KR20090021083A - Colored curable composition - Google Patents

Abstract

A colored curing composition, a pattern formed by using the composition, a color filter containing the pattern, and an LCD device containing the color filter are provided to improve heat resistance and solvent resistance. A colored curing composition comprises a colorant which comprises a dye represented by the formula 1; and a polymerizable compound, wherein k is 0 or 1; M is a metal or a metal oxide; A1 to A16 are independently H, a halogen atom, or a substituent represented by the formula 2, 3, 4 or 5, but 1-8 groups of A1 to A16 are a substituent represented by the formula 2, 3, 4 or 5; G1 to G4 are independently O, S or -N(R14)-; and R14 are H, or a linear or branched C1-C6 saturated aliphatic hydrocarbon group.

Description

Colored curable composition {COLORED CURABLE COMPOSITION}

The present invention relates to a colored curable composition.

Colored curable compositions are used for manufacture of the color filter used for display apparatuses, such as a liquid crystal display panel, an electroluminescence, and a plasma display panel.

It is known to use a pigment or a dye as this coloring curable composition as a coloring agent.

Among these, the colored curable composition using the pigment generally has the characteristics of high light resistance and heat resistance, but the pigment particles have a problem that the light transmittance of the color filter is reduced or the contrast is low (see Patent Document 1 below). .

Moreover, since the coloring curable composition using dye has the characteristic that the contrast of a color filter is high because there is no scattering of light by a pigment particle, there existed a problem that light resistance and heat resistance were low (refer patent document 2, 3 below).

Therefore, various studies have been made to improve the light resistance and heat resistance of a colored curable composition using a dye, and among these, in a green colored curable composition, a phthalocyanine dye having a specific structure and a pyridone azo dye having a specific structure are used in combination. Is proposed (see Patent Document 4 below).

[Patent Document 1] Japanese Patent Laid-Open No. 2000-352610, page 2, right column 24 to 30

[Patent Document 2] Japanese Patent Application Laid-Open No. 2004-157455, page 3, line 42 to page 4, line 8

[Patent Document 3] Japanese Patent Laid-Open No. 2004-246105, page 2, line 35 to page 3, line 3

[Patent Document 4] Japanese Patent Application Laid-Open No. 2006-71822

However, the present inventors found that there is room for improvement in heat resistance and solvent resistance of the color filter obtained in the invention described in Patent Document 4.

An object of the present invention is to provide a colored curable composition capable of forming a color filter excellent in heat resistance and solvent resistance.

The present inventors have found that the colored curable composition containing a kind of phthalocyanine dye different from the phthalocyanine dye conventionally known as a coloring agent can solve the above problem.

That is, this invention provides the following [1]-[10].

[1] A colored curable composition containing (A) a colorant and (B) a polymerizable compound,

(A) The coloring curable composition in which a coloring agent contains the pigment | dye represented by following formula (1).

<Formula 1>

In Chemical Formula 1, k represents an integer of 0 or 1, M represents a metal or a metal oxide, and A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom or a group of substituents represented by the following Chemical Formulas 2 to 5 Wherein substituents selected from A ¹ to A ¹⁶ represent a substituent selected from the group of the substituents represented by Formulas 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 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 group having 1 to 8 carbon atoms,

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 straight 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 from 0 to 5,

Provided that 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 from 1 to 6,

j is an integer of 1 or 2]

[2] The colored curable composition according to the above [1], wherein all of the substituents represented by A ¹ to A ¹⁶ in the general formula (1) are fluorine atoms except for a substituent selected from the group of the substituents represented by the general formulas (2) to (5).

[3] The colored curable composition according to the above [1] or [2], wherein in formula (2), G ¹ is an oxygen atom.

[4] The colorant according to any one of the above [1] to [3], wherein the colorant (A) is a barbituric acid azo dye, a pyridone azo dye, a pyrazolone azo dye, a quinophthalone dye, and a cyanine dye. Colored curable composition containing at least 1 sort (s) of dye chosen from the group which consists of.

[5] The colored curable composition according to the above [4], wherein the barbituric acid azo dye is a dye represented by the following formula (7).

In Formula 7, T <^1> and T <^2> represent an oxygen atom or a sulfur atom each independently,

R ³¹ to R ³⁴ each independently represent a hydrogen atom, a saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms in which a hydroxyl group is substituted, and an alkoxyl group of 1 to 8 carbon atoms is substituted. Saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, Saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with thioalkoxyl group having 1 to 8 carbon atoms, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms or 2 carbon atoms To acyl groups of 10 to 10,

R ³⁵ to R ⁴² each independently represent a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, an alkoxyl group of 1 to 8 carbon atoms, substituted by a halogen atom, Carboxyl group, sulfo group, sulfamoyl group or N-substituted sulfamoyl group;

[6] The colored curable composition according to the above [4], wherein the pyridone azo dye is a dye represented by the following formula (8).

In the formula (8), Z is a phenyl group having one or two or more groups selected from the group consisting of carboxyl group, carbamoyl group, sulfo group, sulfamoyl group and N-substituted sulfamoyl group, or carboxyl group, carbamo A naphthyl group having 1 to 3 or more groups selected from the group consisting of a diary, a sulfo group, a sulfamoyl group and an N-substituted sulfamoyl group,

R ²¹ represents a hydrogen atom, a linear, branched or cyclic saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group or a trifluoromethyl group,

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

R ²³ is a hydrogen atom, a substituted, straight-chain, branched or cyclic saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, an aryl group of 6 to 30 carbon atoms that can be substituted, or an aral of 7 to 20 carbon atoms that can be substituted A group in which a carbon of a kill group, 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 aliphatic oxycarbonyl group having 2 to 20 carbon atoms which may be substituted, and may be substituted An aryloxycarbonyl group having 7 to 30 carbon atoms, an acyl group having 2 to 20 carbon atoms substituted, an aliphatic sulfonyl group having 1 to 30 carbon atoms substituted, or an arylsulfonyl group having 6 to 30 carbon atoms substituted,

Formula 8 may form dimers or multimers at any position;

[7] The colored curable composition according to any one of the above [1] to [6], further comprising (C) a binder resin.

[8] A pattern formed by the photolithography method or the inkjet method using the colored curable composition according to any one of the above [1] to [7].

[9] A color filter comprising the pattern of [8].

[10] A liquid crystal display device comprising the color filter according to the above [9].

According to this invention, the colored curable composition which can form the color filter excellent in heat resistance and solvent resistance can be provided.

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

<Formula 1>

In Chemical Formula 1, k represents an integer of 0 or 1, and M represents 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 the substituents represented by the following formulas (2) to (5). Provided that 1 to 8 of A ¹ to A ¹⁶ represent a substituent selected from the group of the substituents represented by the formulas (2) to (5).

<Formula 2>

<Formula 3>

<Formula 4>

<Formula 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 group having 1 to 8 carbon atoms.

J ¹ to J ³ each independently represent a halogen atom, a straight 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 1-5.

e2, g2 and i2 are each independently an integer of 0-5.

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 1-6.

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, Fe, and the like, and preferably Zn, Cu, Ni, Co, etc. Can be mentioned.

Examples of the metal oxide in M include VO and TiO.

The base metal in M represents that one hydrogen atom is respectively bonded to two nitrogen atoms which should be coordinated with the original 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.

R ¹¹ substituent to an aryl group having 6 to 20 carbon atoms which may have a group from R ^13, there may be mentioned an aryl group which may have a substituent such as a saturated aliphatic hydrocarbon group or a hydroxyl group. 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).

As a saturated aliphatic hydrocarbon group as said substituent, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert- butyl group, etc. are mentioned.

Examples of the linear or branched saturated aliphatic hydrocarbon group having 1 to 8 carbon atoms in R ¹¹ to R ¹³ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group , Linear or branched pentyl groups, linear or branched hexyl groups, linear or branched heptyl groups and linear or branched octyl groups, and the like, and preferably methyl, ethyl and n groups. -Propyl group, isopropyl group, n-butyl group, isobutyl group is mentioned.

As a halogen atom in J <^1> -J <^3> , a fluorine atom, a chlorine atom, a bromine atom, etc. are mentioned, Preferably a fluorine atom is mentioned.

Examples of the linear or branched saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms in J ¹ to J ³ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group. Can be 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, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group and the like. have.

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 include the same as those exemplified in J ¹ to J ³ described above.

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, and more preferably an oxygen atom.

e1 is an integer of 1-5, Preferably it is an integer of 1-3, More preferably, it is an integer of 1 or 2.

e2 is an integer of 0-4, Preferably it is an integer of 0-2, More preferably, it is an integer of 0 or 1.

