group, an alkoxyl group having 1 to 8 carbon atoms (preferably having 1 to 4 carbon atoms), or 1 to 8 carbon atoms ( A thioalkoxyl group (preferably having 1 to 4 carbon atoms) may be substituted. Examples of the substituted saturated aliphatic hydrocarbon group include a hydroxyethyl group (such as 2-hydroxyethyl group), an ethoxyethyl group (such as 2-ethoxyethyl group), and an ethylhexyloxypropyl group (3- (2- An ethylhexyloxy) propyl group), a methylthiopropyl group (such as a 3-methylthiopropyl group), and the like.

The aryl group having 6 to 20 carbon atoms in R ^{31 to} R ³⁴ may be unsubstituted and has a substituent such as a saturated aliphatic hydrocarbon group, an alkoxyl group, a carboxyl group, a sulfo group, or an ester group. May be. The carbon number of the aryl group is counted including the carbon number of the substituent, and preferably 6 to 10. Examples of these aryl groups include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-sulfophenyl. And a substituted or unsubstituted phenyl group such as a 3-sulfophenyl group, a 4-sulfophenyl group, and an ethoxycarbonylphenyl group (such as 4- (COOC ₂ H ₅ ) Ph group).

The alkyl part of the aralkyl group having 7 to 20 carbon atoms in R ^{31 to} R ³⁴ may be linear, branched or cyclic. The carbon number of the aralkyl group is counted including the carbon number of the substituent, and is preferably 7 to 10. Examples of the aralkyl having 7 to 20 carbon atoms include a benzyl group and a phenethyl group.

The acyl group having 2 to 10 carbon atoms in R ^{31 to} R ³⁴ may be unsubstituted, or a substituent such as a saturated aliphatic hydrocarbon group or an alkoxyl group may be bonded thereto. The carbon number of the acyl group is counted including the carbon number of the substituent, and the number is preferably 2 to 10. Examples of the acyl group include an acetyl group, a benzoyl group, and a methoxybenzoyl group (such as a p-methoxybenzoyl group).

As in the case of R ^{31 to} R ³⁴ , the saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ^{35 to} R ⁴² may be linear, branched or cyclic, and the carbon number is preferably Is 2-8, more preferably 3-6.
Specific examples of the saturated aliphatic hydrocarbon group for R ^{35 to} R ⁴² are the same as those exemplified for R ³¹ and R ³² . The saturated aliphatic hydrocarbon group of R ^{35 to} R ⁴² may be substituted with a halogen atom, preferably a fluorine atom. Specific examples of the saturated aliphatic hydrocarbon group substituted with a halogen atom include a trifluoromethyl group.

The number of carbon atoms of the alkoxyl group having 1 to 8 carbon atoms in R ³⁵ to R ⁴² is preferably from 1 to 4. Examples of the alkoxyl group 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.

The N-position-substituted sulfamoyl group in R ^{35 to} R ⁴² is, for example, an N-position-monosubstituted sulfamoyl group, and is represented by the formula —SO ₂ NHR ⁴³ .
R ⁴³ is a C 1-10 saturated aliphatic hydrocarbon group (including a C 1-10 saturated aliphatic hydrocarbon group bonded to a C 1-8 alkoxyl group), C 6-6 A 20 aryl group, a C7-20 aralkyl group or a C2-10 acyl group is represented.

The saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ⁴³ may be linear, branched or cyclic. The carbon number of the saturated aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number is preferably 6 to 10.
Examples of the saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ⁴³ 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, and a tert-butyl group. Group, methylbutyl group (such as 1,1,3,3-tetramethylbutyl group), methylhexyl group (such as 1-methylhexyl group and 1,5-dimethylhexyl group), ethylhexyl group (such as 2-ethylhexyl group), A cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group (such as a 2-methylcyclohexyl group), a cyclohexylalkyl group, and the like can be given.

As described above, the saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ⁴³ may be substituted with a substituent of an alkoxyl group having 1 to 8 carbon atoms (preferably having 1 to 4 carbon atoms). . Examples of the substituted saturated aliphatic hydrocarbon group include a propoxypropyl group (3- (isopropoxy) propyl group and the like).

The aryl group having 6 to 20 carbon atoms in R ⁴³ may be unsubstituted or may have a substituent such as a saturated aliphatic hydrocarbon group or a hydroxyl group. The carbon number of the aryl group is counted including the carbon number of the substituent, and preferably 6 to 10. Examples of these aryl groups include substituted or unsubstituted phenyl groups such as phenyl group, hydroxyphenyl group (such as 4-hydroxyphenyl group), and trifluoromethylphenyl group (such as 4-trifluoromethylphenyl group). .

The alkyl part of the aralkyl group having 7 to 20 carbon atoms in R ⁴³ may be linear or branched. The carbon number of the aralkyl group is usually 7 to 20, preferably 7 to 10. Examples of the aralkyl group include phenylalkyl groups such as a benzyl group, a phenylpropyl group (such as 1-methyl-3-phenylpropyl group), and a phenylbutyl group (such as 3-amino-1-phenylbutyl group).

The acyl group having 2 to 10 carbon atoms in R ⁴³ may be unsubstituted, or a substituent such as a saturated aliphatic hydrocarbon group or an alkoxyl group may be bonded thereto. The carbon number of the acyl group is counted including the carbon number of the substituent, and the number is preferably 6 to 10. Examples of the acyl group include an acetyl group, a benzoyl group, an o-toluyl group, an m-toluyl group, a p-toluyl group, and a methoxybenzoyl group (such as a p-methoxybenzoyl group).

  Examples of the N-substituted sulfamoyl group include groups represented by formulas (9) to (15). When one molecule has two or more N-position-substituted sulfamoyl groups, the N-position-substituted sulfamoyl groups may be the same or different.

  Examples of the barbituric acid azo dyes include compounds represented by formulas (7-1) to (7-7). Preferably, formulas (7-1), (7-3), (7 -4), (7-5) and compounds represented by (7-7).

  The pyridone azo dye is not particularly limited, and a known substance can be used, but a dye represented by the formula (8) is preferably used.

[In Formula (8), Z is a phenyl group having one or two at least one group selected from the group consisting of a carboxyl group, a carbamoyl group, a sulfo group, and a sulfamoyl group optionally substituted at the N-position. Or a naphthyl group having 1 to 3 groups selected from the group consisting of a carboxyl group, a carbamoyl group, a sulfo group and a sulfamoyl group optionally substituted at the N-position.
R ²¹ represents a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group, or a trifluoromethyl group.
R ²² represents any one of a hydrogen atom, a cyano group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, a sulfo group, and an ammonium salt, a lithium salt, a sodium salt, or a potassium salt of each of the above substituents.
R ²³ is a hydrogen atom, an optionally substituted linear, branched or cyclic saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, An optionally substituted aralkyl group having 7 to 20 carbon atoms, a group in which a part of carbon atoms of an alicyclic hydrocarbon group having 3 to 20 carbon atoms is substituted with a hetero atom, a carbamoyl group, an N-substituted carbamoyl group , An optionally substituted alkyloxycarbonyl group having 2 to 20 carbon atoms, an optionally substituted aryloxycarbonyl group having 7 to 30 carbon atoms, an optionally substituted acyl group having 2 to 20 carbon atoms, The C1-C30 aliphatic sulfonyl group which may be substituted or the C6-C30 arylsulfonyl group which may be substituted is represented.
Furthermore, Formula (8) may form a dimer or higher multimer at an arbitrary position. ]

In formula (8), the N-substituted sulfamoyl group of the phenyl group and naphthyl group represented by Z is represented by —SO ₂ N (R ²⁴ ) R ²⁵ .
R ²⁴ and R ²⁵ are each independently a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms (this alkoxy group having 1 to 8 carbon atoms is added to this saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms). Represents an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 2 to 10 carbon atoms (provided that R ²⁴ and R ²⁵ are hydrogen atoms at the same time). Never).
The saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms may be linear, branched or cyclic, and the saturated aliphatic hydrocarbon group preferably has 6 to 10 carbon atoms.

