KR101449044B1 - Colored curable composition - Google Patents

Abstract

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

Wherein k is an integer of 0 or 1, M is a metal or a metal oxide, A ¹ to A ¹⁶ each independently represent a hydrogen atom, a halogen atom or other substituent,

A coloring curable composition, a colorant, a polymerizable compound

Description

COLORED CURABLE COMPOSITION [0002]

The present invention relates to a colored curable composition.

The colored curable composition is used for the production of a color filter used in a display device such as a liquid crystal display panel, an electroluminescence or a plasma display panel.

It is known that a pigment or a dye is used as a coloring agent in this colored curable composition.

Among them, the colored curable composition using a pigment is generally characterized by high light resistance and heat resistance, but there is a problem that the transmittance of light of the color filter is reduced due to the particles of the pigment, or the contrast is lowered (refer to Patent Document 1 below) .

In addition, the color-curable composition using a dye has a characteristic that the color filter has a high contrast because there is no scattering of light by the pigment particles, but there is a problem that the light resistance and the heat resistance are low (see Patent Documents 2 and 3 below).

Accordingly, various attempts have been made to improve the light resistance and heat resistance of a colored curable composition using a dye. In particular, in a green colored curable composition, a phthalocyanine-based dye having a specific structure and a pyridonaphos- (See Patent Document 4 below).

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

[Patent Document 2] Japanese Unexamined Patent Publication (Kokai) No. 2004-157455, page 3, line 42 to page 4, page 8

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

[Patent Document 4] JP-A-2006-71822

However, the inventors of the present invention have found that there is room for improvement in the heat resistance and solvent resistance of the color filter obtained also 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 a colored curable composition comprising a phthalocyanine dye of a kind different from a phthalocyanine dye conventionally known as a colorant can solve the above problems.

That is, the present invention provides the following [1] to [10].

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

(A) the coloring agent contains a dye represented by the following formula (1).

≪ Formula 1 >

[In the formula 1, k represents an integer of 0 or 1, M represents a metal or metal oxide, A ¹ to A ¹⁶ is a group of the substituents represented by each independently represent a hydrogen atom, a halogen atom or the following formula 2 to 5 , Provided that 1 to 8 of A ¹ to A ¹⁶ are substituents selected from the group of substituents represented by the general formulas (2) to (5)

In formulas (2) to (5), G ¹ to G ⁴ each independently represent an oxygen atom, a sulfur atom or an -N (R ¹⁴ )

R ¹⁴ represents a hydrogen atom or a linear or branched saturated aliphatic hydrocarbon group of 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 linear or branched saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms or an alkoxyl group having 1 to 4 carbon atoms,

e1, g1 and i1 are each independently an integer of 1 to 5,

e2, g2 and i2 each independently represent an integer of 0 to 5,

However, the sum of e1 and e2, the sum of g1 and g2, and the sum of i1 and i2 is an integer of 5 or less,

f and h are each independently an integer of 1 to 6,

j is an integer of 1 or 2]

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

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

[4] The dye according to any one of [1] to [3] above, wherein the colorant is at least one selected from the group consisting of a barbituric acid azo dye, a pyridone azo dye, a pyrazolone azo dye, a quinophthalone dye and a cyanine dye ≪ / RTI > and at least one dyestuff selected from the group consisting of dyes.

[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).

[Wherein T ¹ and T ² each independently represents an oxygen atom or a sulfur atom,

R ³¹ to R ³⁴ each independently represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with a hydroxyl group, or an alkoxyl group having 1 to 8 carbon atoms A saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms substituted with a thioalkoxyl group of 1 to 8 carbon atoms, an aryl group of 6 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, To 10 < RTI ID = 0.0 >

Each of R ³⁵ to R ⁴² independently represents a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, an alkoxyl group having 1 to 8 carbon atoms, A carboxyl group, a sulfo group, a sulfamoyl group or an N-position-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).

[Wherein Z in the formula (8) is a phenyl group having one or more groups selected from the group consisting of a carboxyl group, a carbamoyl group, a sulfo group, a sulfamoyl group and an N-position substituted sulfamoyl group, or a carboxyl group, A naphthyl group having from 1 to 3 at least one group selected from the group consisting of a nitrogen atom, a sulfur atom, a sulfamoyl group and an N-position-substituted sulfamoyl group,

R ²¹ represents a hydrogen atom, a straight-chain, branched or cyclic saturated aliphatic hydrocarbon group of 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-position-substituted carbamoyl group, a sulfamoyl group, a sulfo group and an ammonium salt, a lithium salt, a sodium salt or a potassium salt of each substituent,

R ²³ represents a hydrogen atom, a linear, branched or cyclic saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an aralkyl group having 7 to 20 carbon atoms A carbamoyl group, an N-position-substituted carbamoyl group, an aliphatic oxycarbonyl group having 2 to 20 carbon atoms which may be substituted, a substituted or unsubstituted aliphatic oxycarbonyl group having 2 to 20 carbon atoms, An aryloxycarbonyl group having 7 to 30 carbon atoms, an acyl group having 2 to 20 carbon atoms which may be substituted, an aliphatic sulfonyl group having 1 to 30 carbon atoms which may be substituted, or an arylsulfonyl group having 6 to 30 carbon atoms which may be substituted,

The formula (8) may form a dimer or a dimer at an arbitrary position)

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

[8] A pattern formed by a photolithographic method or an ink-jet method using the color-curable composition according to any one of [1] to [7].

[9] A color filter comprising the pattern described in [8] above.

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

According to the present invention, it is possible to provide a colored curable composition capable of forming a color filter excellent in heat resistance and solvent resistance.

The colored curable composition of the present invention comprises (A) a colorant represented by the following formula (1) as a colorant.

≪ Formula 1 >

In the 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 substituent selected from the group consisting of a hydrogen atom, a halogen atom or a substituent represented by the following general formulas (2) to (5) Provided that 1 to 8 of A ¹ to A ¹⁶ represent substituents selected from the group of substituents represented by formulas (2) to (5).

(2)

(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.

Each of R ¹¹ to R ¹³ independently represents 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 linear or branched saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms or an alkoxyl group having 1 to 4 carbon atoms.

e1, g1 and i1 are each independently an integer of 1 to 5;

e2, g2 and i2 are each independently an integer of 0 to 5;

However, the sum of e1 and e2, the sum of g1 and g2, and the sum of i1 and i2 are integers of 5 or less.

f and h are each independently an integer of 1 to 6;

j is an integer of 1 or 2;

Examples of the metal in M include Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co and Fe. .

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

The base metal in M indicates that each hydrogen atom is bonded to two nitrogen atoms originally to be coordinated with a metal or a metal oxide.

^Examples of the halogen atom represented by A ¹ to A ¹⁶ include a fluorine atom, a chlorine atom and a bromine atom.

Examples of the aryl group having 6 to 20 carbon atoms which may have a substituent in R ¹¹ to R ¹³ include an aryl group which may have a substituent such as a saturated aliphatic hydrocarbon group or a hydroxyl group. Examples of the aryl group include a phenyl group, a hydroxyphenyl group (e.g., 4-hydroxyphenyl group), and a trifluoromethylphenyl group (4-trifluoromethylphenyl group).

