JP6440494B2 - Compound - Google Patents

Description

  The present invention relates to a compound useful as a dye (for example, a colored curable resin composition, a color filter, a liquid crystal display device).

  Dyes are used for color display using reflected light or transmitted light in the fields of fiber materials, liquid crystal display devices, ink jets, and the like. Coumarin 6 is known as such a dye (Patent Document 1).

JP 2006-154740 A (Example 8)

  In the process of producing a color filter from the colored curable resin composition containing the coumarin compound, the problem is that the colorant sublimates. As a method for suppressing the sublimation of the colorant, a method of dimerizing the colorant is known, but dimerizing the colorant is a problem in terms of synthesis.

  Therefore, the present invention has an object to provide a technology of a colored curable resin composition that provides a color filter that does not require dimerization of the colorant and that facilitates synthesis of the colorant and that does not sublime the colorant. And

The present invention includes the following inventions.
[1] A compound represented by the formula (I).

[In the formula (I),
X represents an oxygen atom or a sulfur atom.
R ¹ and R ² each independently represent a hydrocarbon group having 1 to 20 carbon atoms.
n represents an integer of 1 to 4.
A represents -SO ₂ -L ¹ -OM.
M represents a hydrogen atom or an alkali metal atom. When a plurality of M are present, they may be the same as or different from each other.
L ¹ represents a divalent hydrocarbon group having ^{1 to} 60 carbon atoms. -CH ₂ -CH = is constituting the divalent hydrocarbon group, may be replaced in -N =, constituting the divalent hydrocarbon group - represents an oxygen atom, a sulfur atom, -N ( R ³ ) —, a sulfonyl group or a carbonyl group may be substituted, and the hydrogen atom contained in the divalent hydrocarbon group is a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, —SO ₃ M , -CO ₂ M, hydroxy group, formyl group, an alkyl group, an alkynyl group or may be substituted with an amino group.
R ³ represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a group represented by the formula (z). The hydrogen atom contained in the monovalent hydrocarbon group may be replaced with a halogen atom, a hydroxy group or a carboxy group, and —CH ₂ — constituting the monovalent hydrocarbon group is replaced with a carbonyl group. May be.
When a plurality of R ³ are present, they may be the same as or different from each other.

In formula (z), L ²² and L ³³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms. —CH═ constituting a divalent hydrocarbon group may be replaced by —N═, and —CH ₂ — constituting the divalent hydrocarbon group may be an oxygen atom, a sulfur atom, or —N (R ⁴⁴ )-, a sulfonyl group or a carbonyl group may be substituted, and the hydrogen atom contained in the divalent hydrocarbon group is a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, hydroxy group, formyl group, alkyl group, alkynyl group or amino group may be substituted.
M ¹ represents a hydrogen atom or an alkali metal atom.
R ⁴⁴ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ⁴⁴ are present, they may be the same as or different from each other. ]

[2] The A is —SO ₂ —O—L ^a —OM, —SO ₂ —NR ³ —L ^b —OM, or —SO ₂ —NR ³ —L ² —OCO—L ³ —CO—OM. The compound according to [1].

[Wherein R ³ is the same as defined above. L ^a and L ^b are divalent hydrocarbon groups having 1 to 20 carbon atoms having at least one of a divalent aromatic hydrocarbon group and a divalent aliphatic hydrocarbon group, —CH ₂ — constituting the hydrogen group may be replaced with an oxygen atom or a carbonyl group. The hydrogen atom contained in the divalent hydrocarbon group may be replaced with a halogen atom, an alkyl group, an alkynyl group or a carboxy group.
L ² and L ³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms. -CH ₂ -CH = is constituting the divalent hydrocarbon group, may be replaced in -N =, constituting the divalent hydrocarbon group - represents an oxygen atom, a sulfur atom, -N ( R ⁵⁵ ) —, a sulfonyl group or a carbonyl group may be substituted, and the hydrogen atom contained in the divalent hydrocarbon group is a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, —SO ₃ M , -CO ₂ M, hydroxy group, formyl group, an alkyl group, an alkynyl group or may be substituted with an amino group.
M represents the same meaning as described above.
^R55 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ⁵⁵ are present, they may be the same as or different from each other. ]

[3] The compound according to [1] or [2] represented by the formula (II).

[In the formula (II),
n, X, R ¹ , R ² , L ² , L ³ and R ⁵⁵ represent the same meaning as described above.
R ³³ represents a hydrogen atom or _{^{-L 22 -OCO-L 33 -CO 2}} M 2.
L ²² and L ³³ represent the same meaning as L ² and L ³ .
M ² represents a hydrogen atom or an alkali metal atom. ]

[4] L ² and L ²² are a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms,
The compound according to any one of [1] to [3], wherein L ³ and L ³³ are a divalent aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be substituted with a carboxy group or a halogen atom.
[5] The compound according to any one of [1] to [4], wherein R ¹ and R ² are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms.
[6] A colored curable resin composition containing a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent containing the compound according to any one of [1] to [5].
[7] A color filter formed from the colored curable resin composition according to [6].
[8] A liquid crystal display device including the color filter according to [7].