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

f is an integer of 1-6, Preferably it is an integer of 1-3, More preferably, it is an integer of 1 or 2.

g1 is an integer of 1-5, Preferably it is an integer of 1-3, More preferably, it is an integer of 1 or 2.

g2 is an integer of 0-4, Preferably it is an integer of 0-2, More preferably, it is an integer of 0 or 1.

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

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, and more preferably an oxygen atom.

h is an integer of 1-6, Preferably it is an integer of 1-3, More preferably, it is an integer of 1 or 2.

i1 is an integer of 1-5, Preferably it is an integer of 1-3, More preferably, it is an integer of 1 or 2.

i2 is an integer of 0-4, Preferably it is an integer of 0-2, More preferably, it is an integer of 0 or 1.

Examples of the substituent represented by the formula (4) include groups represented by the following formulas (4-1) to (4-19) and the like, and preferably (4-1) to (4-4) and (4-7). ), (4-8), (4-10), (4-13), (4-14) and (4-16), and the group represented by (4-1)-( And groups represented by 4-3), (4-7), (4-10), and (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, and more preferably an oxygen atom.

In formula (5), j is an integer of 1 or 2, Preferably it is 1.

Examples of the substituent represented by the formula (5) include groups represented by the following formulas (5-1) to (5-18) and the like, and 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 The group represented by (5-16) is mentioned.

As a pigment | dye represented by General formula (1), the pigment | dye represented by following General formula (1-1)-(1-33) is mentioned, Preferably it is (1-1)-(1-5), (1-7) To (1-11), (1-13), (1-14), (1-16), (1-18), (1-19), (1-22) to (1-24), ( And the 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 is mentioned.

The content of the dye represented by the general formula (1) in the colored curable composition of the present invention is preferably 15 to 65 mass%, more preferably 20 to 60 mass%, particularly preferably in terms of mass fraction relative to the solid content of the colored curable composition. Is 25-60 mass%.

When content of a pigment exists in the said range, since the color density at the time of setting it as a color filter can be sufficient, and a polymeric compound can be contained in a composition in a required amount, solvent resistance tends to improve and it is preferable.

Here, solid content means the total amount of the component except the solvent contained in a colored curable composition in this specification.

The colored curable composition of the present invention further comprises (A) at least one member selected from the group consisting of barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes and cyanine dyes as colorants. Dyes.

It does not specifically limit as said barbituric acid azo dye, A well-known substance can be used, Preferably, the barbituric acid azo dye represented by following formula (7) is used.

<Formula 7>

In Formula 7, T <^1> and T <^2> represent an oxygen atom or a sulfur atom each independently,

R ³¹ to R ³⁴ each independently represent a hydrogen atom, a saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms in which a hydroxyl group is substituted, and an alkoxyl group of 1 to 8 carbon atoms is substituted. Saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, Saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with thioalkoxyl group having 1 to 8 carbon atoms, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms or 2 carbon atoms To acyl groups of 10 to 10,

R ³⁵ to R ⁴² each independently represent a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, an alkoxyl group of 1 to 8 carbon atoms, substituted by a halogen atom, Carboxyl group, sulfo group, sulfamoyl group or N-substituted sulfamoyl group;

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

The saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ³¹ to R ³⁴ may be any of linear, branched or cyclic. Carbon number of the 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 group ( 2-ethylhexyl group etc.), a cyclopentyl group, a cyclohexyl group, a cyclohexyl alkyl group, etc. are mentioned.

In addition, as described above, the saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms includes a hydroxyl group, an alkoxyl group having 1 to 8 carbon atoms (preferably having 1 to 4 carbon atoms) or a 1 to 8 carbon atom (preferably 1 carbon atom). To 4) thioalkoxyl groups 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-ethylhexyl jade). C) propyl group etc.), a methylthio propyl group (3-methylthio propyl group etc.), etc. are mentioned.

The aryl group having 6 to 20 carbon atoms in R ³¹ to R ³⁴ may be unsubstituted or may have a substituent such as a saturated aliphatic hydrocarbon group, an alkoxyl group, a carboxyl group, a sulfo group or an ester group. Carbon number of the said aryl group is calculated including carbon number of a substituent, Preferably it is 6-10. As these aryl groups, a phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-sulfophenyl group, 3- a sulfonyl group, and the like can be mentioned 4-sulfonyl group, ethoxycarbonyl group _{(4- (COOC 2 H 5)} Ph , and so on) substituted or unsubstituted phenyl group, such as a.

The alkyl moiety of the aralkyl group having 7 to 20 carbon atoms in R ³¹ to R ³⁴ may be any of linear, branched or cyclic. Carbon number of an aralkyl group is computed including carbon number of a substituent, Preferably it is 7-10. Examples of aralkyl having 7 to 20 carbon atoms include benzyl group and 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. The carbon number of the acyl group is calculated including the carbon number of the substituent, and the number is preferably 2 to 10. The acyl group is, for example, an acetyl group, a benzoyl group, a methoxy benzoyl group (such as a p-methoxybenzoyl group), or the like.

The saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ³⁵ to R ⁴² may be either linear, branched or cyclic as in the case of R ³¹ to R ³⁴ , and the carbon number is preferably 2 to 8, More preferably, it is 3-6.

Specific examples of the saturated aliphatic hydrocarbon group of 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 by a halogen atom, preferably a fluorine atom. Trifluoromethyl group etc. are mentioned as a specific example of the saturated aliphatic hydrocarbon group substituted by the halogen atom.

Preferably carbon number of the C1-C8 alkoxyl group in R <^35> -R <^42> is 1-4. As said alkoxyl group, a methoxy group, an ethoxy group, isopropoxy group, n-propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, etc. are mentioned, for example.

The N-substituted sulfamoyl group in R ³⁵ to R ⁴² is, for example, an N-substituted sulfamoyl group and is represented by the formula -SO ₂ NHR ⁴³ .

R ⁴³ is a C 1-10 saturated aliphatic hydrocarbon group (including those having a C 1-10 saturated aliphatic hydrocarbon group bonded to an alkoxyl group having 1 to 8 carbon atoms), an aryl group having 6 to 20 carbon atoms, and a 7 to 20 carbon atoms Aralkyl group or the C2-C10 acyl group is shown.

The saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ⁴³ may be any of 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 thereof is preferably 6 to 10.

As a C1-C10 saturated aliphatic hydrocarbon group in R <^43> , a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 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 group, etc.) , A cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group (such as 2-methylcyclohexyl group), a cyclohexylalkyl group, and the like.

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) as described above. As this substituted saturated aliphatic hydrocarbon group, a propoxy propyl group (3- (isopropoxy) propyl group etc.) etc. can be illustrated.

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. Carbon number of the said aryl group is calculated including carbon number of a substituent, Preferably it is 6-10. As these aryl groups, substituted or unsubstituted phenyl groups, such as a phenyl group, a hydroxyphenyl group (4-hydroxyphenyl group etc.), a trifluoromethylphenyl group (4-trifluoromethylphenyl group etc.), etc. are mentioned, for example.

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

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. The carbon number of the acyl group is calculated including the carbon number of the substituent, and the number is preferably 6 to 10. As said acyl group, an acetyl group, benzoyl group, o-toluyl group, m-toluyl group, p-toluyl group, methoxy benzoyl group (p-methoxybenzoyl group etc.) etc. are mentioned, for example.

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

Examples of the barbituric acid azo dye include compounds represented by the following formulas (7-1) to (7-7), and are preferably formulas (7-1), (7-3) and (7-4) ), (7-5) and the compound represented by (7-7), etc. are mentioned.

It does not specifically limit as a pyridone azo dye, Although a well-known substance can be used, The thing represented by following formula (8) is used preferably.

<Formula 8>

In Formula 8, Z is a phenyl group having one or two or more groups selected from the group consisting of a carboxyl group, a carbamoyl group, a sulfo group and a sulfamoyl group which may be substituted with an N position, or a carboxyl group or a carbamoyl group. , A naphthyl group having 1 to 3 or more groups selected from the group consisting of a sulfamoyl group which can be substituted with a sulfo group and an 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, lithium salt, sodium salt, or potassium salt of each of the above substituents,

R ²³ is a hydrogen atom, a substituted, straight-chain, branched or cyclic saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, an aryl group of 6 to 30 carbon atoms that can be substituted, or an aral of 7 to 20 carbon atoms that can be substituted A group in which a carbon of a kill group, 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 alkyloxycarbonyl group having 2 to 20 carbon atoms which may be substituted, and may be substituted An aryloxycarbonyl group having 7 to 30 carbon atoms, an acyl group having 2 to 20 carbon atoms substituted, an aliphatic sulfonyl group having 1 to 30 carbon atoms substituted, or an arylsulfonyl group having 6 to 30 carbon atoms substituted,

Formula 8 may form dimers or multimers at any position;

In the formula (8), N-substituted sulfamoyl groups of the phenyl group and naphthyl group represented by Z are represented by -SO ₂ N (R ²⁴ ) R ²⁵ .