Examples of the saturated aliphatic hydrocarbon group as the substituent include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl.

Examples of the linear or branched C 1 -C 8 saturated aliphatic hydrocarbon group for R ¹¹ to R ¹³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert- , A linear or branched pentyl group, a linear or branched hexyl group, a linear or branched heptyl group and a straight chain or branched octyl group. Of these, a methyl group, an ethyl group, an n -Propyl group, isopropyl group, n-butyl group and isobutyl group.

Examples of the halogen atom in J ¹ to J ³ include a fluorine atom, a chlorine atom and a bromine atom, preferably a fluorine atom.

Examples of the straight chain or branched saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms in J ¹ to J ³ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, .

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

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

In the general formula (2), G 1 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 to 5, preferably an integer of 1 to 3, more preferably an integer of 1 or 2.

e2 is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably an integer of 0 or 1.

Examples of the substituent represented by the general formula (2) include groups represented by the following general formulas (2-1) to (2-26), and preferable examples thereof include (2-1) to (2-7) ) To (2-11), (2-13) to (2-18), (2-20) to (2-22), (2-24), and (2-1) to (2-7), (2-9), (2-11), (2-13) 21).

In the general 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 to 6, preferably an integer of 1 to 3, more preferably an integer of 1 or 2.

g1 is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably an integer of 1 or 2.

g2 is an integer of 0 to 4, preferably 0 to 2, more preferably 0 or 1.

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

In the general 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 to 6, preferably an integer of 1 to 3, more preferably an integer of 1 or 2.

i1 is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably an integer of 1 or 2.

i2 is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably an integer of 0 or 1.

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

In the general formula (5), G 4 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 the general formula (5), j is an integer of 1 or 2, preferably 1.

Examples of the substituent represented by the general formula (5) include groups represented by the following general formulas (5-1) to (5-18), and preferable examples thereof include (5-1) to (5-6) (5-1) to (5-6), (5-10), (5-11), (5-13) and (5-16).

Examples of the dye represented by the formula (1) include a dye represented by the following formulas (1-1) to (1-33), preferably (1-1) to (1-5) (1-11), (1-13), (1-14), (1-16), (1-18), (1-19), (1-22) 1-27) to (1-31) and (1-33), and more preferably, (1-1) to (1-3) (1-12), (1-24), (1-28), and (1-29), (1-14) And the like.

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

When the content of the pigment is within the above range, the color density of the color filter is sufficient and the polymerizable compound can be contained in a required amount in the composition, so that solvent resistance tends to be improved.

Herein, the solid content in the present specification refers to the total amount of components excluding the solvent contained in the colored curable composition.

The colored curable composition of the present invention may further comprise (A) at least one colorant selected from the group consisting of a barbituric acid azo dyestuff, a pyridon azo dyestuff, a pyrazolone azo dyestuff, a quinophthalone dyestuff and a cyanine dyestuff Dyes.

The barbituric acid azo dye is not particularly limited and a known substance can be used. Preferably, a barbituric acid azo dye represented by the following formula (7) is used.

≪ Formula 7 >

[Wherein T ¹ and T ² each independently represents an oxygen atom or a sulfur atom,

R ³¹ to R ³⁴ each independently represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with a hydroxyl group, or an alkoxyl group having 1 to 8 carbon atoms A saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms substituted with a thioalkoxyl group of 1 to 8 carbon atoms, an aryl group of 6 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, To 10 < RTI ID = 0.0 >

Each of R ³⁵ to R ⁴² independently represents a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, an alkoxyl group having 1 to 8 carbon atoms, A carboxyl group, a sulfo group, a sulfamoyl group or an N-position-substituted sulfamoyl group]

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

The saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ³¹ to R ³⁴ may be any of linear, branched or cyclic. The number of carbon atoms of the saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms is preferably 2 to 8, more preferably 3 to 6. Examples of the saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- 2-ethylhexyl group and the like), cyclopentyl group, cyclohexyl group, cyclohexylalkyl group and the like.

In the saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, as described above, a hydroxyl group, an alkoxyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms) or an alkoxyl group having 1 to 8 carbon atoms To 4) thioalkoxyl groups may be substituted. Examples of the substituted saturated aliphatic hydrocarbon group include a hydroxyethyl group (such as a 2-hydroxyethyl group), an ethoxyethyl group (such as a 2-ethoxyethyl group), an ethylhexyloxypropyl group (such as 3- Propyl group, etc.), methylthiopropyl group (3-methylthiopropyl group and the like), and the like.

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. The carbon number of the aryl group is calculated to include the carbon number of the substituent, and is preferably 6 to 10. [ Examples of the aryl group include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, A substituted or unsubstituted phenyl group such as a sulfophenyl group, a 4-sulfophenyl group and an ethoxycarbonylphenyl group (4- (COOC ₂ H ₅ ) Ph group).

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. The carbon number of the aralkyl group is calculated to include the carbon number of the substituent, and is preferably 7 to 10. [ Examples of the aralkyl group having 7 to 20 carbon atoms include a benzyl group and a phenethyl group.

The acyl group having 2 to 10 carbon atoms in R ³¹ to R ³⁴ may be unsubstituted, or a substituent such as a saturated aliphatic hydrocarbon group or an alkoxyl group may be bonded. The carbon number of the acyl group is calculated including the carbon number of the substituent, and the number thereof is preferably 2 to 10. [ The acyl group is, for example, an acetyl group, a benzoyl group, a methoxybenzoyl group (p-methoxybenzoyl group, etc.) and the like.

The saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ³⁵ to R ⁴² may be any of linear, branched and cyclic saturated aliphatic hydrocarbon groups as in the case of R ³¹ to R ³⁴ , and the number of carbon atoms thereof is preferably 2 to 8, More preferably from 3 to 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. Specific examples of the saturated aliphatic hydrocarbon group substituted with a halogen atom include a trifluoromethyl group and the like.

The carbon number of the alkoxyl group having 1 to 8 carbon atoms in R ³⁵ to R ⁴² is preferably 1 to 4. Examples of the alkoxyl group include a methoxy group, an ethoxy group, an isopropoxy group, an n-propoxy group, a n-butoxy group, an isobutoxy group, a sec-butoxy group and a tert-butoxy group.

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

R ⁴³ represents a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms (including a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms and an alkoxyl group having 1 to 8 carbon atoms bonded thereto), an aryl group having 6 to 20 carbon atoms, An aralkyl group or an acyl group having 2 to 10 carbon atoms.

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. [

Examples of the saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms for R ⁴³ include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- Methylhexyl group (such as 1-methylhexyl group and 1,5-dimethylhexyl group), ethylhexyl group (such as 2-ethylhexyl group) , A cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group (such as a 2-methylcyclohexyl group), and a cyclohexylalkyl group.

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 1 to 4 carbon atoms) as described above. As the substituted saturated aliphatic hydrocarbon group, propoxypropyl group (3- (isopropoxy) propyl group, etc.) and the like can be mentioned.