  According to the present invention, since it is not necessary to dimerize the colorant, it is possible to provide a technique for a colored curable resin composition that provides a color filter that facilitates the synthesis of the colorant and does not sublime the colorant. It becomes.

  The compound of the present invention is a compound represented by the formula (I) or the formula (II) (hereinafter sometimes referred to as the compound (I) or the compound (II)). The compounds of the present invention include tautomers and salts thereof.

[In the formula (I),
X represents an oxygen atom or a sulfur atom.
R ¹ and R ² each independently represent a hydrocarbon group having 1 to 20 carbon atoms.
n represents an integer of 1 to 4.
A represents -SO ₂ -L ¹ -OM.
M represents a hydrogen atom or an alkali metal atom. When a plurality of M are present, they may be the same as or different from each other.
L ¹ represents a divalent hydrocarbon group having ^{1 to} 60 carbon atoms. -CH ₂ -CH = is constituting the divalent hydrocarbon group, may be replaced in -N =, constituting the divalent hydrocarbon group - represents an oxygen atom, a sulfur atom, -N ( R ³ ) —, a sulfonyl group or a carbonyl group may be substituted, and the hydrogen atom contained in the divalent hydrocarbon group is a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, —SO ₃ M , -CO ₂ M, hydroxy group, formyl group, an alkyl group, an alkynyl group or may be substituted with an amino group.
R ³ represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a group represented by the formula (z). The hydrogen atom contained in the monovalent hydrocarbon group may be replaced with a halogen atom, a hydroxy group or a carboxy group, and —CH ₂ — constituting the monovalent hydrocarbon group is replaced with a carbonyl group. May be.
When a plurality of R ³ are present, they may be the same as or different from each other.

In formula (z), L ²² and L ³³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms. —CH═ constituting a divalent hydrocarbon group may be replaced by —N═, and —CH ₂ — constituting the divalent hydrocarbon group may be an oxygen atom, a sulfur atom, or —N (R ⁴⁴ )-, a sulfonyl group or a carbonyl group may be substituted, and the hydrogen atom contained in the divalent hydrocarbon group is a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, hydroxy group, formyl group, alkyl group, alkynyl group or amino group may be substituted.
M ¹ represents a hydrogen atom or an alkali metal atom.
R ⁴⁴ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ⁴⁴ are present, they may be the same as or different from each other. ]

[In the formula (II),
n, X, R ¹ , R ² , L ² , L ³ and R ⁵⁵ represent the same meaning as described above.
R ³³ represents a hydrogen atom or _{^{-L 22 -OCO-L 33 -CO 2}} M 2.
L ²² and L ³³ represent the same meaning as L ² and L ³ .
M ² represents a hydrogen atom or an alkali metal atom. ]

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , (2-ethyl) butyl group, pentyl group, isopentyl group, 3-pentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, (3-ethyl) pentyl group, hexyl group Saturated fats such as hexyl, isohexyl, 5-methylhexyl, (2-ethyl) hexyl, heptyl, (3-ethyl) heptyl, octyl, nonyl, decyl, undecyl, dodecyl, octadecyl Group hydrocarbon group, isopropenyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, 1,3-butadienyl group, 2-phenyl group An aliphatic hydrocarbon group such as an unsaturated aliphatic hydrocarbon group such as an ntenyl group;
Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1,2-dimethylcyclohexyl group, 1 , 3-dimethylcyclohexyl group, 1,4-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4 -Dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,2-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, 2,4,6-trimethylcyclohexyl group, 2,2 , 6,6-Te La methylcyclohexyl group, 3,3,5,5 saturated alicyclic hydrocarbon group such as tetramethyl cyclohexyl group, an unsaturated alicyclic hydrocarbon group such as a cyclohexenyl group;
Phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, Aromatic such as 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, 2,6-bis (2-propyl) phenyl group Other examples include aralkyl groups such as a benzyl group, a phenethyl group, a biphenylyl group, a 1-naphthyl group, and a 2-naphthyl group; and combinations thereof.

R ¹ and R ² are preferably each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms. As for the said carbon number, 1-8 are more preferable, More preferably, it is 1-6. The monovalent hydrocarbon group is more preferably a monovalent saturated or unsaturated aliphatic hydrocarbon group, and even more preferably a monovalent saturated aliphatic hydrocarbon group.

R ¹ and R ² are preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a hexyl group, a (2-ethyl) hexyl group and an octyl group, and an ethyl group, a butyl group, a hexyl group, ( 2-Ethyl) hexyl group and octyl group are more preferred. When R ¹ and R ² are these groups, the compound represented by the formula (I) or the compound represented by the formula (II) is easily dissolved in the solvent.

  X represents an oxygen atom or a sulfur atom.

  n represents an integer of 1 to 4. n is preferably 1 to 3, more preferably 1 or 2.

A represents -SO ₂ -L ¹ -OM. A is preferably —SO ₂ —O—L ^a —OM, —SO ₂ —NR ³ —L ^b —OM, or —SO ₂ —NR ³ —L ² —OCO-L ³ —CO—OM. .