Examples of the saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R ²⁴ and R ²⁵ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a sec-butyl group. Tert-butyl group, methylbutyl group (1,1,3,3-tetramethylbutyl group, etc.), methylhexyl group (1-methylhexyl group, 1,5-dimethylhexyl group, etc.), ethylhexyl group (2-ethylhexyl, etc.) Group), cyclopentyl group, cyclohexyl group, methylcyclohexyl group (such as 2-methylcyclohexyl group), cyclohexylalkyl group, etc., preferably isopropyl group, isobutyl group, 1,1,3,3-tetramethylbutyl group 1,5-dimethylhexyl group, 2-ethylhexyl group and the like.
As described above, the saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R ²⁴ and R ²⁵ is substituted with an alkoxyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms). Also good. Examples of the saturated aliphatic hydrocarbon group substituted with the alkoxy group having 1 to 8 carbon atoms include a propoxypropyl group (such as 3- (isopropoxy) propyl group).

The aryl group having 6 to 20 carbon atoms represented by R ²⁴ and R ²⁵ may have a substituent such as an unsaturated aliphatic hydrocarbon group or a hydroxyl group. Carbon number of the said aryl group is counted including carbon number of a substituent, and is 6-20 normally, Preferably it is 6-10. Specific examples of these aryl groups include substituted or unsubstituted phenyl groups such as phenyl group, hydroxyphenyl group (such as 4-hydroxyphenyl group), and trifluoromethylphenyl group (such as 4-trifluoromethylphenyl group). Etc.

The alkyl part of the aralkyl group represented by R ²⁴ and R ²⁵ may be linear or branched. The carbon number of the aralkyl group is usually 7 to 20, preferably 7 to 10. The aralkyl is typically a phenylalkyl group such as a benzyl group, a phenylpropyl group (such as 1-methyl-3-phenylpropyl group), and a phenylbutyl group (such as 3-amino-1-phenylbutyl group).

The acyl group represented by R ²⁴ and R ²⁵ may be unsubstituted, or a substituent such as a saturated aliphatic hydrocarbon group or an alkoxyl group may be bonded thereto. Carbon number of an acyl group is counted including carbon number of a substituent, and the number is 2-10 normally, Preferably it is 6-10. Examples of the acyl group include an acetyl group, a benzoyl group, and a methoxybenzoyl group (such as a p-methoxybenzoyl group).

R ²¹ is represented by any one of a hydrogen atom, a saturated aliphatic hydrocarbon group, a carboxyl group, and a trifluoromethyl group.

The saturated aliphatic hydrocarbon group represented by R ²¹ may be linear, branched or cyclic. The carbon number of the saturated aliphatic hydrocarbon group does not include the carbon number of the substituent. The carbon number is preferably 2 to 8, more preferably 3 to 6. These saturated aliphatic hydrocarbon groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group and the like. Can be mentioned.

R ²² represents any one of a hydrogen atom, a cyano group, a carbamoyl group, or an N-substituted carbamoyl group, a sulfamoyl group, a sulfo group, and an ammonium salt, a lithium salt, a sodium salt, or a potassium salt of each of the above substituents.

As the N-substituted carbamoyl group represented by R ²² , —CON (R ²⁶ ) R ²⁷ (wherein R ²⁶ and R ²⁷ are each independently a hydrogen atom, a saturated aliphatic group having 1 to 10 carbon atoms). A hydrocarbon group, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted by an alkoxyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or the number of carbon atoms Represents an acyl group of 2 to 10).
The explanation and specific examples of the saturated aliphatic hydrocarbon group, aryl group, aralkyl group and acyl group for R ²⁶ and R ²⁷ are the same as those for R ²⁴ and R ²⁵ described above. However, specific examples of the acyl group further include a benzoyl group containing a halogen atom, such as a bromobenzoyl group (p-bromobenzoyl group and the like).

R ²³ is an optionally substituted linear, branched or cyclic saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, and a substituted group. An aralkyl group having 7 to 20 carbon atoms, a group in which part of carbons of the alicyclic hydrocarbon group having 3 to 20 carbon atoms is substituted with a hetero atom, a carbamoyl group optionally substituted at the N-position, An alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group, an aliphatic sulfonyl group, or an arylsulfonyl group is represented.

Examples of the saturated aliphatic hydrocarbon group represented by R ²³ include the same groups as the saturated aliphatic hydrocarbon group in R ²¹ described above.

The aryl groups denoted by R ^23, the carbon number is usually 6 to 30, preferably 6 to 20, more preferably 6 to 16. Specific examples of these aryl groups include phenyl, 4-nitrophenyl, 2-nitrophenyl, 2-chlorophenyl, 2,4-dichlorophenyl, 2,4-dimethylphenyl, 2-methyl. A phenyl group, 4-methoxyphenyl group, 2-methoxyphenyl group, 2-methoxycarbonyl-4-nitrophenyl group, etc. are mentioned.

The group in which a part of carbons of the alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ²³ is substituted with a hetero atom may be saturated or unsaturated, and has a total carbon number. As, 3-20 are preferable, More preferably, it is 5-15. Specific examples of the group having a heterocycle include a pyrazole group, 1,2,4-triazole group, isothiazole group, benzoisothiazole group, thiazole group, benzothiazole group, oxazole group, 1,2, Examples include 4 thiadiazole groups. Furthermore, you may have a substituent.

The aralkyl group represented by R ²³ may be linear or branched, and the carbon number is preferably 7 to 10. Specific examples of the aralkyl include phenylalkyl groups such as a benzyl group, a phenylpropyl group (such as 1-methyl-3-phenylpropyl group), and a phenylbutyl group (such as 3-amino-1-phenylbutyl group). Representative.

The N-substituted carbamoyl group represented by R ²³ is the same as the N-substituted carbamoyl group described above for R ²² .

The alkyloxycarbonyl group denoted by R ^23, may have a substituent be unsubstituted, may be cyclic. The total number of carbon atoms of the alkyloxycarbonyl group is usually 2 to 20, preferably 2 to 16, and more preferably 2 to 10 alkyloxycarbonyl group. Specific examples of this alkyloxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group.

The aryloxycarbonyl group represented by R ²³ may be unsubstituted or substituted, and the total carbon number is usually 7 to 30, preferably 7 to 20, and more preferably. 7-16. Specific examples of the aryloxycarbonyl group include a phenoxycarbonyl group and a 4-methylphenoxycarbonyl group.