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

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

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 thereof is preferably 6 to 10. [ Examples of the acyl group include an acetyl group, a benzoyl group, an o-toluyl group, an m-toluyl group, a p-toluyl group, and a methoxybenzoyl group (p-methoxybenzoyl group and the like).

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

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

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

(8)

Wherein Z represents 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 at the N position, or a carboxyl group, a carbamoyl group , A sulfamoyl group in which the sulfo group and the N-position can be substituted, and a sulfamoyl group in which the N-

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 ammonium salts, lithium salts, sodium salts, and potassium salts of the respective substituents,

R ²³ represents a hydrogen atom, a linear, branched or cyclic saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted, an aryl group having 6 to 30 carbon atoms which may be substituted, an aralkyl group having 7 to 20 carbon atoms A carbamoyl group, an N-position-substituted carbamoyl group, an optionally substituted C2-C20 alkyloxycarbonyl group, a substituted or unsubstituted C2-C20 alkoxycarbonyl group, An aryloxycarbonyl group having 7 to 30 carbon atoms, an acyl group having 2 to 20 carbon atoms which may be substituted, an aliphatic sulfonyl group having 1 to 30 carbon atoms which may be substituted, or an arylsulfonyl group having 6 to 30 carbon atoms which may be substituted,

The formula (8) may form a dimer or a dimer at an arbitrary position)

In the formula (8), the N-substituted sulfamoyl group of the phenyl group and the naphthyl group represented by Z is 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 a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with an alkoxyl group having 1 to 8 carbon atoms) An aralkyl group having 7 to 20 carbon atoms or an acyl group having 2 to 10 carbon atoms (provided that R ²⁴ and R ²⁵ are not hydrogen atoms at the same time).

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

Examples of the saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R ²⁴ and R ²⁵ include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- , Methyl butyl group (1,1,3,3-tetramethyl butyl group etc.), methyl hexyl group (1-methyl hexyl group, 1,5-dimethyl hexyl group etc.), ethylhexyl group ), A cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group (such as a 2-methylcyclohexyl group), a cyclohexylalkyl group and the like, preferably an isopropyl group, an isobutyl group, A 3-tetramethylbutyl group, a 1,5-dimethylhexyl group, and a 2-ethylhexyl group.

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. Examples of the saturated aliphatic hydrocarbon group substituted with an alkoxyl group having 1 to 8 carbon atoms include a propoxypropyl group (such as a 3- (isopropoxy) propyl group) and the like.

The aryl group having 6 to 20 carbon atoms represented by R ²⁴ and R ²⁵ may have a substituent such as an unsaturated aliphatic hydrocarbon group or a hydroxyl group. The number of carbon atoms of the aryl group is calculated to include the number of carbon atoms 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 (4-hydroxyphenyl group) and trifluoromethylphenyl group (4-trifluoromethylphenyl group).

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

The acyl group represented by R ²⁴ and R ²⁵ may be unsubstituted or may be substituted with a substituent such as a saturated aliphatic hydrocarbon group or alkoxyl group. The carbon number of the acyl group is calculated including the carbon number of the substituent, and the number thereof is usually 2 to 10, preferably 6 to 10. The acyl group is, for example, an acetyl group, a benzoyl group, a methoxybenzoyl group (p-methoxybenzoyl group, etc.) and 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.

The saturated aliphatic hydrocarbon group represented by R ²¹ 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. The carbon number thereof is preferably 2 to 8, more preferably 3 to 6. Examples of these saturated aliphatic hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert- butyl, .

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

As the N-position-substituted carbamoyl group represented by R ²² , -CON (R ²⁶ ) R ²⁷ (wherein R ²⁶ and R ²⁷ are each independently a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, A saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms substituted with an alkoxyl group of 8 to 8, an aryl group of 6 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, or an acyl group of 2 to 10 carbon atoms).

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. As specific examples of the acyl group, a benzoyl group further containing a halogen atom, such as a bromobenzoyl group (p-bromobenzoyl group, etc.) and the like can be given.

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

The saturated aliphatic hydrocarbon group represented by R ²³ includes the same groups as the saturated aliphatic hydrocarbon group in R ²¹ described above.

As the aryl group represented by R ²³ , the number of carbon atoms is usually from 6 to 30, preferably from 6 to 20, and more preferably from 6 to 16. Specific examples of these aryl groups include a phenyl group, a 4-nitrophenyl group, a 2-nitrophenyl group, a 2- chlorophenyl group, a 2,4-dichlorophenyl group, a 2,4-dimethylphenyl group, Methoxyphenyl group, 2-methoxycarbonyl-4-nitrophenyl group, and the like.

The group in which a part of carbon atoms of the alicyclic hydrocarbon group represented by R ²³ is substituted with a hetero atom may be saturated or unsaturated and the total number of carbon atoms is preferably from 3 to 20, more preferably from 5 to 15 to be. Specific examples of the group having a heterocyclic ring include a pyrazole group, a 1,2,4-triazole group, an isothiazole group, a benzoisothiazole group, a thiazole group, a benzothiazole group, an oxazole group, And sleeping. Further, it may further have a substituent.

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

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

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

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

The acyl group represented by R ²³ may be an aliphatic carbonyl group, an arylcarbonyl group, and may be either saturated or unsaturated, may be cyclic, and may further have a substituent. The total number of carbon atoms is usually 2 to 20, preferably 2 to 15, more preferably 2 to 10. Specific examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pivaloyl group, and a benzoyl group.

The aliphatic sulfonyl group represented by R ²³ may be saturated, unsaturated, or cyclic. The total number of carbon atoms is usually 1 to 30, preferably 1 to 20, and more preferably 1 to 16. Specific examples of the aliphatic sulfonyl group include a methanesulfonyl group, a butanesulfonyl group, a methoxymethanesulfonyl group, a methoxyethanesulfonyl group, and an ethoxyethanesulfonyl group.

The arylsulfonyl group represented by R ²³ may have a substituent, and the total number of carbon atoms is usually from 6 to 30, preferably from 6 to 20, and more preferably from 6 to 18. Specific examples of the arylsulfonyl group include a benzenesulfonyl group and a toluenesulfonyl group.

Examples of the pyridone azo dyes include the compounds represented by the following formulas (8-1) to (8-9).

The pyridone azo dye represented by the general formula (8) may form a dimer or the like of a dimer or more at an arbitrary position.

The term " multimer " in the formula (8) means that the compound has two or more groups represented by the formula (8) in one molecule, and specific examples thereof include the following compounds.

The pyrazolone azo-based dye is not particularly limited, and known materials can be used. For example, Japanese Patent Application Laid-Open Nos. 2006-276512, 2005-263926, 2006-015669 And the like can be used.

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

The quinophthalone-based dye is not particularly limited, and known materials can be used. For example, JP-A-5-39269, JP-A-6-220339, ) 8-171201 can be used as the quinophthalone dye.

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

The cyanine dye is not particularly limited, and known materials can be used. For example, the cyanine dye described in Japanese Patent Application Laid-Open No. 2005-194509, Japanese Patent Application Laid-Open No. 2007-131818, and Japanese Patent Laid-Open No. 2005-297406 can be used. Specifically, the following compounds and the like can be mentioned.