L ¹ represents a divalent hydrocarbon group having ^{1 to} 60 carbon atoms. L ¹ is preferably a divalent hydrocarbon group having 1 to 30 carbon atoms, and more preferably a divalent hydrocarbon group having 1 to 20 carbon atoms.

In L ¹ , the divalent hydrocarbon group includes a methylene group, an ethylene group, a propane-1,3-diyl group (propylene group), a propane-1,2-diyl group (propylene group), and butane-1,4. -Diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane -1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1, 15-diyl group, hexadecane-1,16-diyl group, heptadecane-1,17-diyl group, octadecane-1,18-diyl group, nonadecane-1,19-diyl group, eicosane-1,20- Linear alkanediyl such as yl group, triacontane-1,30-diyl group, tetracontane-1,40-diyl group, pentacontane-1,50-diyl group, hexacontan-1,60-diyl group Group, methyl-ethyl-1,2-diyl group (methylethylene group), butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group , Pentane-1,4-diyl group, 2-methylbutane-1,4-diyl group, ethane-1,1-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, etc. It may be an aliphatic hydrocarbon group such as a chain alkanediyl group.

In L ¹ , the divalent hydrocarbon group may be an alicyclic hydrocarbon group which may be monocyclic or polycyclic, and may be a cyclobutane-1,3-diyl group, cyclopentane-1,3- Diyl group, cyclohexane-1,2-diyl group, 1-methylcyclohexane-1,2-diyl group, cyclohexane-1,4-diyl group, cyclooctane-1,2-diyl group, cyclooctane-1,5- Monocyclic cycloalkanediyl group such as diyl group, norbornane-2,3-diyl group, norbornane-1,4-diyl group, norbornane-2,5-diyl group, adamantane-1,2-diyl group, adamantane It may be an alicyclic hydrocarbon group such as a polycyclic cycloalkanediyl group such as a -1,5-diyl group or an adamantane-2,6-diyl group.

In L ¹ , the divalent hydrocarbon group may be a monocyclic or polycyclic aromatic hydrocarbon group, a monocyclic aromatic hydrocarbon group such as a phenylene group, a naphthalene group, a biphenylene group, or a triphenylene group. It may be a polycyclic aromatic hydrocarbon group such as.

In L ¹ , the divalent hydrocarbon group may be one or more combinations selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

In L ¹ , —CH═ constituting the divalent hydrocarbon group may be replaced by —N═, and —CH ₂ — constituting the divalent hydrocarbon group is an oxygen atom or a sulfur atom. , —N (R ³ ) —, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the divalent hydrocarbon group includes a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, An alkyl group such as —SO ₃ M, —CO ₂ M, a hydroxy group, a formyl group, or a t-butyl group, an alkynyl group such as a phenylethynyl group, an ethynyl group, or an amino group may be substituted.

Examples of the group represented by L ¹ include groups represented by formula (L1-1) to formula (L1-43). ● represents a bond with a sulfur atom. ○ represents a bond with an oxygen atom.

As the group represented by L ¹ , groups represented by formula (L1-9) to formula (L1-19) and formula (L1-25) to formula (L1-43) are preferable, and formula (L1-9) ) To formula (L1-12), formula (L1-14), formula (L1-17) to formula (L1-19), and groups represented by formula (L1-25) to formula (L1-43) Preferably, formulas (L1-31) to (L1-34) are even more preferable. If the group represented by L1 is any of these groups, the synthesis is easy. In addition, although the aromatic ring in the said chemical formula is illustrated as a compound which has a bond in 1-position and 4 position, or 1-position and 2-position, respectively, the bond of 1-position and 4-position is 1-position and 2 The bond at the first position and the bond at the 1st and 2nd positions may be the bond at the 1st and 4th positions.

L ^a and L ^b are preferably ^a C 1-20 divalent hydrocarbon group having one or more of a divalent aromatic hydrocarbon group and a divalent aliphatic hydrocarbon group, more preferably. Is a C1-C10 divalent hydrocarbon group having one or more of a divalent aromatic hydrocarbon group and a divalent saturated aliphatic hydrocarbon group, more preferably a phenylene group, a methylene group, ethylene One or more selected from the group consisting of a group, a methylethylene group, and a propylene group.

In L ^a and L ^b , —CH ₂ — constituting the divalent hydrocarbon group may be replaced with an oxygen atom or a carbonyl group. The hydrogen atom contained in the divalent hydrocarbon group may be replaced with a halogen atom, an alkyl group such as a t-butyl group, an alkynyl group such as a phenylethynyl group or an ethynyl group, or a carboxy group.

L ² and L ³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms.

L ² and L ³ are, for example, one or more of a saturated or unsaturated divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group having 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Or one or more of a linear or branched divalent aliphatic hydrocarbon group and an aromatic hydrocarbon group. Specific examples of L ² and L ³ include groups described as divalent hydrocarbon groups described in the present specification.