R ²⁴ and R ²⁵ each independently represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms (including one substituted with an alkoxyl group having 1 to 8 carbon atoms), and a carbon atom having 6 to 10 carbon atoms An aryl group of 20, an aralkyl group of 7 to 20 carbon atoms, or an acyl group of 2 to 10 carbon atoms is shown (however, R ²⁴ and R ²⁵ are not simultaneously hydrogen atoms).

The saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms may be linear, branched or cyclic, and the carbon number of the saturated aliphatic hydrocarbon group is preferably 6 to 10.

As a C1-C10 saturated aliphatic hydrocarbon group represented by R <^24> and R <^25> , a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 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 group, etc.) ), A cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group (2-methylcyclohexyl group, etc.), a cyclohexylalkyl group, etc. are mentioned, Preferably isopropyl group, isobutyl group, 1,1,3, 3-tetramethylbutyl group, 1, 5- dimethylhexyl group, 2-ethylhexyl group, etc. are mentioned.

The saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R ²⁴ and R ²⁵ may be substituted with an alkoxyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms) as described above. As a saturated aliphatic hydrocarbon group substituted by the said C1-C8 alkoxyl group, a propoxypropyl group (3- (isopropoxy) propyl group etc.) etc. are mentioned.

As an C6-C20 aryl group represented by R <^24> and R <^25> , you may have substituents, such as an unsaturated aliphatic hydrocarbon group or a hydroxyl group. The carbon number of the aryl group is calculated including the carbon number of the substituent, and is usually 6 to 20, preferably 6 to 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).

The alkyl moiety of the aralkyl group represented by R ²⁴ and R ²⁵ may be either linear or branched. The aralkyl group has usually 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms. As this aralkyl, phenylalkyl groups, such as a benzyl group, the phenylpropyl group (1-methyl-3- phenylpropyl group, etc.), and the phenylbutyl group (3-amino-1-phenylbutyl group, etc.), are typical.

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. The carbon number of the acyl group is calculated including the carbon number of the substituent, and the number is usually 2 to 10, preferably 6 to 10. The acyl group is, for example, an acetyl group, a benzoyl group, a methoxy benzoyl group (such as a p-methoxybenzoyl group), or the like.

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

As a saturated aliphatic hydrocarbon group represented by R <^21> , it may be any of linear, branched, or cyclic. Carbon number of a substituent is not included in carbon number of a saturated aliphatic hydrocarbon group. Preferably carbon number is 2-8, More preferably, it is 3-6. Examples of 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 and cyclohexyl group. .

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, lithium salt, sodium salt, or potassium salt of each substituent.

Examples of the N-substituted carbamoyl group represented by R ²² include —CON (R ²⁶ ) R ²⁷ (wherein R ²⁶ and R ²⁷ each independently represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and 1 carbon atom). A C1-C10 saturated aliphatic hydrocarbon group, a C6-C20 aryl group, a C7-C20 aralkyl group, or a C2-C10 acyl group which the alkoxyl group of 8-8 is substituted) can represent.

The description and specific examples of the saturated aliphatic hydrocarbon group, aryl group, aralkyl group and acyl group of R ²⁶ and R ²⁷ are the same as those of R ²⁴ and R ²⁵ described above. However, as a specific example of an acyl group, the benzoyl group containing a halogen atom, for example, a bromobenzoyl group (p-bromobenzoyl group etc.) etc. are also mentioned.

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

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.

As an aryl group represented by R <^23> , carbon number is 6-30 normally, Preferably it is 6-20, More preferably, it is 6-16. Specific examples of these aryl groups include phenyl group, 4-nitrophenyl group, 2-nitrophenyl group, 2-chlorophenyl group, 2,4-dichlorophenyl group, 2,4-dimethylphenyl group, 2-methylphenyl group, 4-methoxyphenyl group, 2- A methoxyphenyl group, 2-methoxycarbonyl-4-nitrophenyl group, etc. are mentioned.

The group in which a part of the carbon 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 the total carbon number is preferably 3 to 20, more preferably 5 to 15 to be. As a specific example of the group which has these hetero rings, a pyrazole group, a 1,2, 4-triazole group, an isothiazole group, a benzoisothiazole group, a thiazole group, a benzothiazole group, an oxazole group, 1,2,4-thiadia Snoozing and the like. It may further have a substituent.

The aralkyl group represented by R ²³ may be either linear or branched, and carbon number is preferably 7 to 10. As a specific example of this aralkyl, phenylalkyl groups, such as a benzyl group, a phenylpropyl group (1-methyl-3- phenylpropyl group, etc.), a phenylbutyl group (3-amino-1-phenylbutyl group, etc.), are typical.

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

The alkyloxycarbonyl group represented by R ²³ may be unsubstituted, may have a substituent, or may be cyclic. As total carbon number of this alkyloxycarbonyl group, it is 2-20 normally, Preferably it is 2-16, More preferably, it is an alkyloxycarbonyl group of 2-10. As a specific example of this alkyloxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, butoxycarbonyl group, etc. are mentioned.

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

The acyl group represented by R ²³ may be an aliphatic carbonyl group, an arylcarbonyl group, may be either saturated or unsaturated, may be cyclic, or may further have a substituent. As 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 an 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 methanesulfonyl group, butanesulfonyl group, methoxymethanesulfonyl group, methoxyethanesulfonyl group, ethoxyethanesulfonyl group and the like.

The arylsulfonyl group represented by R ²³ may have a substituent, and as a total carbon number, it is usually 6-30, Preferably it is 6-20, More preferably, it is 6-18. As a specific example of this arylsulfonyl group, a benzenesulfonyl, a toluenesulfonyl group, etc. are mentioned.

As said pyridone azo dye, the following compound is mentioned, Preferably, the compound represented by following General formula (8-1)-(8-9) is mentioned.

The pyridoneazo dye represented by the formula (8) may form a dimer or more multimer at any position.

The multimer in general formula (8) means having one or more groups represented by general formula (8) in one molecule, and the following compounds etc. are mentioned specifically ,.

It does not specifically limit as said pyrazolone azo dye, A well-known substance can be used, For example, Unexamined-Japanese-Patent No. 2006-276512, Unexamined-Japanese-Patent No. 2005-263926, and Japan Unexamined-Japanese-Patent No. 2006-015669 The pyrazolone azo dyes described in these publications can be used.

Specifically, C.I. Acid Yellow 17, C.I. Solvent Orange 56, C.I. The solvent yellow 82, the following compound, etc. are mentioned.

It does not specifically limit as said quinophthalone type dye, A well-known substance can be used, For example, Unexamined-Japanese-Patent No. 5-39269, Unexamined-Japanese-Patent No. 6-220339, and Japan Patent Publication ) And the quinophthalone dyes described in Japanese Patent Application Laid-Open No. 8-171201.

Specifically, C.I. Solvent Yellow 33, C.I. Disperse Yellow 54, C.I. Disperse yellow 64, the following compound, etc. are mentioned.

It does not specifically limit as said cyanine dye, A well-known substance can be used. For example, the cyanine pigment | dye described in Unexamined-Japanese-Patent No. 2005-194509, Unexamined-Japanese-Patent No. 2007-131818, 2005-297406, etc. can be used. Specifically, the following compounds etc. are mentioned.

Moreover, as (A) coloring agent, a pigment can be contained in the range which does not impair the effect of this invention.

Examples of the pigment include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists), and specifically, C.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, CI Pigments such as Pigment Green 7, 36, and the like, and preferably C.I. Pigment Yellow 138, 139, 150, C.I. Pigment green 7, 36 is mentioned.

The said pigment can be obtained as a dispersion liquid of the state in which the pigment was disperse | distributed uniformly in solution by containing a dispersing agent and performing a dispersion process as needed.

As said dispersing agent, surfactant, such as cationic, anionic, nonionic, amphoteric, polyester, polyamine type, etc. are mentioned, for example, It can be used individually or in combination of 2 or more types.

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, polyethylene imines, and the like. Other brand names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Kagaku Co., Ltd.), F-Top (manufactured by Tochem Products, Inc.), and Mega Pak (Dain Nippon Ink Chemical Co., Ltd.) ) Manufactured), fluoride (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Suflon (above, manufactured by Asahi Glass Co., Ltd.), Solspas (manufactured by Geneka Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.) And PB821 (manufactured by Ajinomoto Co., Ltd.).