As the colorant (A), a pigment may be included within a range that does not impair the effect of the present invention.

Examples of the pigment include compounds classified in pigment index (published by The Society of Dyers and Colourists) as pigments, 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 , 147, 148, 150, 153, 154, 166, 173, 194, 214, etc., CI Pigment Green 7, and Pigment Green 36, and preferably C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Green 7, 36 can be mentioned.

The pigment may be obtained as a dispersion in which the pigment is uniformly dispersed in a solution by adding a dispersant as necessary and performing a dispersion treatment.

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

Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines and the like (Trade name) manufactured by Shin-etsu Chemical Industry Co., Ltd.), Polyflow (manufactured by Kyowa Chemical Co., Ltd.), F-top (manufactured by TOKEM PRODUCTS CO., LTD.), Megapack (manufactured by Dainippon Ink & (Trade name, manufactured by EFKA CHEMICALS), Sulfur (manufactured by Asahi Glass Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS), Fluorad (manufactured by Sumitomo 3M Ltd.), Asahi Guard, , PB821 (manufactured by Ajinomoto Co., Ltd.), and the like.

When a dispersing agent is used, the amount thereof is preferably 0.1 to 100% by mass, more preferably 5 to 50% by mass, based on 100% by mass of the pigment. When the amount of the dispersing agent used is within the above range, a uniform dispersion tends to be obtained, which is preferable.

The content of the colorant (A) used in the color-curable composition of the present invention is 30 to 65% by mass, preferably 35 to 60% by mass, more preferably 35 to 55% by mass with respect to the solid content of the colored curable composition Mass%.

When the content of the colorant (A) is within the above range, it is preferable since the color density when formed into a color filter is sufficient, a polymerizable compound can be contained in a required amount in the composition, and a pattern having sufficient mechanical strength can be formed.

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

Specific examples of the monomer include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexa methacrylate, dipentaerythritol pentaacrylate derivatives having a carboxyl group, ethylene Oxydized glycerin triacrylate, ethylene oxideated trimethylol propane triacrylate, and propylene oxydized glycerin triacrylate.

Examples of the oligomer include epoxy acrylate, urethane acrylate, polyester acrylate, and the like. For example, oligomers and the like described in the present invention and prospect of UV / EB curing technology (published by CMC) .

The content of the polymerizable compound (B) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, and particularly preferably 12 to 35% by mass, based on the solids content of the colored curable composition . When the content of the polymerizable compound is within the above range, it is preferable because sufficient curing occurs to improve the film thickness ratio before and after development and to make the adhesion good.

Here, the solid content in the present specification refers to the total amount of components (A), (B), and (C) of the colored curable composition, which are not liquid at room temperature.

The colored curable composition of the present invention may further comprise (C) a binder resin. The binder resin (C) preferably contains a constituent unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. The content of the constituent unit derived from the (meth) acrylic acid is preferably 10 mol% or more and 40 mol% or less, more preferably 13 mol% or more and 35 mol% or less in the molar fraction of all the constituent units constituting the binder resin, Or less. When the content of the structural unit derived from (meth) acrylic acid is within the above range, the solubility at the time of development is favorable and the residue tends to remain after development.

Examples of other monomers for deriving constituent units of the binder resin other than the constituent units derived from (meth) acrylic acid include aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, unsaturated carboxylic acids Unsaturated amides, unsaturated imides, aliphatic conjugated dienes, monoacryloyl groups or monomethacryloyl groups at the ends of the polymer molecular chain, such as glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, vinyl cyanide compounds, And the like. Examples of the structural unit include a unit represented by the following general formula (32) and a unit represented by the following general formula (33).

[Wherein R ¹⁶ and R ¹⁷ are each independently a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms]

R ¹⁶ and R ^{17 are preferably} a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a sec- Methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 2-ethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, Ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, sec-butyl group, sec- A butyl group, and a tert-butyl group, more preferably a hydrogen atom, a methyl group, and an ethyl group.

Specific examples of the binder resin (C) include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer Methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / a constituent component represented by Chemical Formula 33 (wherein R ¹⁶ in Chemical Formula 33 represents a methyl group, and R ¹⁷ represents hydrogen Benzylmaleimide / benzyl methacrylate copolymer, methacrylic acid / a constituent component represented by Chemical Formula 33 (wherein R ¹⁶ in Chemical 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 / (33) wherein R ¹⁶ represents a methyl group and R ¹⁷ represents a hydrogen atom / styrene / dicyclopentanyl methacrylate copolymer, and the like.

The acid value of the binder resin (C) used in the present invention is preferably 30 to 150, more preferably 35 to 135, and particularly preferably 40 to 120. When the acid value is in the above range, the solubility in a developing solution is improved, the unexposed portion is easily dissolved, and a high sensitivity is obtained and a pattern of the exposed portion tends to remain at the time of development, thereby improving the residual film ratio. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide.

The content of the binder resin (C) is preferably 5 to 40% by mass, more preferably 8 to 35% by mass, and particularly preferably 10 to 32% by mass, based on the solids content of the colored curable composition . When the content of the binder resin (C) is in the above range, a pattern can be formed, and the resolution and the residual film ratio tend to be improved.

(C) a binder resin having a constituent component represented by the formula (29), for example, a component derived from methacrylic acid / a constituent component represented by the formula (32): wherein R ¹⁶ in the formula (29) represents a methyl group and R ¹⁷ Is a hydrogen atom) / benzyl methacrylate is obtained by polymerizing methacrylic acid and benzyl methacrylate to obtain a two-component polymer, and the obtained two-component polymer is reacted with a (Wherein R ¹⁸ represents a hydrogen atom in the formula (34)).

A constituent component derived from methacrylic acid / a constituent component represented by Chemical Formula 33 (wherein R ¹⁶ in Chemical Formula 33 represents a methyl group and R ¹⁷ represents a hydrogen atom) / a component derived from benzyl methacrylate / Copolymers comprising constituents derived from clopentanyl methacrylate can be obtained by reacting glycidyl methacrylate with a copolymer of benzyl methacrylate, methacrylic acid and dicyclopentanyl methacrylate.

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

The colored curable composition of the present invention may further comprise (D) a photopolymerization initiator. Examples of the photopolymerization initiator include a triazine-based compound, an acetophenone-based compound, a nonimidazole-based compound, an active radical generator, and an acid generator.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) 6,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- (Trichloromethyl) -6- [2- (4-diethylamino-2-pyridin- -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-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5- (Trichloromethyl) -6-piperonyl-1,3,5-triazine, and more preferably 2,4-bis (trichloromethyl) -6- Piperonyl-1,3,5-triazine.

Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2- 2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- 1-one, and oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one. (4-methylthiophenyl) propane-1-one, and preferably 2-methyl-2-morpholino-1- 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- Phenyl) butan-1-one, and more preferably 2-dimethylamino-1- (4-morpholinophenyl) butane-1-one and 2- (4-methylbenzyl) -1-one.

Examples of the nonimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis , 4 ', 5,5'-tetra (4-carboethoxyphenyl) biimidazole, 2,2'-bis (2- chlorophenyl) -4,4', 5,5'- 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 Phenylimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,6-dichlorophenyl) -4,4', 5,5'- Bis (2-nitrophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-methylphenyl) 5'-tetraphenylbiimidazole, and the like, preferably 2,2'-bis (2-chlorophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole.