In L ² and L ³ , —CH═ constituting the divalent hydrocarbon group may be replaced by —N═, and —CH ₂ — constituting the divalent hydrocarbon group is an oxygen atom , A sulfur atom, —N (R ⁵⁵ ) —, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the divalent hydrocarbon group includes a halogen atom, a cyano group, a nitro group, a carbamoyl group, Alkyl groups such as sulfamoyl group, —SO ₃ M, —CO ₂ M, hydroxy group, formyl group, t-butyl group, alkynyl group such as phenylethynyl group, ethynyl group, or amino group may be substituted.

Examples of L ² and L ³ include groups represented by formulas (L23-1) to (L23-22). ● represents a bond.

L ² is preferably a group represented by Formula (L23-1) to Formula (L23-4), and more preferably a group represented by Formula (L23-1) or Formula (L23-2). When L ² is these groups, the synthesis is easy.

L ³ is preferably a group represented by Formula (L23-1), Formula (L23-2), and Formula (L23-5) to Formula (L23-20). Formula (L23-1) and Formula (L23 -2), groups represented by formula (L23-5), formula (L23-7) to formula (L23-10), formula (L23-13) to formula (L23-20) are more preferable. When L ³ is these groups, the synthesis is easy.

R ³ represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a group represented by the formula (z).

  Examples of the group represented by the formula (z) include the following.

In formula (z), L ²² and L ³³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms.

L ²² and L ³³ represent the same meaning as L ² and L ³ described above.

The monovalent hydrocarbon group having 1 to 20 carbon atoms of R ³ is selected from the aliphatic hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group exemplified in the above R ¹ and R ^2. And one or more hydrocarbon groups.

In R ³ , a hydrogen atom contained in the monovalent hydrocarbon group may be replaced by a halogen atom, a hydroxy group or a carboxy group, and —CH ₂ — constituting the monovalent hydrocarbon group is a carbonyl It may be replaced with a group. When a plurality of R ³ are present, they may be the same as or different from each other.

For example, L ² and L ²² are each a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and L ³ and L ³³ are divalent aliphatic hydrocarbon groups that may be substituted with a carboxy group or a halogen atom, or It is preferably an aromatic hydrocarbon group, more preferably L ² and L ²² are an ethylene group or a methylethylene group, and L ³ and L ³³ are ethylenes optionally substituted with a carboxy group or a halogen atom. Group or phenylene group.

In L ²² and L ³³ , —CH═ constituting the divalent hydrocarbon group may be replaced by —N═, and —CH ₂ — constituting the divalent hydrocarbon group is an oxygen atom , A sulfur atom, —N (R ⁴⁴ ) —, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the divalent hydrocarbon group includes a halogen atom, a cyano group, a nitro group, a carbamoyl group, Alkyl groups such as sulfamoyl group, —SO ₃ M, —CO ₂ M, hydroxy group, formyl group, t-butyl group, alkynyl group such as phenylethynyl group, ethynyl group, or amino group may be substituted.

M ¹ represents a hydrogen atom or an alkali metal atom.

R ³³ represents a hydrogen atom or _{^{-L 22 -OCO-L 33 -CO 2}} M 2.

R ⁴⁴ and R ⁵⁵ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ⁴⁴ and R ⁵⁵ are present, they may be the same as or different from each other. R ⁴⁴ and R ⁵⁵ are one or more hydrocarbon groups selected from the aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups exemplified in the above R ¹ and R ^2. Also good.

M and M ² represent a hydrogen atom or an alkali metal atom, preferably a hydrogen atom, a sodium atom or a potassium atom, and more preferably a hydrogen atom. When a plurality of these are present, they may be the same as or different from each other.

  Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.

  Specific examples of the compound represented by the formula (I) and the compound represented by the formula (II) are shown in Tables 1 to 4. In Tables 1 to 8, “Et” represents an ethyl group, “Oct” represents an n-octyl group, and L1-1 to L1-43 represent Formulas (L1-1) to (L1) exemplified above, respectively. -43).

From the viewpoint of easy synthesis,
Formula (I-9) to Formula (I-19),
Formula (I-25) to Formula (I-43),
Formula (I-52) to Formula (I-62),
Formula (I-68) to Formula (I-86),
Formula (I-95) to Formula (I-105),
Formula (I-111) to Formula (I-129),
Compounds represented by formula (I-138) to formula (I-148) and formula (I-154) to formula (I-172) are preferred,
Formula (I-9) to Formula (I-12),
Formula (I-14),
Formula (I-17) to Formula (I-19),
Formula (I-25) to Formula (I-43),
Formula (I-52) to Formula (I-55),
Formula (I-57),
Formula (I-60) to Formula (I-62),
Formula (I-68) to Formula (I-86),
Formula (I-95) to Formula (I-98),
Formula (I-100),
Formula (I-103) to Formula (I-105),
Formula (I-111) to Formula (I-129),
Formula (I-138) to Formula (I-141),
Formula (I-143),
More preferred are compounds represented by formula (I-146) to formula (I-148) and formula (I-154) to formula (I-172),
Formula (I-10), Formula (I-33), Formula (I-34), Formula (I-96), Formula (I-117), Formula (I-118), Formula (I-119), Formula The compound represented by (I-120) is particularly preferable.