The acyl group represented by R ²³ may be an aliphatic carbonyl group or an arylcarbonyl group, may be saturated or unsaturated, may be cyclic, and further has a substituent. It may be. As a total carbon number, it is 2-20 normally, Preferably it is 2-15, More preferably, it is 2-10. Specific examples of the acyl group include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, benzoyl group and the like.

The aliphatic sulfonyl group represented by R ²³ may be saturated, unsaturated, or cyclic. As total carbon number, it is 1-30 normally, Preferably it is 1-20, More preferably, it is 1-16. Specific 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 represented by R ²³ may have a substituent, and the total carbon number is usually 6 to 30, preferably 6 to 20, and more preferably 6 to 18. It is. Specific examples of the arylsulfonyl group include benzenesulfonyl and toluenesulfonyl groups.

Examples of the pyridone azo dye include the following compounds, and compounds represented by formulas (8-1) to (8-9) are preferable.

The pyridone azo dye represented by the formula (8) may form a dimer or more multimer at an arbitrary position.
The multimer in the formula (8) means one having two or more groups represented by the formula (8) in one molecule, and specific examples thereof include the following compounds.

  The pyrazolone azo dye is not particularly limited, and a known substance can be used. For example, as described in JP 2006-276512 A, JP 2005-263926 A, JP 2006-015669 A, and the like. Pyrazolone azo dyes can be used.

  Specifically, C.I. I. Acid Yellow 17, C.I. I. Solvent Orange 56, C.I. I. Examples thereof include Solvent Yellow 82 and the following compounds.

  The quinophthalone dye is not particularly limited, and a known substance can be used. For example, quinophthalone described in JP-A-5-39269, JP-A-6-220339, JP-A-8-171201, and the like. Series dyes can be used.

  Specifically, C.I. I. Solvent Yellow 33, C.I. I. Disperse Yellow 54, C.I. I. Disperse Yellow 64 and the following compounds are exemplified.

The cyanine dye is not particularly limited, and a known substance can be used.
For example, cyanine dyes described in JP-A-2005-194509, JP-A-2007-131818, JP-A-2005-297406, and the like can be used.
Specific examples include the following compounds.

  Further, (A) the colorant may contain a pigment as long as the effects of the present invention are not impaired.

  Examples of the pigment include compounds classified as pigments in the color index (published by The Society of Dyers and Colorists). I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214; I. And green pigments such as C.I. Pigment Green 7 and 36. I. Pigment yellow 138, 139, 150, C.I. I. Pigment Green 7, 36.

  The pigment can be obtained as a dispersion in a state where the pigment is uniformly dispersed in the solution by carrying out a dispersion treatment by containing a dispersant if necessary.

  Examples of the dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine, and may be used alone or in combination of two or more.

  Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, etc. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFuck (manufactured by Dainippon Ink Chemical Co., Ltd.) , FLORARD (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.), PB821 (manufactured by Ajinomoto Co., Inc.) Etc.

When using a dispersing agent, the usage-amount is a mass fraction with respect to 100 mass% of pigments, Preferably it is 0.1-100 mass%, More preferably, it is 5-50 mass%. It is preferable that the amount of the dispersant used be in the above range because a uniform dispersion tends to be obtained.
The content of the colorant (A) used in the colored curable composition of the present invention is 30 to 65% by mass, preferably 35 to 60% by mass, based on the solid content of the colored curable composition. %, More preferably 35 to 55% by mass.

  (A) When the content of the colorant is in the above range, the color density when the color filter is obtained is sufficient, and the polymerizable compound can be contained in the composition in a necessary amount or more. This is preferable because a pattern with sufficient strength can be formed.

As the polymerizable compound (B) used in the present invention, monomers or oligomers that are cured by heat or light, or both can be used, and these may be used in combination. A known substance can be used as the monomer or oligomer.

  Specific examples of monomers include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate derivatives having a carboxyl group, ethylene oxide glycerin triacrylate and ethylene Oxidized trimethylolpropane triacrylate, propylene oxided glycerin triacrylate and the like can be mentioned.

  Examples of the oligomer include epoxy acrylate, urethane acrylate, polyester acrylate, and the like. For example, the current state and prospects of UV / EB curing technology (CMC Publishing) pages 18 to 20 can be used.

  (B) Content of a polymeric compound is a mass fraction with respect to solid content of a colored curable composition, Preferably it is 5-50 mass%, More preferably, it is 10-40 mass%, Most preferably It is 12-35 mass%. When the content of the polymerizable compound is within the above range, curing is sufficiently performed, the film thickness ratio before and after development is improved, and the adhesiveness tends to be good, which is preferable.

  Here, the solid content in the present specification is the total of the components that are not liquid at room temperature among the (A) colorant, the (B) polymerizable compound, and the components added as necessary, in the colored curable composition. Say quantity.

  The colored curable composition of the present invention may further contain (C) a binder resin. The (C) binder resin preferably contains a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. The content of the structural unit derived from the (meth) acrylic acid is preferably 10 mol% or more and 40 mol% or less, more preferably 13 mol% or more in terms of mole fraction in all the structural units constituting the binder resin. 35 mol% or less. When the content of the structural unit derived from meth (acrylic) acid is in the above range, it is preferable because the solubility is good at the time of development and the residue hardly remains after development.

  Examples of the other monomer that leads to the constituent unit of the binder resin other than the constituent unit derived from (meth) acrylic acid include, for example, aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, and unsaturated compounds. Carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, monoacryloyl group or mono at the end of the polymer molecular chain And macromonomers having a methacryloyl group. For example, examples of the structural unit include a unit represented by the formula (32) and a unit represented by the formula (33).

[In Formula (32) and Formula (33), R ¹⁶ and R ¹⁷ each independently represents a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms. ]

R ¹⁶ and R ¹⁷ are a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a 1-methylbutyl group, 2 -Methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 2-ethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group and the like can be mentioned, preferably hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert- A butyl group is mentioned, More preferably, a hydrogen atom, a methyl group, and an ethyl group are mentioned.

Specific examples of the binder resin (C) include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, methacrylic acid, Acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / constituent component represented by formula (33) (wherein, in formula (33), R ¹⁶ represents a methyl group, R ¹⁷ Represents a hydrogen atom.) / N-benzylmaleimide / benzyl methacrylate copolymer, methacrylic acid / constituent component represented by formula (33) (wherein, in formula (33), R ¹⁶ represents a methyl group) represents, R ¹⁷ represents a hydrogen atom.) / N-cyclohexyl maleimide / benzyl methacrylate copolymer , Components represented by methacrylic acid / formula (32) (However, in this case, the formula (32), R ¹⁶ represents a methyl group, R ¹⁷ represents a hydrogen atom.) / Benzyl methacrylate copolymer, Component represented by formula (32) (wherein, in formula (32), R ¹⁶ represents a methyl group and R ¹⁷ represents a hydrogen atom) / benzyl methacrylate copolymer, methacrylic acid / formula (33) (wherein, in formula (33), R ¹⁶ represents a methyl group and R ¹⁷ represents a hydrogen atom) / styrene / dicyclopentanyl methacrylate copolymer, etc. Is preferred.

  The acid value of the binder resin (C) used in the present invention is preferably 30 to 150, more preferably 35 to 135, and particularly preferably 40 to 120. When the acid value is in the above range, the solubility in the developer is improved and the unexposed area is easily dissolved, and the sensitivity is increased so that the pattern of the exposed area remains during development and the remaining film ratio tends to be improved. Is preferable. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration with an aqueous potassium hydroxide solution. .