Active radical generators generate active radicals when irradiated with light. Examples of the active radical generator include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and oxime-based compounds.

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

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

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

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

Examples of the active radical generator other than the above examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10- Phenanthrene quinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds, and the like.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium-p-toluene Sulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium-p-toluenesulfo And onium salts such as diphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylates, and benzoin tosylates.

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

The content of the (D) photopolymerization initiator is preferably 0.1 to 25% by mass, more preferably 1 to 20% by mass with respect to the total amount of the polymerizable compound (B) and the binder resin (C) . When the content of the photopolymerization initiator (D) is in the above range, the sensitivity is improved and the productivity is improved by reducing the exposure time. On the other hand, if the sensitivity is too high, the line width is not excessively thickened at the minimum line width at which the line- .

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

Examples of the photopolymerization initiator (E) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate , 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'-dimethylaminopyridine, -Bis (ethylmethylamino) benzophenone, and among these, 4,4'-bis (diethylamino) benzophenone is preferable.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, etc. .

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

The photopolymerization initiator (E) may be used alone or in combination of two or more. Commercially available (E) photopolymerization initiators may be used as commercially available photopolymerization initiators. Examples of commercially available photopolymerization initiators (E) include EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd., 4,4 '-Bis (diethylamino) benzophenone), and the like.

Examples of the combination of the (D) photopolymerization initiator / (E) photopolymerization initiation assistant in the tinting curable composition of the present invention include 2,4-bis (trichloromethyl) -6-piperonyl- (Diethylamino) benzophenone, diethoxyacetophenone / 4,4'-bis (diethylamino) benzophenone, 2-methyl- (4-methylthiophenyl) propan-1-one / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy- (Diethylamino) benzophenone, benzyldimethylketal / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl- 1- [4- (2-hydroxyethoxy) phenyl ] Propane-1-one / 4,4'-bis (diethylamino) benzophenone, 1-hydroxycyclohexyl phenyl ketone / 4,4'-bis (diethylamino) benzophenone, Oligomers of 4,4'-bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4'- Bis (diethylamino) benzophenone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butan- 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- -Dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4'-bis (diethylamino) benzophenone.

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

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

Examples of the ethers include tetrahydrofuran, tetrahydropyrane, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether 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, Pentylpentyl Three, and the like lactate, anisole, phenetole, methyl anisole.

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

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

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

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, butyl butyrate, Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, Ethoxypropionate, ethyl 3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, Propyl, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 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-oxobutanoate, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, .

Examples of the amide include N, N-dimethylformamide, N, N-dimethylacetamide and the like.

Examples of the other (F) solvent include N-methylpyrrolidone, dimethylsulfoxide and the like.

The (F) solvent may be used alone or in combination of two or more.

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

The content of the (F) solvent is preferably 70 to 90% by mass, and more preferably 75 to 88% by mass, based on the mass of the colored curable composition. When the content of the solvent is within the above range, it is preferable that the in-plane uniformity at the time of coating is good, the color density when the color filter is formed is sufficient, and the display characteristics are good.

Also, (G) a surfactant may be included. Examples of the (G) surfactant include a silicone surfactant, a fluorine surfactant, and a silicon surfactant having a fluorine atom.

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

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Concretely, as the trade name, Fluorad FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Megafac F142D, Copper F171, Copper F172, Copper F173, Copper F177, Copper F183, Copper F470, Copper F475, Copper R30 (Manufactured by Shin-Akita Kasei Co., Ltd.), Surflon S381, S382, SC101 and SC105 (manufactured by Asahi Glass Co., Ltd.) (manufactured by Dainippon Ink and Chemicals, Inc.), Eftop EF301, EF303, EF351 and EF352 Ltd.), E5844 (manufactured by Daikin Fine Chemical Co., Ltd.), BM-1000 and BM-1100 (manufactured by BM Chemie), and the like.

Examples of the silicon-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specifically, Megapack R08, BL20, F475, F477, and F443 (manufactured by Dainippon Ink and Chemicals, Inc.) may be mentioned as trade names.

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

The colored curable composition of the present invention may contain an organic acid having a molecular weight of 1,000 or less. Examples of the organic acid include organic acids disclosed in JP-A-5-343631. Specific examples thereof 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 , And preferably malonic acid, oxalic acid, fumaric acid, and phthalic acid. Containing an organic acid having a molecular weight of 1,000 or less is preferable because the residue tends to be better.

(C) a polymer compound other than the binder resin, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, an organic amine compound, and (H) a curing agent may be added to the colored curable composition of the present invention .

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

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

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

Examples of the antioxidant include 4,4'-thio-bis (6-tert-butyl-3-methylphenol), triethylene glycol-bis [3- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- , 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,6- Butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'- butylphenol), 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), 1,1,3- Butylphenyl) butane, 1,3,5-tris (4-hydroxybenzyl) benzene and tetrakis [methylene-3- (3,5'-di- )] Methane, and the like.

Examples of the ultraviolet absorber include benzotriazole compounds such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole;

Benzophenone-based compounds such as 2-hydroxy-4-octyloxybenzophenone;

2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate;

And triazine systems such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol.

The anti-aggregation agent includes, for example, sodium polyacrylate.

By the addition of the organic amine compound, it is possible to provide a pixel having excellent adhesion to the substrate without causing residue on the substrate of the unexposed portion at the time of development.

Examples of the organic amine compound include n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, Monoalkylamines such as amine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine and n-dodecylamine;

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

Di-n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di- Dialkylamines such as butylamine, di-tert-butylamine, di-n-pentylamine and di-n-hexylamine;

Monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;

Dicycloalkylamines such as dicyclohexylamine;

Propylamine, dimethyl-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine Trialkylamines such as triethylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, Amines;

Dialkylmonocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;

Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine and tricyclohexylamine;

Amino alcohols such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, All amines;

Monocycloalkanolamines such as 4-amino-1-cyclohexanol;

Dialkanol amines 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, tri-n-pentanolamine and tri-n-hexanolamine;

Tricycloalkanolamines such as tri (4-cyclohexanol) amine;

Amino-1,2-propanediol, 4-amino-1,2-butanediol, 4-amino- Aminoalkanediols such as propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol and 2-diethylamino-1,3-propanediol;

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

Amino group-containing cycloalkanemonols such as 1-aminocyclopentanone methanol and 4-aminocyclopentanone methanol;

1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentane methanol, 4-diethylaminocyclopentane methanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexane methanol and the like Amino group-containing cycloalkane methanol;

aminobutyric acid, 1-aminobutyric acid, 2-aminobutyric acid, 2-aminobutyric acid, 3-aminoisothiazoic acid, 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- , 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;

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

Examples of the (H) curing agent include (C) a compound capable of reacting with a carboxyl group in the binder resin to (C) crosslinking the binder resin by heating, a compound capable of curing the coloring pattern by being polymerized singly have. As the above compound, for example, an epoxy compound, an oxetane compound and the like can be mentioned, and an oxetane compound is preferably used.