  As a method for producing compound (I), a compound represented by formula (pa2) is reacted with chlorosulfonic acid to produce a compound represented by formula (pa2), and then represented by formula (pa2). The compound represented by the formula (pa3) can be produced by reacting in the presence of a solvent.

  The reaction temperature between the compound represented by the formula (pa1) and chlorosulfonic acid is preferably 0 ° C to 200 ° C, more preferably 30 ° C to 150 ° C, and more preferably 50 ° C to 150 ° C.

  The reaction temperature of the compound represented by the formula (pa2) and the compound represented by the formula (pa3) is preferably −100 ° C. to 100 ° C., more preferably −78 ° C. to 80 ° C., and of these, 0 ° C. to 60 ° C. Is more preferable.

  Solvents used for the reaction of the compound represented by the formula (pa2) and the compound represented by the formula (pa3) include methanol, ethanol, isopropyl alcohol, acetonitrile, tetrahydrofuran, acetone, 3-methyl-2-pentanone, acetic acid. Examples thereof include ethyl, hexane, toluene, methylene chloride, chloroform, N, N-dimethylformaldehyde and N-methylpyrrolidone, and acetonitrile, N, N-dimethylformaldehyde and N-methylpyrrolidone are preferable.

  The compound represented by the formula (pa2) and the compound represented by the formula (pa3) can also be reacted in the presence of a base or an alkali metal. As the base, tertiary amine, a compound having a pyridine skeleton and an organometallic compound are preferable. Specifically, triethylamine, pyridine, 4-dimethylaminopyridine, methyllithium, phenyllithium, butyllithium, sec-butyllithium and Examples include tert-butyllithium, and pyridine, 4-dimethylaminopyridine and butyllithium are preferable. Examples of the alkali metal include sodium and lithium, and lithium is preferable.

[In formula (pa1), formula (pa2) and formula (pa3), R ^{1 to} R ² , X, n, L ¹ and M represent the same meaning as described above.
In formula (pa3), XX represents a hydrogen atom, a halogen atom, * -O-tosyl group or * -O-mesyl group. * Represents a bond. ]

  In the production of the compound (pa2), the amount of chlorosulfonic acid used is usually 1 mol to 100 mol, preferably 5 mol to 60 mol, relative to 1 mol of the compound represented by the formula (pa1). More preferably, it is 10 mol-40 mol.

  In the production of compound (I), the amount of the compound represented by formula (pa3) to be used is generally 1 mol to 100 mol, preferably 1 mol, relative to 1 mol of compound represented by formula (pa2). It is -80 mol, More preferably, it is 1-60 mol.

The compound (II) can be produced by reacting the compound represented by the formula (pa4) and the compound represented by the formula (pa5) in the presence of a base and a solvent.
The reaction temperature is preferably 0 ° C to 200 ° C, more preferably 0 ° C to 150 ° C, and more preferably 50 ° C to 150 ° C.

  The reaction time is preferably 1 hour to 36 hours, more preferably 2 hours to 30 hours, and further preferably 3 hours to 28 hours.

  As the base, a compound having a tertiary amine and a pyridine skeleton is preferable, and specific examples include triethylamine, pyridine and 4-dimethylaminopyridine, and pyridine and 4-dimethylaminopyridine are preferable.

  Examples of the solvent include acetonitrile, tetrahydrofuran, acetone, 3-methyl-2-pentanone, ethyl acetate, hexane, toluene, methylene chloride, chloroform, N, N-dimethylformaldehyde, N-methylpyrrolidone, and the like. -Dimethylformaldehyde and N-methylpyrrolidone are preferred.

[In formula (pa4) and formula (pa5), X, R ^{1 to} R ² , L ^{2 to} L ³ , R ³³ and n represent the same meaning as described above. ]

  In the production of compound (II), the amount of the compound represented by formula (pa5) to be used is generally 1 mol to 200 mol, preferably 1 mol, per 1 mol of compound represented by formula (pa4). It is -160 mol, More preferably, it is 1 mol -140 mol.

  In the production of compound (II), the amount of the compound having a tertiary amine and a pyridine skeleton is usually 0.1 mol to 80 mol with respect to 1 mol of the compound represented by formula (pa4), preferably It is 0.1 mol-60 mol, More preferably, it is 0.1-45 mol.

  As a manufacturing method of Formula (pa4), it can manufacture by making the compound represented by Formula (pa2) and the compound represented by Formula (pa6) react in solvent presence.

  The reaction temperature of the compound represented by the formula (pa2) and the compound represented by the formula (pa6) is preferably 0 ° C to 100 ° C, more preferably 0 ° C to 80 ° C, and more preferably 0 ° C to 60 ° C. preferable.