  (C) Content of binder resin is a mass fraction with respect to solid content of a colored curable composition, Preferably it is 5-40 mass%, More preferably, it is 8-35 mass%, Most preferably 10 to 32% by mass. (C) It is preferable that the content of the binder resin is in the above range because a pattern can be formed and the resolution and the remaining film ratio tend to be improved.

(C) binder resin having a component represented by formula (29), for example, a component derived from methacrylic acid / a component represented by formula (32) (here, in formula (29), R ¹⁶ represents a methyl group, and R ¹⁷ represents a hydrogen atom.) / A copolymer comprising components derived from benzyl methacrylate is obtained by polymerizing methacrylic acid and benzyl methacrylate to obtain a two-component polymer. The obtained two-component polymer can be obtained by reacting the compound represented by the formula (34) (wherein R ¹⁸ represents a hydrogen atom in the formula (34)).

Constituent derived from methacrylic acid / constituent represented by formula (33) (wherein, in formula (33), R ¹⁶ represents a methyl group and R ¹⁷ represents a hydrogen atom) / benzyl methacrylate. A copolymer derived from dicyclopentanyl methacrylate / a copolymer derived from dicyclopentanyl methacrylate is obtained by reacting a copolymer of benzyl methacrylate, methacrylic acid and dicyclopentanyl methacrylate with glycidyl methacrylate. Can do.

  (C) The polystyrene-reduced weight average molecular weight of the binder resin is preferably 5,000 to 100,000, more preferably 6,000 to 80,000, and particularly preferably 7,000 to 60,000. . When the molecular weight is within the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution tends to be improved, which is preferable.

  The colored curable composition of the present invention may further contain (D) a photopolymerization initiator. Examples of the photopolymerization initiator include triazine compounds, acetophenone compounds, biimidazole compounds, active radical generators, and acid generators.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl ] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine and the like. 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl)- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1 3,3-triazine, more preferably 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine.

  Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropane-1. -One, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino- 1- (4-morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl- And oligomers of 1- [4- (1-methylvinyl) phenyl] propan-1-one, etc. Preferred examples include 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) propane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butane- 1-one, more preferably 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4, 4 ′, 5,5′-tetra (4-carboethoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (4-bromophenyl) biimidazole 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (2,4-dichlorophenyl) biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2- Chlorophenyl)- , 4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2, 2′-bis (2,6-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-nitrophenyl) -4,4 ′, 5,5′- Examples include tetraphenylbiimidazole, 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and preferably 2,2′-bis (2-chlorophenyl). Examples include -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

  An active radical generator generates an active radical when irradiated with light. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, and oxime compounds.

  Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the oxime compounds include O-acyloxime compounds, and specific examples thereof include 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O—. Benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1-one oxime-O-acetate 1- (4-phenylsulfanyl-phenyl) -butan-1-one oxime-O-acetate and the like.

  Examples of active radical generators other than those exemplified above include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, and 9,10-phenanthrenequinone. Camphorquinone, methyl phenylglyoxylate, titanocene compounds, and the like can also be used.

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium-p-toluenesulfonate, 4-acetoxyphenyl. Onium salts such as methylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium-p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.

  Among the compounds described above as the active radical generator, there are compounds that generate an acid simultaneously with the active radical. For example, a triazine photopolymerization initiator is also used as an acid generator.

  Content of said (D) photoinitiator is a mass fraction with respect to the total amount of (B) polymeric compound and (C) binder resin, Preferably it is 0.1-25 mass%, More Preferably it is 1-20 mass%. (D) When the content of the photopolymerization initiator is within the above range, the sensitivity is increased and the exposure time is shortened and the productivity is improved. On the other hand, the line and space pattern is resolved due to the sensitivity being too high. This is preferable because the line width tends not to be too large at the minimum line width.

The colored curable composition of the present invention may further contain (E) a photopolymerization initiation assistant. (E) The photopolymerization initiation assistant is usually used in combination with (D) a photopolymerization initiator, and (D) is used to promote polymerization of a photopolymerizable compound that has been polymerized by the photopolymerization initiator. Compound.
(E) Examples of the photopolymerization initiation assistant include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.
Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylbenzoate. Aminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (Ethylmethylamino) benzophenone and the like can be mentioned, among which 4,4′-bis (diethylamino) benzophenone is preferable.

  Examples of the alkoxyanthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  (E) The photopolymerization initiation assistant may be used alone or in combination of two or more. In addition, as the (E) photopolymerization initiation assistant, commercially available products can be used, and as the commercially available (E) photopolymerization initiation assistant, for example, EAB-F (Hodogaya Chemical Co., Ltd. And 4,4′-bis (diethylamino) benzophenone) and other organic amine compounds.

  Examples of the combination of (D) photopolymerization initiator / (E) photopolymerization initiation assistant in the colored curable composition of the present invention include, for example, 2,4-bis (trichloromethyl) -6-piperonyl-1,3, 5-triazine / 4,4′-bis (diethylamino) benzophenone, diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propane-1- ON / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4,4′-bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4′- Bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phen L] propan-1-one / 4,4′-bis (diethylamino) benzophenone, 1-hydroxycyclohexyl phenyl ketone / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (1-Methylvinyl) phenyl] propan-1-one oligomer / 4,4′-bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone, 2- (4- Methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butan-1-o / 4,4′-bis (diethylamino) benzophenone and the like, preferably 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) Benzophenone, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine / 4,4′-bis (diethylamino) benzophenone, 2- (4-methylbenzyl) -2-dimethylamino-1 -(4-morpholinophenyl) butan-1-one / 4,4'-bis (diethylamino) benzophenone.

  When these (E) photopolymerization initiation assistants are used, the amount used is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, per 1 part by mass of the (D) photopolymerization initiator. Part.

  The colored curable composition of the present invention may further contain (F) a solvent. Examples of the solvent (F) include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, and the like.

  Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. , Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Over DOO, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, methoxy pentyl acetate, anisole, phenetole, and the like methyl anisole.

  Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.

  Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and 4-hydroxy-4-methyl-2. Examples include pentanone.

  Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diacetone alcohol, and glycerin.

  Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3 -Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2- Ethyl methyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutane Examples include methyl acid, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone.

  Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide.

Examples of other (F) solvents include N-methylpyrrolidone and dimethyl sulfoxide.
The above (F) solvents may be used alone or in combination of two or more.

  Among the solvents (F), a solvent containing propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diacetone alcohol is preferably used.

  (F) Content of a solvent is a mass fraction with respect to a colored curable composition, Preferably it is 70-90 mass%, More preferably, it is 75-88 mass%. When the content of the solvent is in the above range, in-plane uniformity at the time of coating is good, and the color density when the color filter is formed is sufficient, and the display characteristics are good.

  Further, (G) a surfactant may be contained. Examples of the surfactant (G) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom.

  Examples of the silicone surfactant include surfactants having a siloxane bond. Specifically, it is the Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA, SH30PA, polyether-modified silicone oil SH8400 (manufactured by Torresilicone), KP321, KP322, KP323 under the trade names. , KP324, KP326, KP340, KP341 (made by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (made by GE Toshiba Silicone Co., Ltd.).

  Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, under the product names Florard FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFuck F142D, F171, F172, F173, F177, F183, F470, F475, and R30 ( Dainippon Ink & Chemicals Co., Ltd.), EFTOP EF301, EF303, EF351, EF352 (made by Shin-Akita Kasei), Surflon S381, S382, SC101, SC105 (made by Asahi Glass Co., Ltd.) ), E5844 (manufactured by Daikin Fine Chemical Laboratory), BM-1000, BM-1100 (manufactured by BM Chemie), and the like.

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specific examples include Megafax R08, BL20, F475, F477, F443 (Dainippon Ink Chemical Co., Ltd.).
These surfactants may be used alone or in combination of two or more.

  The colored curable composition of the present invention may contain an organic acid having a molecular weight of 1,000 or less. As said organic acid, the organic acid disclosed by Unexamined-Japanese-Patent No. 5-34363 is mentioned, for example. Specifically, malonic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, citraconic acid, itaconic acid, mesaconic acid, fumaric acid, phthalic acid, acrylic acid, Methacrylic acid is mentioned, Preferably malonic acid, oxalic acid, fumaric acid, and phthalic acid are mentioned. By containing an organic acid having a molecular weight of 1,000 or less, the residue tends to be even better, which is preferable.

  The colored curable composition of the present invention further includes a filler, (C) a polymer compound other than the binder resin, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, an organic amine compound, (H) You may contain additives, such as a hardening | curing agent.

  Examples of the filler include fine particles such as glass and alumina.

  Examples of the polymer compound other than the (C) binder resin include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

  Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Examples include ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  Examples of the antioxidant include 4,4′-thio-bis (6-tert-butyl-3-methylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-). 4-hydroxyphenyl) propionate], 1,6-hexanediol-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4, 6-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,6-di-tert-butyl-4 Methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-thio-bis (3-methyl-6) -Tert-butylphenol), 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane 1,3,5-tris (4-hydroxybenzyl) benzene and tetrakis [methylene-3- (3,5′-di-tert-butyl-4′-hydroxyphenylpropionate)] methane.

Examples of the ultraviolet absorber include benzotriazoles such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole;
Benzophenone series such as 2-hydroxy-4-octyloxybenzophenone;
Benzoate systems such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate;
And triazines such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol.

  Examples of the aggregation preventing agent include sodium polyacrylate.

By adding the organic amine compound, a residue is not generated on the unexposed substrate during development, and a pixel having excellent adhesion to the substrate can be provided.
Examples of the organic amine compound include n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n- Monoalkylamines such as octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine;
Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine;
Methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, Dialkylamines such as di-n-pentylamine and di-n-hexylamine;
Monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;
Dicycloalkylamines such as dicyclohexylamine;
Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n -Trialkylamines such as butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine;
Dialkylmonocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;
Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine;
Monoalkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, and 6-amino-1-hexanol Kind;
Monocycloalkanolamines such as 4-amino-1-cyclohexanol;
Dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine;
Dicycloalkanolamines such as di (4-cyclohexanol) amine;
Trialkanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine;
Tricycloalkanolamines such as tri (4-cyclohexanol) amine;
3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1 , 2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, aminoalkanediols such as 2-diethylamino-1,3-propanediol;
Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol and 4-amino-1,3-cyclohexanediol;
Amino group-containing cycloalkanone methanols such as 1-aminocyclopentanone methanol and 4-aminocyclopentanone methanol;
Amino group-containing cycloalkanemethanols such as 1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid;
Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, p-isopropylaniline, pn-butylaniline, p-tert-butylaniline, 1- Aromatic amines such as naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline;
aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol;
Examples include aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, and p-diethylaminobenzoic acid.

  Examples of the (H) curing agent include, for example, a compound capable of reacting with a carboxyl group in the (C) binder resin by being heated to crosslink the (C) binder resin; And a compound capable of curing. As said compound, an epoxy compound, an oxetane compound, etc. are mentioned, for example, An oxetane compound is used preferably.

  Here, as the epoxy compound, for example, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac type epoxy resin, other aromatic epoxy resins , Alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxy resins such as epoxidized oil, brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof Aliphatic, alicyclic or aromatic epoxy compounds, epoxidized products of butadiene (co) polymers, epoxidized products of isoprene (co) polymers, (co) polymers of glycidyl (meth) acrylates, triglycidyl Examples include isocyanurate.

  Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and bisoxetane cyclohexanedicarboxylate.

  When the colored curable composition of the present invention contains an epoxy compound, an oxetane compound or the like as a curing agent, it may contain a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound or the oxetane skeleton of the oxetane compound. . Examples of the compound include polyvalent carboxylic acids, polyvalent carboxylic acid anhydrides, and acid generators.

Examples of the polyvalent carboxylic acids include phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3 Aromatic polycarboxylic acids such as 3,3 ', 4,4'-benzophenonetetracarboxylic acid;
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid;
Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid And alicyclic polyvalent carboxylic acids such as 1,2,4,5-cyclohexanetetracarboxylic acid.

Examples of the polyvalent carboxylic acid anhydrides include aromatic phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride. Carboxylic anhydrides;
Aliphatic polycarboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Kind;
Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polycarboxylic acid anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic anhydride, and nadic anhydride;
Examples include ester group-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitic acid and glycerin tristrimellitic anhydride.

  As said carboxylic acid anhydride, you may use what is marketed as an epoxy resin hardening | curing agent. Examples of the epoxy resin curing agent include ADEKA HARDNER EH-700 (manufactured by Asahi Denka Kogyo Co., Ltd.), RIKACID HH, MH-700 (both manufactured by Shin Nippon Rika Co., Ltd.) and the like. It is done.

  The above curing agents may be used alone or in combination of two or more.

  As a method of forming a color filter pattern using the colored curable composition of the present invention, for example, the colored curable composition of the present invention is first formed on a substrate or another resin layer (for example, on the substrate). Applied to another colored curable composition layer, etc.), removing a volatile component such as a solvent to form a colored layer, exposing the colored layer through a photomask, developing, and In response to this, the so-called photolithography method or a colored curable composition is applied to a substrate or another resin layer using an inkjet apparatus, and a volatile component such as a solvent is removed to form a colored layer. And an ink jet method for curing by at least one of the above.

  The color filter thus obtained contains a pattern, and a suitable liquid crystal display device can be obtained by using the color filter.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.

  In the colored curable composition of the present invention, the method for producing the phthalocyanine compound represented by the formula (1) used as the colorant (A) is disclosed in JP-A-63-3066, JP-A-63-141982, JP-A-1-45474, JP-A-2-282386, JP-A-4-39361, JP-A-5-222302, JP-A-6-107663, JP-A-5-221952, JP-A-5-345861, etc. It can be produced by the method described in the publication.

Synthesis example 1
<Synthesis of Colorant (A-1)>
Synthesis of Compound Represented by Formula (1-1) In a 100 mL four-necked flask, 9.29 g (20 mmol) of 3,6-difluoro-4,5-bis (p-methoxycarbonylphenoxy) phthalonitrile, anhydrous First, 0.59 g (6 mmol) of cuprous chloride and 20 mL of benzonitrile were charged and reacted at 175 ° C. for 12 hours. After completion of the reaction, the reaction mixture was poured into methanol, and the resulting solid was washed with methanol and then with water, and dried at 60 ° C. under reduced pressure to obtain 5.45 g of the desired green compound (yield). Rate 75.1%).
When the obtained green compound was dissolved in ethyl lactate and the visible absorption spectrum was measured, the maximum absorption wavelength was 654.0 nm, and the molar extinction coefficient (ε) was 1.026 × 10 ⁵ .