Examples of the epoxy compound include epoxy resins such as bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolac epoxy resin, other aromatic epoxy resin, alicyclic epoxy Aliphatic, alicyclic or aromatic compounds other than the epoxy resin such as a resin, a heterocyclic epoxy resin, a glycidyl ester resin, a glycidylamine resin and an epoxidized oil, or a brominated derivative of these epoxy resins, an epoxy resin and a brominated derivative thereof (Co) polymer of isoprene, (co) polymer of glycidyl (meth) acrylate, triglycidyl isocyanurate, and the like can be given .

Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like.

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

Examples of the polyvalent carboxylic acids include phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, , 4,4'-benzophenonetetracarboxylic acid, and other aromatic polycarboxylic acids;

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

Hexahydrophthalic acid, hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentane Tetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, and other alicyclic polycarboxylic acids.

Examples of the polycarboxylic acid anhydrides include aromatic polycarboxylic acids such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride and the like Anhydrous logistics;

Aliphatic polycarboxylic acid anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarvalylic anhydride, maleic anhydride and 1,2,3,4-butanetetracarboxylic acid dianhydride logistics;

Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic acid anhydride, 1,2,4-cyclohexanetricarboxylic acid anhydride, cyclopentanetetracarboxylic acid anhydride, Alicyclic polycarboxylic anhydrides such as water, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, hymic acid anhydride, and nadic acid anhydride;

And ester group-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitate acid and glycerin tristrimellitate anhydride.

As the carboxylic acid anhydrides, those commercially available as epoxy resin curing agents may be used. Examples of the epoxy resin curing agent include Adeka Hardener EH-700 (manufactured by Asahi Denka Kogyo K.K.), Ricacid HH, and MH-700 (all manufactured by Shin-Nippon Chemical Co., Ltd.) under trade names.

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

As a method of forming a pattern of a color filter using the color-curable composition of the present invention, for example, a method of forming a color filter using a substrate or a separate resin layer (for example, a separate colored curable composition layer A so-called photolithography method in which a colored layer is formed by removing a volatile component such as a solvent, and the colored layer is exposed through a photomask, developed and further heated as necessary, or a so- And an inkjet method in which the composition is applied to a substrate or a separate resin layer using an apparatus to remove a volatile component such as a solvent to form a colored layer and cured by heating or exposure or the like.

The color filter thus obtained includes a pattern, and a preferable liquid crystal display device is obtained by using the color filter.

Use of the color-curable composition of the present invention makes it possible to manufacture a color filter that is excellent in heat resistance and solvent resistance and does not deteriorate light resistance and contrast.

<Examples>

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Examples of the method for producing the phthalocyanine compound represented by the formula (1) used as the (A) coloring agent in the colored curable composition of the present invention include Japanese Patent Application Laid-Open Nos. 63-30566, 63-141982, Japanese Patent Application Laid-Open No. 45474, Japanese Patent Application Laid-Open No. 2-282386, Japanese Patent Application Laid-Open No. 4-39361, Japanese Patent Application Laid-Open No. 5-222302, -107663, 5-221952, 5-345861, and the like can be produced.

Synthesis Example 1

&Lt; Synthesis of colorant (A-1) >

Synthesis of Compound Represented by Formula (1-1)

In a 100 mL four-necked flask, 9.29 g (20 mmol) of 3,6-difluoro-4,5-bis (p-methoxycarbonylphenoxy) phthalonitrile, 0.59 g ) And 20 mL of benzonitrile were charged and reacted at 175 DEG C for 12 hours. After completion of the reaction, the reaction mixture was poured into methanol, and the resulting solid was washed with methanol and then with water, and dried under reduced pressure at 60 ° C to obtain 5.45 g of the objective green compound (yield: 75.1%).

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

Synthesis Example 2

&Lt; Synthesis of colorant (A-2) >

Synthesis of phthalocyanine compound represented by the formula (1-14)

7.83 g (20 mmol) of 3,4,6-trifluoro-5- (2-methyl-6-methoxyethoxycarbonylphenoxy) phthalonitrile and 0.94 g 6 mmol) and 25 mL of benzonitrile were charged and reacted at 175 ° C for 4 hours. After completion of the reaction, the insoluble matter was separated by filtration, the solvent was distilled off, washed with 200 mL of methanol twice, and dried under reduced pressure at 60 DEG C to obtain 4.42 g of the objective green compound (yield: 54.2%).

The obtained green compound was dissolved in ethyl lactate and the visible absorption spectrum was measured. The maximum absorption wavelength was 714.0 nm and the molar extinction coefficient (?) Was 1.055 × 10 ⁵ .

Synthesis Example 3

&Lt; Synthesis of colorant (A-3) >

Synthesis of a barbituric acid azo dye represented by the formula (7-4)

300 g of water was added to 30 g (61 mmol) of 2,2'-benzidine disulfonic acid represented by the following formula (35) (containing 30% of water), and the mixture was adjusted to a pH of 7 to 8 with 30% aqueous sodium hydroxide under ice- . The following operation was carried out under ice-cooling. 12.6 g (183 mmol) of sodium nitrite was added, and the mixture was stirred for 30 minutes. 38.1 g of 35% hydrochloric acid was added in small portions to make a brown solution, which was then stirred for 2 hours. Amide sulfuric acid in 57.4 g of water was added to the reaction solution and stirred to obtain a suspension containing the diazonium salt.

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

The following operation was carried out under ice-cooling. The above aqueous solution of barium bitartric acid was stirred to obtain a colorless solution, and the suspension containing the diazonium salt was poured dropwise while adjusting the pH to 8 to 9 with 30% sodium hydroxide aqueous solution. After completion of the dropwise addition, stirring was further carried out for 3 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 캜 under reduced pressure to obtain 15 g (21 mmol, yield: 34%) of an azo compound represented by the following formula (37).

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 fed into a flask equipped with a stirrer and a cooling tube, And thionyl chloride (6 g, 54 mmol) was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 DEG C, and the mixture was allowed to react at the same temperature for 5 hours, followed by cooling to 20 DEG C. [ The cooled reaction solution was added dropwise with stirring to a mixture of 3 g (20 mmol) of 3-aminophenylbutane and 10 g (103 mmol) of triethylamine while maintaining the temperature at 20 ° C or less. Thereafter, the reaction was carried out by stirring at the same temperature for 5 hours. Subsequently, the obtained reaction mixture was distilled off with a rotary evaporator, and a small amount of methanol was added thereto, followed by vigorous stirring. This mixture was added to a mixed solution 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 an azo compound represented by the following formula (7-4).

LC-MS analysis was performed on the azo compound obtained in this Example under the following conditions.

Device; Agilent 1100 (manufactured by Agilent Technologies)

Detector; UV detector; 254 nm

column; Sumipax ODS (manufactured by Sumika Corporation)

Eluting solvent; A solvent system in which 0.1% of trifluoromethylacetic acid was added to a water-acetonitrile mixed solvent

The content of each azo compound was calculated 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 an area percentage value to the entire peak area thereof was 98%.