  As a solvent used for the reaction of the compound represented by the formula (pa2) and the compound represented by the formula (pa6), methanol, ethanol, isopropyl alcohol, acetonitrile, tetrahydrofuran, acetone, 3-methyl-2-pentanone, acetic acid Examples thereof include ethyl, hexane, toluene, methylene chloride, chloroform, N, N-dimethylformaldehyde and N-methylpyrrolidone, and acetonitrile, N, N-dimethylformaldehyde and N-methylpyrrolidone are preferable.

[In the formula (pa6), R ³³ and L ² represent the same meaning as described above. ]

  In the production of compound (pa4), the amount of the compound represented by formula (pa6) to be used is generally 1 mol to 100 mol, preferably 1 mol, per 1 mol of compound represented by formula (pa2). It is -80 mol, More preferably, it is 1-60 mol.

  The compound represented by the formula (pa2) is represented by the formula (pa7) by a Vilsmeier reaction using N, N-dimethylformamide and thionyl chloride, phosphorus oxychloride, phosphorus pentachloride or oxalyl chloride in the presence of a solvent. It can be synthesized from a compound.

[In the formula (pa7), R ^{1 to} R ² , X and n represent the same meaning as described above.
M ′ represents a hydrogen atom, an alkali metal atom or NH ₄ . When a plurality of M ′ are present, they may be the same as or different from each other. ]

  The reaction temperature is preferably 0 ° C to 200 ° C, more preferably 0 ° C to 150 ° C, and more preferably 0 ° C to 100 ° C.

  The reaction time is preferably 1 hour to 72 hours, more preferably 1 hour to 48 hours, and further preferably 1 hour to 24 hours.

  Examples of the solvent include acetonitrile, tetrahydrofuran, acetone, 3-methyl-2-pentanone, ethyl acetate, hexane, toluene, methylene chloride, chloroform, 1,4-dioxane, N, N-dimethylformaldehyde and N-methylpyrrolidone. Acetonitrile, 1,4-dioxane, N, N-dimethylformaldehyde and N-methylpyrrolidone are preferable.

  In the production of the compound represented by the formula (pa2), the amount of N, N-dimethylformamide used is usually 1 mol to 50 mol with respect to 1 mol of the compound represented by the formula (pa7), preferably It is 1 mol-40 mol, More preferably, it is 1 mol-30 mol.

  In the production of the compound represented by the formula (pa2), the amount of thionyl chloride, phosphorus oxychloride, phosphorus pentachloride or oxalyl chloride used is usually 1 mol to 1 mol of the compound represented by the formula (pa7). It is 50 mol, Preferably it is 1 mol-40 mol, More preferably, it is 1 mol-30 mol.

  The method for obtaining the compound (I), compound (II), compound represented by formula (pa2) or compound represented by formula (pa4) of the present invention from the reaction mixture is not particularly limited, and various known techniques Can be adopted.

  For example, the reaction mixture is added to a solvent in which the compound (I), the compound (II), the compound represented by the formula (pa2) or the compound represented by the formula (pa4) is not dissolved, and the crystals are precipitated. The method of filtration, the reaction mixture is dissolved in tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, toluene, chloroform or a mixed solution thereof, water, aqueous sodium hydroxide, aqueous acetic acid, hydrochloric acid, aqueous sodium chloride, sodium bicarbonate Examples include a method of washing with an aqueous solution or an aqueous solution of sodium carbonate and then drying, or a method of purifying by column chromatography after distilling off the solvent of the reaction mixture.

  Further, it may be further purified by a known technique such as column chromatography or recrystallization.

<Colorant of the present invention>
The colorant of the present invention (hereinafter sometimes referred to as “colorant (A)”) contains compound (I) or compound (II) as an active ingredient. The colorant (A) may consist solely of the compound (I) or the compound (II), or may contain a dye or pigment other than the compound (I) or the compound (II). The colorant (A) preferably contains a pigment in addition to the compound (I) or the compound (II). The content ratio of the compound (I) or the compound (II) in the colorant (A) is usually 1 to 100% by mass, preferably 3 to 100% by mass, and preferably 3 to 70% by mass. More preferably, it is more preferably 3 to 60% by mass.

  The colorant (A) is useful as a colorant contained in a colored photosensitive resin composition used for a color filter of a display device such as a liquid crystal display device.

  As dyes other than Compound (I) or Compound (II), Color Index (published by The Society of Dyers and Colorists), Solvent, Acid, Basic, Reactive ( Examples include compounds classified as reactive, direct, disperse, or vat, and known dyes described in dyeing notes (color dyeing). In addition, according to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, and the like can be given. These dyes may be used alone or in combination of two or more.

Specific examples include dyes having the following color index (CI) numbers.
C. I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Reactive Yellow 2, 76, 116;
C. I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;
C. I. Disperse Yellow 51, 54, 76;
C. I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;
C. I. Reactive Orange 16;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C. I. Acid Red 73, 80, 91, 92, 97, 138, 151, 211, 274, 289;
C. I. Acid Violet 34, 102;
C. I. Disperse violet 26, 27;
C. I. Solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112;
C. I. Direct blue 40;
C. I. Disperse Blue 1, 14, 56, 60;
C. I. Solvent Green 1, 3, 5, 28, 29, 32, 33;
C. I. Acid Green 3, 5, 9, 25, 27, 28, 41;
C. I. Basic Green 1;
C. I. Bat Green 1 etc.