Synthesis example 2
<Synthesis of Colorant (A-2)>
Synthesis of phthalocyanine compound represented by formula (1-14) In a 100 mL four-necked flask, 3,4,6-trifluoro-5- (2-methyl-6-methoxyethoxycarbonylphenoxy) phthalonitrile 7 .83 g (20 mmol), vanadium trichloride 0.94 g (6 mmol) and benzonitrile 25 mL were charged and reacted at 175 ° C. for 4 hours. After completion of the reaction, the insoluble matter was filtered off, the solvent was distilled off, washed twice with 200 mL of methanol, and dried under reduced pressure at 60 ° C. to obtain 4.42 g of the desired green compound ( Yield 54.2%).
When the obtained green compound was dissolved in ethyl lactate and the visible absorption spectrum was measured, the maximum absorption wavelength was 714.0 nm, and the molar extinction coefficient (ε) was 1.055 × 10 ⁵ .

Synthesis example 3
<Synthesis of Colorant (A-3)>
Synthesis of Barbituric Acid Azo Dye Represented by Formula (7-4) 300 g of water was added to 30 g (61 mmol) of 2,2′-benzidinedisulfonic acid (containing 30% water) represented by Formula (35) Thereafter, the pH was adjusted to 7 to 8 with a 30% aqueous sodium hydroxide solution under ice cooling. The following operations were performed under ice cooling. 12.6 g (183 mmol) of sodium nitrite was added and stirred for 30 minutes. After adding 38.1 g of 35% hydrochloric acid little by little to give a brown solution, the mixture was stirred for 2 hours. An aqueous solution in which 5.3 g (61 mmol) of amidosulfuric acid was dissolved in 57.4 g of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

  372 g of water was added to 18.6 g (146 mmol) of N, N′-dimethylbarbituric acid represented by the formula (36), and then adjusted to pH 8-9 with 30% aqueous sodium hydroxide solution under ice cooling.

  The following operations were performed under ice cooling. The aqueous barbiturate aqueous solution was stirred to give a colorless solution, and then a suspension containing a diazonium salt was added dropwise with a pump while adjusting the pH to 8 to 9 with a 30% aqueous sodium hydroxide solution. After completion of dropping, the mixture was further stirred for 3 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 15 g (21 mmol, yield 34%) of the azo compound represented by the formula (37).

  A flask equipped with a condenser and a stirrer is charged with 5 g (7 mmol) of the azo compound represented by the formula (37), 50 g of chloroform and 2 g (3 mmol) of N, N-dimethylformamide, and is stirred at 20 ° C. or lower. While maintaining the temperature, 6 g (54 mmol) of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 3 g (20 mmol) of 3-aminophenylbutane and 10 g (103 mmol) of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixed liquid of 29 g of acetic acid and 300 g of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion exchange water, and dried under reduced pressure at 60 ° C. to obtain 6 g (6 mmol, yield 78%) of the azo compound represented by the formula (7-4).

The azo compound obtained in this example was subjected to LC-MS analysis under the following conditions.
Apparatus: Agilent 1100 (manufactured by Agilent Technology)
Detector; UV detector; 254 nm
Column; Sumipax ODS (manufactured by Sumika Chemical Analysis Co., Ltd.)
Elution solvent: Solvent system in which 0.1% of trifluoromethylacetic acid was added to water-acetonitrile mixed solvent The content of each azo compound was calculated from the peak area. As a result, the azo compound represented by formula (7-4) was detected as a compound having a molecular weight of 940, and the area percentage value with respect to the total peak area was 98%.

Synthesis example 4
<Synthesis of Colorant (A-4)>
Synthesis of Pyridoneazo Dye Represented by Formula (16) After adding 3000 g of water to 100 g (203 mmol) of 2,2′-benzidinedisulfonic acid (containing 30% water) represented by Formula (35), The pH was adjusted to 7-8 with a 30% aqueous sodium hydroxide solution. The following operations were performed under ice cooling. 56 g (812 mmol) of sodium nitrite was added and stirred for 30 minutes. After adding 150 g of 35% hydrochloric acid little by little to make a brown solution, the mixture was stirred for 2 hours. An aqueous solution in which 38 g (406 mmol) of amidosulfuric acid was dissolved in 380 g of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.
After adding 1000 g of water to 76 g (426 mmol) of 1-ethyl-3-cyano-4-methyl-6-hydroxypyrid-2-one represented by the formula (38), 30% hydroxylation was performed under ice cooling. The pH was adjusted to 8-9 with an aqueous sodium solution.

  The following operations were performed under ice cooling. The aqueous alkaline solution of pyridones was stirred to give a colorless solution, and then a suspension containing a diazonium salt was added dropwise with a pump while adjusting the pH to 8 to 9 with a 30% aqueous sodium hydroxide solution. After completion of dropping, the mixture was further stirred for 3 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 137 g (204 mmol, yield 100%) of the azo compound represented by the formula (39).

  In a flask equipped with a condenser and a stirrer, 5 g (7 mmol) of the azo compound represented by the formula (39) obtained by the above operation, 50 g of chloroform and 2.4 g (33 mmol) of N, N-dimethylformamide were obtained. Then, 7 g (59 mmol) of thionyl chloride was added dropwise while maintaining the temperature at 20 ° C. or lower with stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 4 g (30 mmol) of 1,5-dimethylhexylamine and 12 g (119 mmol) of triethylamine was added dropwise. Thereafter, the reaction was carried out by stirring overnight at the same temperature. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixed liquid of 29 g of acetic acid and 300 g of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion exchange water, and dried under reduced pressure at 60 ° C. to obtain 6 g (6 mmol, yield 80%) of the azo compound represented by the formula (16).

  When the same structural analysis as described above was performed on the azo compound obtained in this example, the azo compound represented by the formula (16) was detected as a compound having a molecular weight of 944, and the area percentage value relative to the total peak area. Was 58.3%. Furthermore, the monosulfonamidated azo compound represented by the formula (40) was detected as a compound having a molecular weight of 833, and the area percentage value with respect to the total peak area was 30.1%.

Synthesis example 5
<Synthesis of Resin (C-1)>
333 g of propylene glycol monomethyl ether acetate was introduced into a 1 L flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Thereafter, after the temperature of the solution in the flask was raised to 100 ° C., 22.0 g (0.10 mol) of dicyclopentanyl methacrylate (FA-513M; manufactured by Hitachi Chemical Co., Ltd.), 70.5 g of benzyl methacrylate ( 0.40 mol), 43.0 g (0.5 mol) of methacrylic acid, 3.6 g of azobisisobutyronitrile and 164 g of propylene glycol monomethyl ether acetate were added to the flask using a dropping funnel over 2 hours. After the completion of the dropwise addition, stirring was further continued at 100 ° C. for 5 hours.