When using a dispersing agent, the usage-amount is preferably 0.1-100 mass% in mass fraction with respect to 100 mass% of pigments, More preferably, it is 5-50 mass%. When the usage-amount of a dispersing agent exists in the said range, since a uniform dispersion liquid tends to be obtained, it is preferable.

Content of the (A) coloring agent used for the colored curable composition of this invention is 30-65 mass% in mass fraction with respect to solid content of a colored curable composition, Preferably it is 35-60 mass%, More preferably, it is 35-55 It is mass%.

When content of the (A) coloring agent exists in the said range, since the color density at the time of setting it as a color filter is enough, a polymeric compound can be contained in a composition more than a required amount, and since a pattern with sufficient mechanical strength can be formed, it is preferable.

As (B) polymeric compound used for this invention, the monomer or oligomer hardened | cured by heat or light, or both can be used, These can also be used together. As this monomer or oligomer, a known substance can be used.

Specific examples of the monomer include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, and dipentaerythritol pentaacrylate derivatives having a carboxyl group, and ethylene. Oxidized glycerin triacrylate, ethylene oxide trimethylol propane triacrylate, a propylene oxide glycerin triacrylate, etc. are mentioned.

Examples of the oligomers include epoxy acrylates, urethane acrylates, polyester arc releasing agents, and the like. For example, oligomers described on pages 18 to 20 of the present conditions and prospects of UV / EB curing technology can be used. Can be.

The content of the polymerizable compound (B) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, particularly preferably 12 to 35% by mass with respect to the solids content of the colored curable composition. . When content of a polymeric compound exists in the said range, since hardening generate | occur | produces sufficiently, the film thickness ratio before and behind image development improves, and adhesiveness tends to become favorable, it is preferable.

Here, solid content means the total amount of the component which is not a liquid at normal temperature among the (A) coloring agent, (B) polymeric compound, and the component further added as needed of a colored curable composition.

The colored curable composition of this invention can contain (C) binder resin further. As said (C) binder resin, Preferably, the structural unit guide | induced from (meth) acrylic acid is contained. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. Content of the structural unit guide | induced from the said (meth) acrylic acid is 10 mol% or more and 40 mol% or less in molar fraction among all the structural units which comprise binder resin, More preferably, it is 13 mol% or more and 35 mol% It is as follows. When content of the structural unit derived from (meth) acrylic acid exists in the said range, since solubility is favorable at the time of image development and a residue tends to remain hard after image development, it is preferable.

As another monomer which guides the structural unit of binder resin other than the structural unit derived from (meth) acrylic acid, For example, an aromatic vinyl compound, unsaturated carboxylic acid ester, unsaturated carboxylic acid aminoalkyl ester, unsaturated carboxylic acid Glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, monoacryloyl groups or monomethacryloyl groups at the ends of the polymer molecular chains The macromonomers which have a thing are mentioned. For example, the unit represented by following formula (32), the unit represented by formula (33), etc. are mentioned as said structural unit.

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

R ¹⁶ and R ¹⁷ as a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 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 And 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group and the like, preferably hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec- A butyl group and a tert- butyl group are mentioned, More preferably, a hydrogen atom, a methyl group, and an ethyl group are mentioned.

Specifically as said (C) binder resin, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate public Copolymer, methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / components represented by the formula (33) wherein R ¹⁶ in formula 33 represents a methyl group, and R ¹⁷ represents hydrogen Atom) / N-benzylmaleimide / benzyl methacrylate copolymer, methacrylic acid / component represented by the formula (33), wherein R ¹⁶ in formula 33 represents a methyl group, and R ¹⁷ represents a hydrogen atom ) / N- cyclohexylmaleimide / benzyl methacrylate copolymer, methacrylic acid / ingredients of the formula 32 (where, where 32 of the formula R ¹⁶ is methyl, R ¹⁷ is a hydrogen atom or Clearance) / benzyl methacrylate copolymer, a composition represented by the formula 32 (where, in which formula 32 of R ¹⁶ is methyl, R ¹⁷ represents a hydrogen atom) / benzyl methacrylate copolymer, methacrylic acid A structural component represented by the general formula (33) wherein R ¹⁶ represents a methyl group and R ¹⁷ represents a hydrogen atom in formula (33) / styrene / dicyclopentanyl methacrylate copolymer and the like.

The acid value of (C) binder resin used by this invention becomes like this. Preferably it is 30-150, More preferably, it is 35-135, Especially preferably, it is 40-120. When the acid value is in the above range, the solubility in the developing solution is improved, so that the unexposed portion is easily dissolved, the sensitivity is increased, and since the pattern of the exposed portion remains at the time of development, the remaining film ratio is preferable. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be determined by titration using an aqueous potassium hydroxide solution.

The content of the (C) binder resin is preferably 5 to 40% by mass, more preferably 8 to 35% by mass, particularly preferably 10 to 32% by mass with respect to the solids content of the colored curable composition. . (C) Since content of binder resin exists in the said range, since a pattern can be formed and a resolution and a residual film rate tend to improve, it is preferable.

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

Constituents derived from methacrylic acid / components represented by formula (33) wherein R ¹⁶ in formula 33 represents a methyl group and R ¹⁷ represents a hydrogen atom / components derived from benzyl methacrylate The copolymer which comprises the structural component derived from clofentanyl methacrylate can be obtained by making glycidyl methacrylate react with the copolymer of benzyl methacrylate, methacrylic acid, and dicyclopentanyl methacrylate.

The polystyrene reduced weight average molecular weight of (C) binder resin becomes like this. Preferably it is 5,000-100,000, More preferably, it is 6,000-80,000, Especially preferably, it is 7,000-60,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is also high, solubility in the developing solution of the unexposed part is good, and since the resolution tends to be improved, it is preferable.

The colored curable composition of this invention can contain (D) photoinitiator further. As said photoinitiator, a triazine type compound, an acetophenone type compound, a biimidazole type compound, an active radical generator, an acid generator, etc. are mentioned.

As said triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl)-, for example. 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, and preferably 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- Lysine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, and more preferably 2,4-bis (trichloromethyl) -6- Piperonyl-1,3,5-triazine.

As said acetophenone type compound, diethoxy acetophenone, 2-methyl- 2-morpholino-1- (4-methylthio phenyl) propane- 1-one, 2-hydroxy- 2-methyl- 1, for example -Phenylpropane-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) Oligomers of butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and the like, and preferably 2-methyl-2- Morpholino-1- (4-methylthiophenyl) propane-1-one, and the like, 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-morpholino Phenyl) butan-1-one, and more preferably 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butane -1-one can be mentioned.

As said biimidazole type compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 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'-tetra Phenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 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'-tetraphenylbiimi Dazole, 2,2'-bis (2-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-methylphenyl) -4,4', 5, 5'-tetraphenylbiimidazole etc. are mentioned, Preferably 2,2'-bis (2-chlorophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole are mentioned.

Active radical generators generate active radicals upon irradiation with light. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, oxime compounds and the like.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As said benzophenone type compound, for example, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'- methyldiphenyl sulfide, 3,3 ', 4,4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro- 4-propoxy thioxanthone etc. are mentioned.

As said oxime type compound, O-acyl oxime type compound is mentioned, for example, As a specific example, 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-phenylsulfanylphenyl) -octane-1-one oxime-O-acetate And 1- (4-phenylsulfanylphenyl) -butan-1-one oxime-O-acetate.

As active radical generators other than the above examples, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10- Phenanthrene quinone, camphor quinone, methyl phenylglyoxylate, a titanocene compound, etc. can be used.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-acetoxyphenyldimethylsulfonium-p-toluene Sulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium-p-toluenesulfo Onium salts, such as a nitrate and diphenyl iodonium hexafluoro antimonate, nitrobenzyl tosylates, benzoin tosylate, etc. are mentioned.

In addition, among the compounds described above as the active radical generator, there are also compounds which generate an acid simultaneously with the active radical. For example, a triazine-based photopolymerization initiator is also used as the acid generator.

The content of the photopolymerization initiator (D) is preferably 0.1 to 25% by mass, more preferably 1 to 20% by mass, based on the mass fraction with respect to the total amount of the (B) polymerizable compound and (C) binder resin. . (D) When the content of the photopolymerization initiator is in the above range, the sensitivity is increased, the exposure time is shortened, and the productivity is improved. On the other hand, when the sensitivity is too high, the line width does not become too thick at the minimum line width at which the pattern of the line and space is resolved. This is preferable because there is.

The colored curable composition of the present invention may further contain (E) a photopolymerization initiation aid. The photopolymerization initiation aid (E) is usually used in combination with the photopolymerization initiator (D), and is a compound used to promote polymerization of the photopolymerizable compound in which polymerization is initiated by the photopolymerization initiator (D).