  The pigment is not particularly limited, and a known pigment can be used. For example, pigments classified as pigments in the color index (published by The Society of Dyers and Colorists) can be mentioned, and these can be used alone or in combination of two or more.

Specifically, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. A brown pigment such as CI Pigment Brown 23 and 25; and C.I. I. And black pigments such as CI Pigment Black 1 and 7.

  Among the green pigments and blue pigments, phthalocyanine pigments are preferable, and at least one selected from the group consisting of halogenated copper phthalocyanine pigments and halogenated zinc phthalocyanine pigments is more preferable. I. Particularly preferred is at least one selected from the group consisting of CI Pigment Green 7, 36 and 58. These pigments are suitable as green colorants, and by using a colorant containing these pigments, it is easy to optimize the transmission spectrum, and it is possible to form a color filter with good light resistance and chemical resistance. it can.

  If necessary, the pigment is atomized by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment to the pigment surface with a polymer compound, sulfuric acid atomization method, etc. A treatment, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment by an ion exchange method of ionic impurities, or the like may be performed. The pigment particle size is preferably substantially uniform. The pigment can be made into a pigment dispersion in a state of being uniformly dispersed in the pigment dispersant solution by carrying out a dispersion treatment by containing a pigment dispersant. The pigments may be subjected to a dispersion treatment alone, or a plurality of types may be mixed and dispersed.

  Examples of the pigment dispersant include surfactants, and any of cationic, anionic, nonionic, and amphoteric surfactants may be used. Specific examples include polyester-based, polyamine-based, acrylic-based surfactants, and the like. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersants, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Geneca Corporation), EFKA (registered trademark) ) (Manufactured by BASF), Azisper (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK Chemie) and the like.

  When the pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, a pigment dispersion having a more uniform dispersion state tends to be obtained.

<Colored curable resin composition of the present invention>
The colored curable resin composition of the present invention is a colorant (A), a resin (hereinafter sometimes referred to as “resin (B)”), a polymerizable compound (hereinafter referred to as “polymerizable compound (C)”). A polymerization initiator (hereinafter sometimes referred to as “polymerization initiator (D)”) and a solvent (hereinafter sometimes referred to as “solvent (E)”). The colored curable resin composition of the present invention may contain a leveling agent in addition to these components. The colored curable resin composition of the present invention may contain a polymerization initiation assistant in addition to these components. In another aspect of the present invention, the colored curable resin composition may contain a colorant (A), a resin (B), a solvent (E), and, if necessary, a surfactant.

  The content of the colorant (A) in the colored curable resin composition is usually 1% by mass or more and 70% by mass or less, preferably 1% by mass or more and 60% by mass or less, based on the total amount of the solid content. More preferably, it is 5 mass% or more and 60 mass% or less, Most preferably, it is 5 mass% or more and 50 mass% or less. When the content of the colorant (A) is within the above range, a desired spectrum and color density can be easily obtained. In addition, in this specification, "the total amount of solid content" means the total amount of the component remove | excluding the solvent from the colored curable resin composition of this invention. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography and gas chromatography, for example.

<Resin (B)>
The resin (B) contained in the colored curable resin composition of the present invention is preferably an alkali-soluble resin and has a structure derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. More preferred are addition polymers having units. Examples of such a resin include the following resins [K1] to [K6].

Resin [K1]: at least one (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), and a cyclic ether structure having 2 to 4 carbon atoms And a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”) Resin [K2]: (a), (b), (a) A copolymer with a monomer (c) copolymerizable with (but different from (a) and (b)) (hereinafter sometimes referred to as “(c)”) Resin [K3]: (a ) And (c) Copolymer Resin [K4]: Resin obtained by reacting (b) with copolymer of (a) and (c) Resin [K5]: (b) and (c Resin [K6]: a resin obtained by reacting a copolymer with (a) with a copolymer with (a) The reacted resin obtained by further reacting a carboxylic acid anhydride.

As (a), unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] bicyclounsaturated compounds containing a carboxy group such as hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl]. ;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule such as α- (hydroxymethyl) acrylic acid.

  Of these, acrylic acid, methacrylic acid and maleic anhydride are preferred from the viewpoint of copolymerization reactivity and solubility of the resulting resin in an aqueous alkali solution.

  (B) refers to a polymerizable compound having a C2-C4 cyclic ether structure (for example, an oxirane ring, oxetane ring, tetrahydrofuran ring, etc.) and an ethylenically unsaturated bond. (B) is preferably a monomer having a C2-C4 cyclic ether structure and a (meth) acryloyloxy group. In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid, and the notation of “(meth) acryloyl” and “(meth) acrylate” is also used. Indicate the same meaning.

  (B) includes a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a monomer having an oxetanyl group and an ethylenically unsaturated bond. (B2) (hereinafter sometimes referred to as “(b2)”) and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”).

  (B1) may be a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) ) And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).