Synthesis Example 4

&Lt; Synthesis of colorant (A-4) >

Synthesis of pyridone azo dye represented by formula (16)

3000 g of water was added to 100 g (203 mmol) of 2,2'-benzidine disulfonic acid represented by the general formula (35) (containing 30% of water), and the pH was adjusted to 7 to 8 with 30% aqueous sodium hydroxide solution under ice cooling. The following operation was carried out under ice-cooling. 56 g (812 mmol) of sodium nitrite was added, and the mixture was stirred for 30 minutes. 150 g of 35% hydrochloric acid was added in small portions to make a brown solution, which was then stirred for 2 hours. Amide sulfuric acid (38 g, 406 mmol) in 380 g of water was added to the reaction solution and stirred to obtain a suspension containing the diazonium salt.

After adding 1000 g of water to 76 g (426 mmol) of 1-ethyl-3-cyano-4-methyl-6-hydroxypyrido-2-one represented by the following chemical formula 38, 30% The pH was adjusted to 8 to 9 with aqueous solution.

The following operation was carried out under ice-cooling. The alkali aqueous solution of the pyridone was stirred to obtain a colorless solution, and the suspension containing the diazonium salt was poured dropwise while adjusting the pH to 8 to 9 with 30% sodium hydroxide aqueous solution. After completion of the dropwise addition, stirring was further carried out for 3 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 캜 under reduced pressure to obtain 137 g (204 mmol, yield 100%) of an azo compound represented by the following formula (39).

5 g (7 mmol) of the azo compound represented by the formula (39) obtained in the above procedure, 50 g of chloroform and 2.4 g (33 mmol) of N, N-dimethylformamide were placed in a flask equipped with a stirrer, 7 g (59 mmol) of thionyl chloride was added dropwise while stirring at 20 캜 or lower. After completion of the dropwise addition, the temperature was raised to 50 DEG C, and the mixture was allowed to react at the same temperature for 5 hours, followed by cooling to 20 DEG C. [ The cooled reaction solution was added dropwise with stirring to a mixture of 4 g (30 mmol) of 1,5-dimethylhexylamine and 12 g (119 mmol) of triethylamine while maintaining the temperature below 20 ° C. Thereafter, the reaction was carried out at the same temperature overnight by stirring. Subsequently, the obtained reaction mixture was distilled off with a rotary evaporator, and a small amount of methanol was added thereto, followed by vigorous stirring. This mixture was added to a mixed solution 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 80%) of an azo compound represented by the formula (16).

&Lt; Formula 16 >

The azo compound obtained in this Example was subjected to the same structural analysis as described above. As a result, the azo compound represented by Chemical Formula 16 was detected as a compound having a molecular weight of 944, and an area percentage value to the entire peak area was 58.3%. Further, the monosulfonamidated azo compound represented by the formula (40) was detected as a compound having a molecular weight of 833, and the area percentage value to the entire peak area thereof was 30.1%.

Synthesis Example 5

&Lt; 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 inlet tube. Thereafter, nitrogen gas was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Thereafter, the solution in the flask was heated to 100 DEG C, 22.0 g (0.10 mol) of dicyclopentyl methacrylate (FA-513M; manufactured by Hitachi Kasei Kogyo K.K.), 70.5 g (0.40 mol) of benzyl methacrylate, , 43.0 g (0.5 mole) of methacrylic acid, 3.6 g of azobisisobutyronitrile and 164 g of propylene glycol monomethyl ether acetate was added dropwise to the flask over a period of 2 hours using a dropping funnel, Stirring was continued at 100 &lt; 0 &gt; C further for 5 hours.

After the completion of the stirring, air was introduced into the flask through the gas introduction pipe. After the atmosphere in the flask became air, 35.5 g (0.25 mol) of glycidyl methacrylate (in terms of molar ratio with respect to the methacrylic acid used in the present reaction 50 mol%), 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into a flask and the reaction was continued at 110 캜 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 necessary for neutralizing 1 g of an acid group-containing acid such as carboxylic acid, and is generally determined by titration using an aqueous potassium hydroxide solution whose concentration is already known .

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

The weight average molecular weight of the (C-1) binder resin in terms of polystyrene was measured by the GPC method under the following conditions.

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

column; TSK-GELG2000HXL

Column temperature; 40 ℃

menstruum; THF

Flow rate; 1.0 mL / min

Solid concentration of the test solution; 0.001 to 0.01 mass%

Dose; 50 μL

Detector; RI

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

The components used in this embodiment are as follows, and may be omitted and displayed in some cases.

(A-1) Colorant: The colorant obtained in Synthesis Example 1

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

(A-3) Colorant: The colorant obtained in Synthesis Example 3

(A-4) Colorant: The colorant obtained in Synthesis Example 4

(A-5) Colorant: A compound represented by the formula (29) (cyanine dye: NK-3212: manufactured by Hayashibara Seibutsu Kagaku Kagaku Co., Ltd.)

(29)

(A-6) Colorant: A compound represented by the formula (41) (FB-22: phthalocyanine dye manufactured by Yamada Chemical Industry Co., Ltd.)

(A-7) Colorant: A compound represented by the formula (42) (FB-24: phthalocyanine dye manufactured by Yamada Chemical Industry Co., Ltd.)

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

(B-2) Photopolymerizable compound: A-GLY-3E (Shin Nakamura Chemical Industry Co., Ltd.)

Ethylene oxydation (3) Glycerine triacrylate

(C-1) Binder resin: Resin (C-1) (38.5 mass% of propylene glycol monomethyl ether acetate solution) obtained in Synthesis Example 5,

(D-1) Photopolymerization initiator: 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-

(E-1) Photopolymerization initiator: 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 and Chemicals, Inc.)

(H-1) Curing agent: Sumi-epoxy ESCN-195XL-80 [Orthocresol novolak type epoxy resin (Sumitomo Chemical Co., Ltd.)]

Example 1

[Preparation of colored curable composition 1]

(A-1) 7.650 parts by mass

(B-1) 4.712 parts by mass

8.160 parts by mass (C-1) (3.141 parts by mass in terms of solid content)

(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

To obtain a colored curable composition 1.

[Formation of coating film]

Subsequently, the colored curable composition 1 obtained above was coated on glass (# 1737; Corning) by spin coating, and then the volatile components were volatilized at 100 ° C for 3 minutes to form a colored curable composition film. After cooling, this colored curable composition film was exposed by irradiating i-line (wavelength: 365 nm). A high-pressure mercury lamp was used as a light source for the i-line, which was irradiated after being made into parallel light. The irradiation light amount was set to 500 mJ / cm 2. Subsequently, post-baking was performed at 220 占 폚 for 20 minutes to obtain a colored curable composition film having a thickness of 2 占 퐉.

[Evaluation 1] Evaluation of heat resistance

The chromaticity of the resultant colored curable composition film was measured using a colorimeter (OSP-SP-200, manufactured by OLYMPUS CO., LTD.).

Subsequently, the resulting colored curable composition film was heated in an oven at 230 캜 for 120 minutes in an oven, and the color of the colored curable composition film after heating was measured in the same manner to obtain a color difference (ΔEab *) before and after heating.