Examples of the (E) photopolymerization initiation aid include an amine compound, an alkoxy anthracene compound, a thioxanthone compound, and the like.

Examples of the amine compound include triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate. , 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4 ' -Bis (ethylmethylamino) benzophenone etc. are mentioned, Among these, 4,4'-bis (diethylamino) benzophenone is preferable.

As said alkoxy anthracene type compound, 9,10- dimethoxy anthracene, 2-ethyl-9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2-ethyl-9, 10- diethoxy anthracene etc. Can be mentioned.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro- 4-propoxy thioxanthone etc. are mentioned.

(E) A photoinitiator can be used individually or in combination of 2 or more types. In addition, a commercially available thing can be used as (E) photoinitiation start adjuvant, As a commercially available (E) photoinitiation adjuvant, EAB-F (Hodogaya Chemical Co., Ltd. product, 4,4) is a brand name, for example. Organic amine compounds such as' -bis (diethylamino) benzophenone), and the like.

As a combination of (D) photoinitiator / (E) photoinitiator in the colored curable composition of this invention, it is 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) propan-1-one / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4,4'- Bis (diethylamino) benzophenone, benzyldimethylketal / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] Propan-1-one / 4,4'-bis (diethylamino) benzophenone, 1-hydroxycyclohexylphenylketone / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2 Oligomer / 4,4'-bis (diethylamino) benzophenone of 2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) Tan-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-one / 4,4'-bis (diethylamino) Benzophenone, etc., 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 using these (E) photoinitiator, the usage-amount is preferably 0.01-10 mass parts, More preferably, 0.01-5 mass parts per 1 mass part of (D) photoinitiators.

The colored curable composition of this invention can contain the (F) solvent further. 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 and 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, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, meth Oxypentyl Three, and the like lactate, anisole, phenetole, methyl anisole.

As said aromatic hydrocarbons, benzene, toluene, xylene, mesitylene, etc. are mentioned, for example.

As said ketones, for example, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, 4-hydroxy 4-methyl-2 pentanone etc. are mentioned.

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

As said ester, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoam 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 butyl acetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, Ethyl 3-oxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxypropionic acid Propyl, 2-methoxy propionate, 2-methoxy ethylpropionate, 2-methoxy propylpropionate, 2-ethoxypropionate, 2-ethoxy Ethyl propionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ-butyrolactone, etc. Can be mentioned.

As said amides, N, N-dimethylformamide, N, N-dimethylacetamide, etc. are mentioned, for example.

As another (F) solvent, N-methylpyrrolidone, dimethyl sulfooxide, etc. are mentioned, for example.

The said (F) solvent can be used individually or in combination of 2 types or more, respectively.

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

The content of the solvent (F) is preferably 70 to 90% by mass, and more preferably 75 to 88% by mass based on the mass fraction with respect to the colored curable composition. When content of a solvent exists in the said range, in-plane uniformity at the time of application | coating is favorable, since the color density at the time of forming a color filter is enough, and display characteristics are favorable, it is preferable.

In addition, (G) surfactants may be included. (G) As surfactant, silicone type surfactant, a fluorine-type surfactant, and the silicone type surfactant which has a fluorine atom are mentioned.

As said silicone type surfactant, surfactant etc. which have a siloxane bond are mentioned. Specifically, Toray Silicone DC3PA, Copper SH7PA, Copper DC11PA, Copper SH21PA, Copper SH28PA, Copper 29SHPA, Copper SH30PA, Polyether modified silicone oil SH8400 (manufactured by Toray Silicon, Ltd.), KP321, KP322, KP323, and KP324 And KP326, KP340, KP341 (manufactured by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (manufactured by GE Toshiba Silicon Co., Ltd.), and the like.

As said fluorine-type surfactant, surfactant etc. which have a fluorocarbon chain | strand are mentioned. Specifically, fluorine FC430, copper FC431 (manufactured by Sumitomo 3M Co., Ltd.), megapack F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F470, copper F475, copper R30 (trade name). Dainippon ink Kagaku Kogyo Co., Ltd.), F-top EF301, East EF303, East EF351, East EF352 (Shin Akita Kasei Co., Ltd.), Suplon S381, East S382, East SC101, East SC105 (Asahi Glass ( Ltd.), E5844 (made by Daikin Fine Chemical Co., Ltd.), BM-1000, BM-1100 (made by BM Chemie), etc. are mentioned.

As silicone type surfactant which has the said fluorine atom, surfactant etc. which have a siloxane bond and a fluorocarbon chain | strand are mentioned. Specifically, Mega Pack R08, Copper BL20, Copper F475, Copper F477, Copper F443 (manufactured by Dainippon Ink & Chemicals Co., Ltd.) and the like can be cited as trade names.

These surfactant can be used individually or in combination of 2 or more types.

The colored curable composition of this invention can contain the organic acid of molecular weight 1,000 or less. As said organic acid, the organic acid disclosed by Unexamined-Japanese-Patent No. 5-343631 is mentioned, for example. Specific examples include 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 and methacrylic acid. Preferably, malonic acid, oxalic acid, fumaric acid, and phthalic acid are mentioned. Since the residue tends to be better by containing an organic acid having a molecular weight of 1,000 or less, it is preferable.

The colored curable composition of the present invention may further contain additives such as fillers, polymer compounds other than the (C) binder resin, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerates, organic amine compounds, and (H) curing agents. .

As said filler, microparticles | fine-particles, such as glass and alumina, are mentioned, for example.

As high molecular compounds other than said (C) binder resin, polyvinyl alcohol, polyacrylic acid, polyethyleneglycol monoalkyl ether, polyfluoroalkyl acrylate, etc. are mentioned, for example.

Examples of the adhesion promoter include vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane, etc. are mentioned.

As said antioxidant, 4,4'- thio-bis (6-tert- butyl- 3-methyl phenol), 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], pentaerythritol-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'-hydroxyphenylpropione )] Methane, and the like.

As said ultraviolet absorber, For example, Benzotriazole system, such as 2- (2-hydroxy-3- tert- butyl- 5-methylphenyl) -5-chloro benzotriazole;

Benzophenones such as 2-hydroxy-4-octyloxybenzophenone;

Benzoate systems such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate;

Triazine system, such as 2- (4, 6- diphenyl- 1, 3, 5- triazin- 2-yl) -5-hexyloxyphenol, etc. are mentioned.

As said aggregation inhibitor, sodium polyacrylate etc. are mentioned, for example.

By the addition of the organic amine compound, a pixel excellent in adhesion to the substrate can be provided without generating residue on the substrate of the unexposed portion at the time of development.

As said organic amine compound, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptyl, for example Monoalkyl amines such as amine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine;

Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine and 4-methylcyclohexylamine;

Methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec- Dialkylamines such as butylamine, di-tert-butylamine, di-n-pentylamine and di-n-hexylamine;

Monoalkyl monocycloalkylamines 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 , Trialkyl such as triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine and tri-n-hexylamine Amines;

Dialkyl monocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;

Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine and tricyclohexylamine;

Monoalkanes such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol Olamines;

Monocycloalkanolamines such as 4-amino-1-cyclohexanol;

Dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine and di-n-hexanolamine;

Dicycloalkanolamines such as di (4-cyclohexanol) amine;

Trialkanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, iri-n-pentanolamine and 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 Aminoalkanediols such as propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol and 2-diethylamino-1,3-propanediol;

Aminocycloalkanediols, such as 4-amino-1,2-cyclohexanediol and 4-amino-1,3-cyclohexanediol;

Amino group-containing cycloalkanonemethanols such as 1-aminocyclopentanonemethanol and 4-aminocyclopentanonemethanol;

1-aminocyclohexanonemethanol, 4-aminocyclohexanonemethanol, 4-dimethylaminocyclopentanmethanol, 4-diethylaminocyclopentanmethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol Amino group-containing cycloalkanethanols;

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 Aminocarboxylic acids such as aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid;

Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, p-isopropylaniline, pn-butylaniline, p-tert-butylaniline, 1-naphthylamine Aromatic amines such as 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline and p-methyl-N, N-dimethylaniline;

aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol and p-diethylaminobenzyl alcohol;

aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol and p-diethylaminophenol;

and aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid.

As said (H) hardening | curing agent, the compound which can react with the carboxyl group in (C) binder resin by crosslinking, and can crosslink (C) binder resin, the compound which can superpose | polymerize independently and harden a coloring pattern, etc. are mentioned, for example. have. As said compound, an epoxy compound, an oxetane compound, etc. are mentioned, for example, An oxetane compound is used preferably.