  After the stirring was completed, air was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was changed to air. Then, 35.5 g of glycidyl methacrylate [0.25 mol (based on methacrylic acid used in this reaction)] In a molar fraction, 50 mol%)], 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours to contain the resin (C-1). A solution was obtained (solid content 38.5% by mass, acid value 80 mg KOH / g).

Here, the acid value is a value measured as an amount (mg) of potassium hydroxide necessary to neutralize 1 g of a polymer having an acid group such as carboxylic acid, and is usually a potassium hydroxide aqueous solution having a known concentration. It is calculated | required by titrating using.
The obtained resin (C-1) had a polystyrene equivalent weight average molecular weight of 9,000.

The measurement of the weight average molecular weight in terms of polystyrene of the (C-1) binder resin was performed using the GPC method under the following conditions.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent; THF
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

The components used in this example are as follows, and may be omitted below.
(A-1) Colorant: Dye obtained in Synthesis Example 1 (A-2) Colorant: Dye obtained in Synthesis Example 2 (A-3) Colorant: Dye obtained in Synthesis Example 3 (A -4) Colorant: Colorant obtained in Synthesis Example 4 (A-5) Colorant: Compound represented by formula (29) (cyanine dye; NK-3212: manufactured by Hayashibara Biochemical Laboratories)

(A-6) Colorant: Compound represented by formula (41) (FB-22: Phthalocyanine dye manufactured by Yamada Chemical Co., Ltd.)

(A-7) Colorant: Compound represented by formula (42) (FB-24: Phthalocyanine dye manufactured by Yamada Chemical Co., Ltd.)

(B-1) Photopolymerizable compound: DPHA (manufactured by Nippon Kayaku Co., Ltd.)
(B-2) Photopolymerizable compound: A-GLY-3E (manufactured by Shin-Nakamura Chemical Co., Ltd.)
Ethylene oxide (three) glycerin triacrylate (C-1) binder resin: Resin (C-1) obtained in Synthesis Example 5 (propylene glycol monomethyl ether acetate solution having a solid content of 38.5% by mass)
(D-1) Photopolymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (E-1) Photopolymerization initiator assistant: 4,4′-bis ( Diethylamino) benzophenone (F-1) Solvent: Propylene glycol monomethyl ether (F-2) Solvent: Ethyl 3-ethoxypropionate (G-1) Surfactant: Megafac F475 (manufactured by Dainippon Ink & Chemicals, Inc.)
(H-1) Curing agent: Sumiepoxy ESCN-195XL-80 [Orthocresol novolac type epoxy resin (manufactured by Sumitomo Chemical Co., Ltd.)]

Example 1
[Preparation of colored curable composition 1]
(A-1) 7.650 parts by mass (B-1) 4.712 parts by mass (C-1) 8.160 parts by mass (solid content conversion value: 3.141 parts by mass)
(D-1) 1.257 parts by mass (E-1) 0.236 parts by mass (F-1) 73.831 parts by mass (F-2) 4.150 parts by mass (G-1) 0.004 parts by mass Were mixed to obtain a colored curable composition 1.

[Formation of coating film]
Next, the colored curable composition 1 obtained above is applied onto glass (# 1737; Corning) by spin coating, and then the volatile components are volatilized at 100 ° C. for 3 minutes to form a colored curable composition film. did. After cooling, the colored curable composition film was exposed to i-line (wavelength 365 nm) for exposure. An ultra-high pressure mercury lamp was used as the i-line light source, and the light was irradiated after being converted into parallel light. The amount of irradiation light was 500 mJ / cm ² . Subsequently, post-baking was performed at 220 ° C. for 20 minutes to obtain a colored curable composition film having a thickness of 2 μm.

[Evaluation 1] Evaluation of heat resistance The chromaticity of the obtained colored curable composition film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS).
Subsequently, the obtained colored curable composition film was further heated in an oven in an air atmosphere at 230 ° C. for 120 minutes, and the chromaticity of the colored curable composition film after heating was measured in the same manner. The color difference (ΔEab *) was determined to be 3.6.
As an evaluation standard for color difference, if ΔEab * is 5 or less, almost no hue change is observed, showing good characteristics as a color filter, and if ΔEab * is more than 5 and less than 10, slight hue change is recognized. However, if the color filter has a practically no problem level and ΔEab * is 10 or more, a clear hue change can be confirmed, which is a problematic level for the color filter.

[Evaluation 2] Light resistance evaluation An ultraviolet cut filter (COLORED OPICAL GLASS L38; manufactured by Hoya Co., Ltd .; cuts light of 380 nm or less) is placed on the obtained colored curable composition film, and a light resistance test is performed. Xenon lamp light was irradiated for 48 hours with a machine (SUNTEST CPS +: manufactured by Toyo Seiki Co., Ltd.).
The chromaticity of the colored curable composition film after irradiation was measured, and the color difference before and after irradiation was determined to be 0.6.
As the evaluation criteria for the color difference, as described above, when ΔEab * is 5 or less, there is almost no change in hue, showing good characteristics as a color filter, and when ΔEab * is more than 5 and 10 or less, However, when ΔEab * is 10 or more, a clear hue change can be confirmed, which is a problematic level for a color filter.

[Evaluation 3] Evaluation of solvent resistance The chromaticity of the obtained colored curable composition film was measured using the same colorimeter as described above.
Next, the obtained colored curable composition film was immersed in a large excess amount of propylene glycol monomethyl ether kept at a constant temperature of 23 ° C. for 30 minutes, and the chromaticity of the colored curable composition film after immersion was made the same. The color difference before and after heating was determined to be 1.8.
As an evaluation standard for color difference, if ΔEab * is 5 or less, almost no hue change is observed, showing good characteristics as a color filter, and if ΔEab * is more than 5 and less than 10, slight hue change is recognized. However, if the color filter has a practically no problem level and ΔEab * is 10 or more, a clear hue change can be confirmed, which is a problematic level for the color filter.

[Evaluation 4] Contrast Evaluation When the contrast value of the obtained colored curable composition film was measured using a contrast colorimeter (CT-1; manufactured by Aisaka Electric Co., Ltd.) with a blank value of 10,000, it was 9112. It was.
As a criterion for evaluating the contrast of the colored curable composition film, if the contrast value is 8000 or more, depolarization is hardly recognized, and the color filter exhibits good characteristics, and the contrast value exceeds 6000 and is 8000 or less. For example, a slight degree of depolarization is recognized, but it is at a level where there is no problem in practical use of the color filter. Is a level.

Example 2
[Preparation of colored curable composition 2]
A colored curable composition 2 was obtained by mixing in the same manner as in Example 1 except that the colorant (A-1) in Example 1 was changed to the colorant (A-2).

[Formation and evaluation of coating film]
A colored curable composition film having a thickness of 2 μm was prepared and evaluated in the same manner as in Example 1. As a result, the color difference in the heat resistance evaluation was 4.8, and the color difference in the light resistance evaluation was 3.5. The color difference in solvent resistance was 0.8 and the contrast value was 9057.

Example 3
[Preparation of colored curable composition 3]
(A-1) 4.590 mass parts (A-3) 3.060 mass parts (B-1) 4.712 mass parts (C-1) 8.160 mass parts (solid content conversion value: 3.141 mass) Part)
(D-1) 1.257 parts by mass (E-1) 0.236 parts by mass (F-1) 73.831 parts by mass (F-2) 4.150 parts by mass (G-1) 0.004 parts by mass Were mixed to obtain a colored curable composition 3.