As a criterion for evaluating the chromaticity, when ΔEab * is 5 or less, color change is hardly observed, and good color filter characteristics are exhibited. When ΔEab * is more than 5 and less than 10, slight color change is observed. There is no problem in practical use, and if? Ab * is 10 or more, reliable color change can be confirmed, which is a problem at a color filter.

[Evaluation 2] Evaluation of light resistance

(COLORED OPTICAL GLASS L38, manufactured by Hoya Co., Ltd., blocking light of 380 nm or less) was placed on the resultant colored curable composition film, and a light resistance tester (SUNTEST CPS + manufactured by Toyo Seiki Co., Ltd.) Were irradiated for 48 hours.

The chromaticity of the film of the color-curable composition after irradiation was measured, and the color difference before and after irradiation was found to be 0.6.

As a criterion for evaluating the color difference, similar to the above, when ΔEab * is 5 or less, color change is hardly observed and good color filter characteristics are exhibited. When ΔEab * is more than 5 and less than 10, slight color change is observed, There is no problem in practical use of the color filter, and if? Ab * is 10 or more, a reliable color change can be confirmed, and there is a problem as a color filter.

[Evaluation 3] Evaluation of Solvent Resistance

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

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

As a criterion for evaluating color difference, when ΔEab * is 5 or less, color change is hardly observed, and good color filter characteristics are exhibited. When ΔEab * is more than 5 and less than 10, slight color change is observed, There is practically no problem, and if? Eab * is 10 or more, a reliable color change can be confirmed, and there is a problem as a color filter.

[Evaluation 4] Contrast evaluation

The contrast value of the resultant colored curable composition film was measured by using a contrast colorimeter (CT-1; manufactured by Tsubo Chemical) and the blank value was 10,000, which was 9112.

As a criterion for evaluating the contrast of the colored curable composition film, the color filter exhibits good characteristics when the contrast value is 8000 or more, and the color filter exhibits good characteristics. When the contrast value is more than 6000 and less than 8000, However, there is no problem in practical use of the color filter, and if the contrast value is 6000 or less, reliable certainty can be confirmed, and there is a problem as a color filter.

Example 2

[Preparation of colored curable composition 2]

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

[Formation and Evaluation of Coating Film]

A color curable composition film having a thickness of 2 占 퐉 was prepared and evaluated in the same manner as in Example 1. As a result, the color difference in the heat resistance evaluation was 4.8, 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

[Preparation 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

8.160 parts by mass (C-1) (3.141 parts by mass in terms of solid content)

(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

To obtain a colored curable composition 3.

[Formation and Evaluation of Coating Film]

A color curable composition film having a thickness of 2 占 퐉 was prepared and evaluated in the same manner as in Example 1. As a result, the color difference in the heat resistance evaluation was 2.6, 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

[Preparation of colored curable resin composition 4]

A colored curable composition 4 was obtained in the same manner as in Example 1 except that (A-3) in Example 3 was changed to (A-4).

[Formation and Evaluation of Coating Film]

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

Example 5

[Preparation of colored curable composition 5]

A colored curable composition 5 was obtained in the same manner as in Example 1 except that (A-3) in Example 3 was changed to (A-5).

[Formation and Evaluation of Coating Film]

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

Example 6

[Preparation of colored curable composition 6]

(A-1) 4.590 parts by mass

(A-3) 3.060 parts by mass

(B-2) 4.319 parts by mass

(C-1) 7.139 parts (solid value conversion: 2.749 parts)

(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

Were mixed to obtain a colored curable composition 6.

[Formation and Evaluation of Coating Film]

A color curable composition film having a thickness of 2 占 퐉 was prepared and evaluated in the same manner as in Example 1. As a result, the color difference in evaluation of heat resistance was 2.9, the color difference in evaluation of light resistance was 2.4, the color difference in solvent resistance was 1.6, The contrast value was 8652.

Comparative Example 1

[Preparation of colored curable composition 7]

A colored curable composition 7 was obtained in the same manner as in Example 1 except that (A-1) in Example 1 was changed to (A-6).

[Formation and Evaluation of Coating Film]

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

Comparative Example 2

[Preparation of colored curable composition 8]

A colored curable composition 8 was obtained in the same manner as in Example 1 except that (A-1) in Example 1 was changed to (A-7).

[Formation and Evaluation of Coating Film]

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

Comparative Example 3

[Preparation of colored curable composition 9]

A colored curable composition 9 was obtained in the same manner as in Example 1 except that (A-1) in Example 3 was changed to (A-6).

[Formation and Evaluation of Coating Film]

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

Claims (10)

A colored curable composition comprising (A) a colorant and (B) a polymerizable compound, wherein (A) the colorant comprises a dye represented by the following formula (1) and a barbituric acid azo dye. &Lt; Formula 1 >

[In the formula 1, k represents an integer of 0 or 1, M represents a metal or metal oxide, A ¹ to A ¹⁶ is a group of the substituents represented by each independently represent a hydrogen atom, a halogen atom or the following formula 2 to 5 , Provided that 1 to 8 of A ¹ to A ¹⁶ are substituents selected from the group of substituents represented by the general formulas (2) to (5) (2)

(3)

&Lt; Formula 4 >

&Lt; 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 ) R ¹⁴ represents a hydrogen atom or a linear or branched saturated aliphatic hydrocarbon group of 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 linear or branched saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms or an alkoxyl group having 1 to 4 carbon atoms, e1, g1 and i1 are each independently an integer of 1 to 5, e2, g2 and i2 each independently represent an integer of 0 to 5, However, the sum of e1 and e2, the sum of g1 and g2, and the sum of i1 and i2 is an integer of 5 or less, f and h are each independently an integer of 1 to 6, j is an integer of 1 or 2] The colored curable composition according to claim 1, wherein, in the substituent represented by A ¹ to A ¹⁶ in the general formula (1), all of the substituents other than the substituent selected from the group of the substituents represented by the general formulas (2) to (5) are fluorine atoms. According to claim 1, wherein the colored curable composition is a G ¹ oxygen atom in the formula (2). The colored curable composition according to claim 1, wherein the barbituric acid azo dye is a dye represented by the following formula (7). &Lt; Formula 7 >

[Wherein T ¹ and T ² each independently represents an oxygen atom or a sulfur atom, R ³¹ to R ³⁴ each independently represent a hydrogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with a hydroxyl group, or an alkoxyl group having 1 to 8 carbon atoms A saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group of 1 to 10 carbon atoms substituted with a thioalkoxyl group of 1 to 8 carbon atoms, an aryl group of 6 to 20 carbon atoms, an aralkyl group of 7 to 20 carbon atoms, To 10 &lt; RTI ID = 0.0 &gt; Each of R ³⁵ to R ⁴² independently represents a hydrogen atom, a halogen atom, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms substituted with a halogen atom, an alkoxyl group having 1 to 8 carbon atoms, A carboxyl group, a sulfo group, a sulfamoyl group or an N-position-substituted sulfamoyl group] The colored curable composition of claim 1 further comprising (C) a binder resin. A pattern formed by a photolithography method or an ink-jet method using the color-curable composition according to any one of claims 1 to 5. A color filter comprising the pattern according to claim 6. A liquid crystal display device comprising the color filter according to claim 7. delete delete