Here, as an epoxy compound, a bisphenol-A epoxy resin, a hydrogenated bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, a hydrogenated bisphenol F-type epoxy resin, a novolak-type epoxy resin, another aromatic epoxy resin, an alicyclic epoxy, for example Epoxy resins such as resins, heterocyclic epoxy resins, glycidyl ester resins, glycidylamine resins, and epoxidized oils, and aliphatic, alicyclic or aromatic groups other than brominated derivatives, epoxy resins and brominated derivatives of these epoxy resins. The epoxy compound of the, the epoxide of the (co) polymer of butadiene, the epoxide of the (co) polymer of isoprene, the (co) polymer of glycidyl (meth) acrylate, triglycidyl isocyanurate, etc. are mentioned. .

As said oxetane compound, carbonate bis oxetane, xylylene bis oxetane, adipate bis oxetane, a terephthalate bis oxetane, a cyclohexane dicarboxylic acid bis oxetane, etc. are mentioned, for example.

When the colored curable composition of this invention contains an epoxy compound, an oxetane compound, etc. as a hardening | curing agent, the compound which can ring-open-polymerize the epoxy group of an epoxy compound, the oxetane skeleton of an oxetane compound can be included. As said compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example.

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-naphthalene tetracarboxylic acid, 3,3 '. Aromatic polyhydric carboxylic acids such as, 4,4'-benzophenonetetracarboxylic acid;

Aliphatic polyhydric carboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid and itaconic acid;

Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentane Alicyclic polyhydric carboxylic acids, such as tetracarboxylic acid and a 1, 2, 4, 5- cyclohexane tetracarboxylic acid, etc. are mentioned.

As said polyhydric carboxylic anhydride, aromatic polyhydric carboxylic acids, such as a phthalic anhydride, a pyromellitic anhydride, a trimellitic anhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, for example Anhydrides;

Aliphatic polyhydric carboxylic acid anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarvallylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride logistics;

Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polyhydric carboxylic acid anhydrides such as water, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, himic acid anhydride, and hydride anhydride;

Ester group containing carboxylic anhydrides, such as ethylene glycol bistrimellitate acid and glycerol tristrimellitate anhydride, etc. are mentioned.

As said carboxylic anhydrides, what is marketed as an epoxy resin hardener can also be used. As said epoxy resin hardening | curing agent, Adeka hardener EH-700 (made by Asahi Denka Kogyo Co., Ltd.), Rikaside HH, MH-700 (all are Shin Nippon Chemical Co., Ltd.) etc. are mentioned, for example.

The said hardening | curing agent can be used individually or in combination of 2 or more types.

As a method of forming the pattern of a color filter using the colored curable composition of this invention, the colored curable composition of this invention is made into the board | substrate or another resin layer (for example, the other colored curable composition layer previously formed on the board | substrate). Etc.), a volatile component such as a solvent is removed to form a colored layer, the photolithography method or a colored curable composition which is exposed to the colored layer through a photomask, developed and further heated as necessary, or inkjet The inkjet method etc. which apply | coat to a board | substrate or another resin layer using an apparatus, remove a volatile component, such as a solvent, form a colored layer, and harden | cure by any one or more of heating or exposure are mentioned.

The color filter obtained in this way contains a pattern, and a preferable liquid crystal display device is obtained by using the said color filter.

By using the colored curable composition of this invention, it becomes possible to manufacture the color filter which is excellent in heat resistance and solvent resistance, and does not fall light resistance and contrast.

<Example>

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

In the colored curable composition of this invention, as a manufacturing method of the phthalocyanine compound represented by General formula (1) used as a coloring agent (A), Unexamined-Japanese-Patent No. 63-30566, Unexamined-Japanese-Patent No. 63-141982, Japan Patent Publication No. 1-45474, Japanese Patent Publication No. 2-282386, Japanese Patent Publication No. 4-39361, Japanese Patent Publication No. 5-222302, Japanese Patent Publication No. 6 -107663, Unexamined-Japanese-Patent No. 5-221952, Unexamined-Japanese-Patent No. 5-345861, etc. can be manufactured by the method as described.

Synthesis Example 1

<Synthesis of Coloring Agent (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, 0.59 g (6 mmol) of cuprous anhydride ) And 20 mL of benzonitrile were injected and reacted at 175 ° C. for 12 hours. After completion | finish of reaction, the reaction mixture was thrown in methanol, the solid content produced was wash | cleaned with methanol, then water, and it dried under reduced pressure at 60 degreeC, and obtained 5.45 g of the green compound which is a target object (yield 75.1%).

The obtained green compound was dissolved in ethyl lactate, and the visible absorption spectrum was measured. As a result, the maximum absorption wavelength was 654.0 nm and the molar extinction coefficient (ε) was 1.026 × 10 ⁵ .

Synthesis Example 2

<Synthesis of Coloring Agent (A-2)>

Synthesis of Phthalocyanine Compounds Represented by Formula (1-14)

7.83 g (20 mmol) of 3,4,6-trifluoro-5- (2-methyl-6-methoxyethoxycarbonylphenoxy) phthalonitrile, 0.94 g of vanadium trichloride in a 100 mL four-necked flask 6 mmol) and 25 mL of benzonitrile were injected and reacted at 175 ° C. for 4 hours. After completion of the reaction, the insoluble 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 a green compound (yield 54.2%).

The obtained green compound was dissolved in ethyl lactate, and the visible absorption spectrum was measured, and the maximum absorption wavelength was 714.0 nm and the molar extinction coefficient (epsilon) was 1.055x10 <^5> .

Synthesis Example 3

<Synthesis of Coloring Agent (A-3)>

Synthesis of barbiturate azo dyes represented by the formula (7-4)

300 g of water was added to 30 g (61 mmol) of 2,2'-benzidine disulfonic acid (containing 30% of water) represented by the following Chemical Formula 35, and then adjusted to pH 7 to 8 with 30% aqueous sodium hydroxide solution under ice cooling. . The following operation was performed under ice cooling. 12.6 g (183 mmol) of sodium nitrite was added thereto, followed by stirring for 30 minutes. A small amount of 38.1 g of 35% hydrochloric acid was added to give a brown solution, followed by stirring for 2 hours. An aqueous solution in which 5.3 g (61 mmol) of amid sulfate was dissolved in 57.4 g of water was added to the reaction solution, followed by stirring 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 following Formula 36, and then adjusted to pH 8 to 9 with an aqueous 30% sodium hydroxide solution under ice-cooling.

The following operation was performed under ice cooling. The aqueous barbituric acid 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 to pH 8-9 with an aqueous 30% sodium hydroxide solution. After completion of dropping, a yellow suspension was obtained by stirring for further 3 hours. The yellow solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 15 g (21 mmol, 34% of yield) of the azo compound represented by following formula (37) was obtained.

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 were added to a flask equipped with a cooling tube and a stirring apparatus, and stirred at 20 ° C. or less. 6 g (54 mmol) of thionyl chloride was added dropwise while maintaining the mixture as it is. After completion of the dropwise addition, the temperature was raised to 50 ° C, the reaction was maintained at the same temperature for 5 hours, and then cooled to 20 ° C. A mixture of 3 g (20 mmol) of 3-aminophenylbutane and 10 g (103 mmol) of triethylamine was added dropwise while the reaction solution after cooling was kept at 20 DEG C or lower under stirring. Thereafter, the reaction was stirred at the same temperature for 5 hours. Subsequently, the solvent was distilled off from the reaction mixture by a rotary evaporator, and then a small amount of methanol was added thereto, followed by vigorous stirring. This mixture was added to the mixture 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 with ion-exchanged water, and dried under reduced pressure at 60 ° C. to obtain 6 g (6 mmol, yield 78%) of the azo compound represented by the following formula (7-4).

About the azo compound obtained in the present Example, LC-MS analysis was performed on condition of the following.

Device; Agilent 1100 (manufactured by Agilent Technology, Inc.)

Detectors; UV detectors; 254 nm

column; Sumipax ODS (manufactured by Sumika Bunshoe Center Co., Ltd.)

Elution solvent; Solvent system in which 0.1% of trifluoromethylacetic acid is added to a water-acetonitrile mixed solvent

Content of each azo compound was computed from the peak area. As a result, the azo compound represented by the 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 Coloring Agent (A-4)>

Synthesis of pyridoneazo dyes represented by Formula 16

To 100 g (203 mmol) of 2,2'-benzidine disulfonic acid (containing 30% of water) represented by the formula (35) was added 3000 g of water, and then adjusted to pH 7 to 8 with 30% aqueous sodium hydroxide solution under ice-cooling. The following operation was performed under ice cooling. 56 g (812 mmol) of sodium nitrite was added thereto, followed by stirring for 30 minutes. 150 g of 35% hydrochloric acid was added in small portions to obtain a brown solution, followed by stirring for 2 hours. An aqueous solution in which 38 g (406 mmol) of amid sulfate was dissolved in 380 g of water was added to the reaction solution, followed by stirring to obtain a suspension containing a diazonium salt.