[Formation and evaluation of coating film]
A colored curable composition film having a thickness of 2 μm was prepared and evaluated in the same manner as in Example 1. As a result, the color difference in the heat resistance evaluation was 2.6, and the color difference in the light resistance evaluation was 0.7. The color difference in solvent resistance was 1.8, and the contrast value was 8971.

Example 4
[Preparation of colored curable resin composition 4]
A colored curable composition 4 was obtained by mixing in the same manner as in Example 1 except that (A-3) in Example 3 was changed to (A-4).

[Formation and evaluation of coating film]
A colored curable composition film having a thickness of 2 μm was prepared and evaluated in the same manner as in Example 1. As a result, the color difference in the heat resistance evaluation was 3.8, and the color difference in the light resistance evaluation was 0.9. The color difference in solvent resistance was 4.3 and the contrast value was 9232.

Example 5
[Preparation of colored curable composition 5]
A colored curable composition 5 was obtained by mixing in the same manner as in Example 1 except that (A-3) in Example 3 was changed to (A-5).

[Formation and evaluation of coating film]
A colored curable composition film having a thickness of 2 μm was prepared and evaluated in the same manner as in Example 1. As a result, the color difference in the heat resistance evaluation was 8.9, and the color difference in the light resistance evaluation was 2.8. The color difference in solvent resistance was 2.6 and the contrast value was 9151.

Example 6
[Preparation of colored curable composition 6]
(A-1) 4.590 parts by mass (A-3) 3.060 parts by mass (B-2) 4.319 parts by mass (C-1) 7.139 parts by mass (solid content conversion value: 2.749 parts by mass) Part)
(D-1) 1.257 parts by mass (E-1) 0.236 parts by mass (F-1) 73.831 parts by mass (F-2) 4.150 parts by mass (G-1) 0.004 parts by mass (H-1) A colored curable composition 6 was obtained by mixing 0.785 parts by mass.

[Formation and evaluation of coating film]
A colored curable composition film having a thickness of 2 μm was prepared and evaluated in the same manner as in Example 1. As a result, the color difference in the heat resistance evaluation was 2.9, and the color difference in the light resistance evaluation was 2.4. The color difference in solvent resistance was 1.6, and the contrast value was 8,652.

Comparative Example 1
[Preparation of colored curable composition 7]
A colored curable composition 7 was obtained by mixing in the same manner as in Example 1 except that (A-1) in Example 1 was changed to (A-6).

[Formation and evaluation of coating film]
A colored curable composition film having a thickness of 2 μm was prepared and evaluated in the same manner as in Example 1. As a result, the color difference in the heat resistance evaluation was 20.1, and the color difference in the light resistance evaluation was 4.2. The color difference in solvent resistance was 13.4 and the contrast value was 9036.

Comparative Example 2
[Preparation of colored curable composition 8]
A colored curable composition 8 was obtained by mixing in the same manner as in Example 1 except that (A-1) in Example 1 was changed to (A-7).

[Formation and evaluation of coating film]
A colored curable composition film having a thickness of 2 μm was prepared and evaluated in the same manner as in Example 1. As a result, the color difference in the heat resistance evaluation was 32.3, and the color difference in the light resistance evaluation was 6.2. The color difference in solvent resistance was 15.1 and the contrast value was 8725.

Comparative Example 3
[Preparation of colored curable composition 9]
A colored curable composition 9 was obtained by mixing in the same manner as in Example 1 except that (A-1) in Example 3 was changed to (A-6).

[Formation and evaluation of coating film]
A colored curable composition film having a thickness of 2 μm was prepared and evaluated in the same manner as in Example 1. As a result, the color difference in the heat resistance evaluation was 17.5, and the color difference in the light resistance evaluation was 7.5. The color difference in solvent resistance was 30.6 and the contrast value was 8120.

Claims (10)

(A) a colored curable composition containing a colorant and (B) a polymerizable compound, and a dye (A) a colorant is represented by formula (1), and barbituric acid azo dye fees A colored curable composition comprising:

[In formula (1), M represents a non-metal, a metal, or a metal oxide.
A ^{1 to} A ¹⁶ each independently represent a hydrogen atom, a halogen atom, or a substituent selected from the group of substituents represented by formulas (2) to (5). Provided ^{that at} 1-8 of A 1 ^{to A 16} represents a substituent selected from the group of substituents represented by the formula (2) to (5).

In formulas (2) to (5), G ^{1 to} G ⁴ each independently represent an oxygen atom, a sulfur atom, or a —N (R ¹⁴ ) — group.
R ¹⁴ represents a hydrogen atom or a linear or branched saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms.
R ^{11 to} R ¹³ each independently represents a hydrogen atom, an optionally substituted aryl group having 6 to 20 carbon atoms, or a linear or branched saturated aliphatic hydrocarbon having 1 to 8 carbon atoms. Represents a group.
J ^{1 to} J ³ each independently represent a halogen atom, a linear or branched saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, or an alkoxyl group having 1 to 4 carbon atoms.
L represents a halogen atom, a linear or branched saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms, or an alkoxyl group having 1 to 4 carbon atoms.
e1, g1 and i1 are each independently an integer of 1 to 5.
e2, g2 and i2 are each independently an integer of 0 to 5.
However, the sum of e1 and e2, the sum of g1 and g2, and the sum of i1 and i2 are integers of 5 or less.
f and h are each independently an integer of 1 to 6.
j is an integer of 1 or 2. ] In the formula (1), among the substituents represented by A ^{1 to} A ¹⁶ , all the substituents selected from the group of substituents represented by the formulas (2) to (5) are all fluorine atoms. The colored curable composition according to claim 1. The colored curable composition according to claim 1 or 2, wherein G ¹ in formula (2) is an oxygen atom. The colored curable composition according to any one of claims 1 to 3, wherein the barbituric acid azo dye is a dye represented by the formula (7).

Wherein (7), ^{T 1} and ^{T 2} each independently represent an oxygen atom or a sulfur atom.
R ^{31 to} R ³⁴ are each independently a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted by a hydroxyl group, or 1 carbon atom. A saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted by an alkoxyl group having 8 to 8 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with a thioalkoxyl group having 1 to 8 carbon atoms, An aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an acyl group having 2 to 10 carbon atoms is represented.
R ^{35 to} R ⁴² are each independently a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted by a halogen atom, An alkoxyl group having 1 to 8 carbon atoms, a carboxyl group, a sulfo group, a sulfamoyl group or an N-substituted sulfamoyl group is represented. ]   Furthermore, the coloring curable composition in any one of Claims 1-4 containing (C) binder resin. The colored curable composition according to claim 5, wherein (C) the binder resin is a resin containing a structural unit derived from (meth) acrylic acid and a structural unit represented by formula (33).

[In Formula (33), R < ¹⁶ > and R < ¹⁷ > represent a hydrogen atom or a C1-C6 saturated aliphatic hydrocarbon group each independently. ]   Furthermore, the coloring curable composition in any one of Claims 1-6 containing a photoinitiator (D).   The pattern formed by the photolithographic method or the inkjet method using the colored curable composition in any one of Claims 1-7.   A color filter comprising the pattern according to claim 8.   A liquid crystal display device comprising the color filter according to claim 9.