76 g (426 mmol) of 1-ethyl-3-cyano-4-methyl-6-hydroxypyrido-2-one represented by the following Chemical Formula 38 was added with 1000 g of water, followed by 30% sodium hydroxide under ice-cooling. The aqueous solution was adjusted to pH 8-9.

The following operation was performed under ice cooling. After stirring the alkali aqueous solution of the said pyridones to make it a colorless solution, the suspension containing diazonium salt was dripped by the pump, adjusting to pH 8-9 with 30% sodium hydroxide aqueous solution. After completion of dropping, a yellow suspension was obtained by stirring for further 3 hours. The yellow solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 137 g (204 mmol, 100% of yield) of the azo compound represented by following formula (39) was obtained.

5 g (7 mmol) of the azo compound represented by the formula 39 obtained in the above operation, 50 g of chloroform and 2.4 g (33 mmol) of N, N-dimethylformamide were charged into a flask equipped with a cooling tube and a stirring device. 7 g (59 mmol) of thionyl chloride was added dropwise while maintaining the temperature below 20 ° C under stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C, the reaction was maintained at the same temperature for 5 hours, and then cooled to 20 ° C. A mixture of 4 g (30 mmol) of 1,5-dimethylhexylamine and 12 g (119 mmol) of triethylamine was added dropwise while the reaction solution after cooling was kept at 20 DEG C or lower under stirring. Thereafter, the reaction was stirred overnight at the same temperature. Subsequently, the solvent was distilled off from the reaction mixture by a rotary evaporator, and then a small amount of methanol was added thereto, followed by vigorous stirring. This mixture was added to the 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 with ion exchanged water, and dried under reduced pressure at 60 ° C to obtain 6 g (6 mmol, 80% yield) of the azo compound represented by the formula (16).

<Formula 16>

When the azo compound obtained in the present Example was subjected to the same structural analysis as above, the azo compound represented by the formula (16) was detected as a compound having a molecular weight of 944, and the area percentage value with respect to the total peak area was 58.3%. In addition, a monosulfonated azo compound represented by the formula (40) was detected as a compound having a molecular weight of 833, and an 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. Then, after the solution in a flask was heated up at 100 degreeC, dicyclopentanyl methacrylate (FA-513M; Hitachi Kasei Kogyo Co., Ltd.) 22.0 g (0.10 mol), benzyl methacrylate 70.5 g (0.40 mol) , A mixture containing 43.0 g (0.5 mol) of methacrylic acid, 3.6 g of azobisisobutyronitrile and 164 g of propylene glycol monomethyl ether acetate was added dropwise to the flask over 2 hours using a dropping funnel, and then Further stirring was continued at 100 ° C. for 5 hours.

After completion of the stirring, air was introduced into the flask through the gas introduction tube, and the atmosphere in the flask became air, followed by 35.5 g [0.25 mol of glycidyl methacrylate (in mole fraction with respect to methacrylic acid used in this reaction). 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 obtain a solution containing the resin (C-1) (solid content 38.5). Mass%, acid value 80 mgKOH / g).

Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of a polymer having an acid group such as carboxylic acid, and is usually determined by titration using an aqueous potassium hydroxide solution having a known concentration. .

The polystyrene reduced weight average molecular weight of obtained resin (C-1) was 9,000.

About the measurement of the polystyrene conversion weight average molecular weight of said (C-1) binder resin, it carried out on condition of the following using GPC method.

Device; HLC-8120GPC (manufactured by Tosoh Corporation)

column; TSK-GELG2000HXL

Column temperature; 40 ℃

menstruum; THF

Flow rate; 1.0 mL / min

Test liquid solids concentration; 0.001 to 0.01 mass%

Injection amount; 50 μL

Detectors; RI

Calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

The component used by a present Example is as follows, and may abbreviate | omit it and display it below.

(A-1) Colorant: Dye obtained in Synthesis Example 1

(A-2) Colorant: The dye obtained in Synthesis Example 2

(A-3) Colorant: Dye obtained in Synthesis Example 3

(A-4) Colorant: Dye obtained in Synthesis Example 4

(A-5) Colorant: A compound represented by the formula (Cyanine-based dye: NK-3212: manufactured by Hayashibara Seibutsu Chemical Co., Ltd.)

<Formula 29>

(A-6) Colorant: Compound represented by the formula (FB-22: Yamada Kagaku Kogyo Co., Ltd. phthalocyanine dye)

(A-7) Coloring agent: A compound represented by the chemical formula (FB-24: Yamada Chemical Co., Ltd. phthalocyanine dye)

(B-1) Photopolymerizable Compound: DPHA (manufactured by Nippon Kayaku Co., Ltd.)

(B-2) Photopolymerizable Compound: A-GLY-3E (manufactured by Shinnakamura Kagaku Kogyo Co., Ltd.)

Ethylene Oxide (3) Glycerin Triacrylate

(C-1) Binder resin: Resin (C-1) obtained by the synthesis example 5 (propylene glycol monomethyl ether acetate solution of 38.5 mass% of solid content)

(D-1) Photoinitiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one

(E-1) Photoinitiation start adjuvant: 4,4'-bis (diethylamino) benzophenone

(F-1) Solvent: Propylene glycol monomethyl ether

(F-2) Solvent: Ethyl 3-ethoxypropionate

(G-1) Surfactant: Megapack F475 (manufactured by Dainippon Ink Chemical Industries, Ltd.)

(H-1) Curing agent: Sumiepoxy ESCN-195XL-80 [ortho cresol novolak type epoxy resin (manufactured by Sumitomo Chemical Co., Ltd.)]

Example 1

[Production 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: 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

Was mixed to obtain colored curable composition 1.

[Formation of Coating Film]

Subsequently, after apply | coating the colored curable composition 1 obtained above on the glass (# 1737; Corning) by the spin coating method, the volatile component was volatilized for 3 minutes at 100 degreeC, and the colored curable composition film was formed. After cooling, this colored curable composition film was irradiated with i line | wire (wavelength 365nm), and was exposed. The light source of i line | wire was irradiated after making it into parallel light using the ultrahigh pressure mercury lamp. The irradiation light amount was 500 mJ / cm 2. Subsequently, post-baking was performed at 220 degreeC for 20 minutes, and the coloring curable composition film | membrane of 2 micrometers of film thicknesses was obtained.

[Evaluation 1] heat resistance evaluation

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 heated at 230 degreeC for 120 minutes in the air atmosphere in oven, the chromaticity of the colored curable composition film after heating was measured to be the same, and the color difference ((DELTA) Eab *) before and after heating was 3.6.

As evaluation criteria for chromaticity, almost no color change is observed when ΔEab * is 5 or less, and exhibits good characteristics as a color filter, and when ΔEab * is more than 5 and 10 or less, a slight color change is observed. It is a level which is satisfactory practically, and when (DELTA) Eab * is 10 or more, a sure color change can be confirmed and there is a problem level as a color filter.

[Evaluation 2] light resistance evaluation

A UV blocking filter (COLORED OPTICAL GLASS L38; manufactured by Hoya Co., Ltd .; blocking light of 380 nm or less) was placed on the obtained colored curable composition film, and the xenon lamp light was subjected to a light resistance tester (SUNTEST CPS +: manufactured by Toyo Seiki Co., Ltd.). Was investigated for 48 hours.

It was 0.6 when the chromaticity of the colored curable composition film | membrane after irradiation was measured, and the color difference before and behind irradiation was calculated | required.

As a criterion for evaluating the color difference, almost no color change is observed when ΔEab * is 5 or less, as described above, showing good characteristics as a color filter, and a slight color change is observed when ΔEab * exceeds 5 and 10 or less. It is a level which is satisfactory practically in a color filter, and if (DELTA) Eab * is 10 or more, a certain color change can be confirmed and there is a problem as a color filter.

[Evaluation 3] solvent resistance evaluation

The chromaticity of the obtained colored curable composition film was measured using the colorimeter same as the above.

Subsequently, the obtained colored curable composition film was immersed in a large excess amount of propylene glycol monomethyl ether maintained at 23 ° C. for 30 minutes, the chromaticity of the colored curable composition film after immersion was measured in the same manner, and the color difference before and after heating was obtained. It was 1.8.

As a criterion for evaluating the color difference, almost no color change is observed when ΔEab * is 5 or less, showing good characteristics as a color filter, and when ΔEab * is more than 5 and 10 or less, a slight color change is observed. It is a level which is satisfactory practically, and if (DELTA) Eab * is 10 or more, a certain color change can be confirmed and there is a problem as a color filter.

[Evaluation 4] contrast evaluation

It was 9112 when the contrast value of the obtained colored curable composition film was measured at 10000 using the contrast colorimeter (CT-1; the Tsubasa Denki Co., Ltd. product).

As an evaluation criterion of the contrast of the colored curable composition film, when the contrast value is 8000 or more, small fragmentation is hardly observed, showing good characteristics as a color filter, and when the contrast value is greater than 6000 and 8000 or less, slight fragmentation Although it is observed, it is a level which is satisfactory practically in a color filter, and when the contrast value is 6000 or less, a certain fragmentation can be confirmed, and it is a level which has a problem as a color filter.

Example 2

[Production of Colored Curable Composition 2]

Except having changed the coloring agent (A-1) of Example 1 into the coloring agent (A-2), it mixed similarly to Example 1 and obtained the colored curable composition 2.

[Formation and Evaluation of Coating Film]

In the same manner as in Example 1, a colored curable composition film having a thickness of 2 μm was produced and evaluated, the color difference in the heat resistance evaluation was 4.8, the color difference in the light resistance evaluation was 3.5, the color difference in the solvent resistance was 0.8, The contrast value was 9057.

Example 3

[Production of Colored Curable Composition 3]

(A-1) 4.590 parts by mass

(A-3) 3.060 parts by mass

(B-1) 4.712 parts by mass

(C-1) 8.160 parts by mass (solid content: 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

Was mixed to obtain colored curable composition 3.

[Formation and Evaluation of Coating Film]

In the same manner as in Example 1, a colored curable composition film having a film thickness of 2 μm was produced and evaluated. The color difference in the heat resistance evaluation was 2.6, the color difference in the light resistance evaluation was 0.7, the color difference in the solvent resistance was 1.8, The contrast value was 8971.

Example 4

[Production of Colored Curable Resin Composition 4]

Except having changed (A-3) of Example 3 into (A-4), it mixed similarly to Example 1 and obtained colored curable composition 4.

[Formation and Evaluation of Coating Film]

The color difference in heat resistance evaluation was 3.8, the color difference in light resistance evaluation is 0.9, the color difference in solvent resistance is 4.3, as a result of making and coloring the colored curable composition film | membrane of film thickness 2 micrometers similarly to Example 1, The contrast value was 9232.

Example 5

[Production of Colored Curable Composition 5]

Except having changed (A-3) of Example 3 into (A-5), it mixed similarly to Example 1 and obtained colored curable composition 5.

[Formation and Evaluation of Coating Film]

In the same manner as in Example 1, a colored curable composition film having a film thickness of 2 μm was produced and evaluated. The color difference in the heat resistance evaluation was 8.9, the color difference in the light resistance evaluation was 2.8, and the color difference in the solvent resistance was 2.6, The contrast value was 9151.

Example 6

[Production 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: 2.749 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

(H-1) 0.785 parts by mass

Was mixed to obtain colored curable composition 6.

[Formation and Evaluation of Coating Film]

The color difference in heat resistance evaluation was 2.9, the color difference in light resistance evaluation was 2.4, the color difference in solvent resistance was 1.6, as a result of making and coloring the colored curable composition film | membrane of 2 micrometers in the same manner as Example 1, The contrast value was 8652.

Comparative Example 1

[Preparation of Colored Curable Composition 7]

Except having changed (A-1) of Example 1 into (A-6), it mixed similarly to Example 1 and obtained colored curable composition 7.

[Formation and Evaluation of Coating Film]

The color difference in heat resistance evaluation was 20.1, the color difference in light resistance evaluation was 4.2, the color difference in solvent resistance was 13.4, as a result of having manufactured and evaluated the coloring curable composition film | membrane of film thickness 2 micrometers similarly to Example 1. The contrast value was 9036.

Comparative Example 2

[Production of Colored Curable Composition 8]

Except having changed (A-1) of Example 1 into (A-7), it mixed like Example 1 and obtained the colored curable composition 8.

[Formation and Evaluation of Coating Film]

The color difference in heat resistance evaluation was 32.3, the color difference in light resistance evaluation was 6.2, the color difference in solvent resistance was 15.1, when the colored curable composition film | membrane of 2 micrometers of film thicknesses was produced and evaluated similarly to Example 1. The contrast value was 8725.

Comparative Example 3

[Production of Colored Curable Composition 9]

Except having changed (A-1) of Example 3 into (A-6), it mixed like Example 1 and obtained the colored curable composition 9.

[Formation and Evaluation of Coating Film]

The color difference in heat resistance evaluation was 17.5, the color difference in light resistance evaluation was 7.5, the color difference in solvent resistance was 30.6, The contrast value was 8120.

Claims (10)

It is a colored curable composition containing (A) a coloring agent and (B) polymeric compound, The coloring curable composition containing the pigment | dye represented by following formula (A) by (A) coloring agent. <Formula 1>

In Chemical Formula 1, k represents an integer of 0 or 1, M represents a metal or a metal oxide, and A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom or a group of substituents represented by the following Chemical Formulas 2 to 5 Wherein substituents selected from A ¹ to A ¹⁶ represent a substituent selected from the group of the substituents represented by Formulas 2 to 5, <Formula 2>

<Formula 3>

<Formula 4>

<Formula 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 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 group having 1 to 8 carbon atoms, 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 straight 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 from 0 to 5, Provided that 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 from 1 to 6, j is an integer of 1 or 2] The colored curable composition according to claim 1, wherein all of the substituents represented by A ¹ to A ¹⁶ in the general formula (1) are fluorine atoms except for a substituent selected from the group of the substituents represented by the general formulas (2) to (5). The colored curable composition according to claim 1 or 2, wherein in formula (2), G ¹ is an oxygen atom. The group according to any one of claims 1 to 3, wherein the (A) colorant further comprises a barbiturate azo dye, a pyridone azo dye, a pyrazolone azo dye, a quinophthalone dye, and a cyanine dye. A colored curable composition comprising at least one dye selected from. The colored curable composition according to claim 4, wherein the barbituric acid azo dye is a dye represented by the following general formula (7). <Formula 7>

In Formula 7, T <^1> and T <^2> represent an oxygen atom or a sulfur atom each independently, R ³¹ to R ³⁴ each independently represent a hydrogen atom, a saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms in which a hydroxyl group is substituted, and an alkoxyl group of 1 to 8 carbon atoms is substituted. Saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, Saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with thioalkoxyl group having 1 to 8 carbon atoms, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms or 2 carbon atoms To acyl groups of 10 to 10, R ³⁵ to R ⁴² each independently represent a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, an alkoxyl group of 1 to 8 carbon atoms, substituted by a halogen atom, Carboxyl group, sulfo group, sulfamoyl group or N-substituted sulfamoyl group; The colored curable composition according to claim 4, wherein the pyridone azo dye is a dye represented by the following formula (8). <Formula 8>

In the formula (8), Z is a phenyl group having one or two or more groups selected from the group consisting of carboxyl group, carbamoyl group, sulfo group, sulfamoyl group and N-substituted sulfamoyl group, or carboxyl group, carbamo A naphthyl group having 1 to 3 or more groups selected from the group consisting of a diary, a sulfo group, a sulfamoyl group and an N-substituted sulfamoyl group, R ²¹ represents a hydrogen atom, a linear, branched or cyclic saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group or a trifluoromethyl group, R ²² represents a hydrogen atom, a cyano group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, a sulfo group and any one of ammonium salts, lithium salts, sodium salts or potassium salts of the above substituents, R ²³ is a hydrogen atom, a substituted, straight-chain, branched or cyclic saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, an aryl group of 6 to 30 carbon atoms that can be substituted, or an aral of 7 to 20 carbon atoms that can be substituted A group in which a carbon of a kill group, 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 aliphatic oxycarbonyl group having 2 to 20 carbon atoms, which may be substituted, and may be substituted An aryloxycarbonyl group having 7 to 30 carbon atoms, an acyl group having 2 to 20 carbon atoms substituted, an aliphatic sulfonyl group having 1 to 30 carbon atoms substituted, or an arylsulfonyl group having 6 to 30 carbon atoms substituted, Formula 8 may form dimers or multimers at any position; The colored curable composition according to any one of claims 1 to 6, further comprising (C) a binder resin. The pattern formed by the photolithographic method or the inkjet method using the colored curable composition in any one of Claims 1-7. The color filter containing the pattern of Claim 8. The liquid crystal display device provided with the color filter of Claim 9.