  (B1-1) is preferably a monomer having a glycidyl group and an ethylenically unsaturated bond. Specific examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinyl. Benzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis ( Glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris ( Glycidyl oxime Chill) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene and 2,4,4 Examples include 6-tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide (registered trademark) 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) Acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), represented by Formula (1) And a compound represented by the formula (2).

(Wherein, R ^a and R ^b each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group. X ^a and X ^b are each independently a single ^{bond, -R c -, * - R} c -O -, * - R c -S- or * -R represents the ^c -NH- .R ^c is the number of carbon atoms Represents an alkanediyl group of 1 to 6. * represents a bond to O.)

Examples of the alkyl group having 1 to 4 carbon atoms of R ^a and R ^b include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group and tert-butyl group. Examples of the alkyl group in which the hydrogen atoms of R ^a and R ^b are substituted with a hydroxy group include a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, Examples include hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group. .

R ^a and R ^b are each independently preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl having 1 to 4 carbon atoms. Specifically, a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group is preferable, and a hydrogen atom or a methyl group is more preferable.

Examples of the alkanediyl group having 1 to 6 carbon atoms of R ^c include a linear or branched alkanediyl group, and specifically include a methylene group, an ethylene group, a propane-1,3-diyl group, Linear alkanediyl group of butane-1,4-diyl group, pentane-1,5-diyl group and hexane-1,6-diyl group; branched chain alkanediyl group such as propane-1,2-diyl group ;

X ^a and X ^b are each independently a single bond, * - R ^c -, or * -R ^c -O-, more preferably a single bond, or * -R ^c -O-, and specifically Are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— or * —CH ₂ CH ₂ —O—, preferably a single bond or * —CH ₂ CH ₂ —O—. It is more preferable. In the above formula, * represents a bond with O.

  Examples of the compound represented by the formula (1) include compounds represented by the formula (1-1) to the formula (1-15). Among them, the formula (1-1) and the formula (1-3) And compounds represented by formula (1-5), formula (1-7), formula (1-9) and formula (1-11) to formula (1-15) are preferred, The compounds represented by formula (1-7), formula (1-9) and formula (1-15) are more preferred.

  Examples of the compound represented by the formula (2) include compounds represented by the formula (2-1) to the formula (2-15). Among them, the formula (2-1) and the formula (2-3) And compounds represented by formula (2-5), formula (2-7), formula (2-9) and formula (2-11) to formula (2-15) are preferred, and formula (2-1), The compounds represented by formula (2-7), formula (2-9) and formula (2-15) are more preferred.

  The compound represented by the formula (1) and the compound represented by the formula (2) may be used alone, or the compound represented by the formula (1) and the compound represented by the formula (2) May be used in combination. When these are used in combination, the ratio of the compound represented by formula (1) and the compound represented by formula (2) (compound represented by formula (1): compound represented by formula (2)) is mol. The standard is preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still more preferably 20:80 to 80:20.

  (B2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. (B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane and 3-ethyl-3-acryloyloxyethyl oxetane.

  (B3) is more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

  (B) is preferably (b1), and the storage stability of the colored curable resin composition is excellent in that the reliability of the obtained color filter such as heat resistance and chemical resistance can be further increased. In this respect, (b1) is preferably (b1-2).

As (c), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] Decan-8-yl (meth) acrylate (in this technical field, it is said to be “dicyclopentanyl (meth) acrylate” as a common name. It may also be referred to as “tricyclodecyl (meth) acrylate”) ), Tricyclo [ .2.1.0 ^2,6] (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) Decene-8-yl (meth) acrylate, dicyclopentenyl oxyethyl (Meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. ) Acrylic acid ester;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclo unsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide compounds such as maleimide propionate, N- (9-acridinyl) maleimide;
Vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene; vinyl group-containing nitriles such as acrylonitrile and methacrylonitrile; vinyl chloride and vinylidene chloride Halogenated hydrocarbons such as: vinyl group-containing amides such as acrylamide and methacrylamide; esters such as vinyl acetate; 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene dienes; .

Among these, a vinyl group-containing aromatic compound, a dicarbonylimide compound, and a bicyclounsaturated compound are preferable from the viewpoints of copolymerization reactivity and heat resistance. Specifically, styrene, vinyl toluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N -Benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferred.

In the resin [K1], the ratio of the structural unit derived from each is the total structural unit constituting the resin [K1]
Structural unit derived from (a): 2 to 60 mol%
Structural unit derived from (b): 40 to 98 mol%
It is preferable that
Structural unit derived from (a): 10 to 50 mol%
Structural unit derived from (b): 50 to 90 mol%
It is more preferable that

  When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter are more improved. It tends to be excellent.

  Resin [K1] is, for example, the method described in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, by substituting oxygen with nitrogen to create a deoxygenated atmosphere and stirring. The method of heating and heat retention is mentioned. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) Any solvent may be used as long as it dissolves each monomer. Examples of the solvent for the colored curable resin composition of the present invention include the solvents described later.

  As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation. May be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction is used as it is for the preparation of the colored curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of the present invention can be simplified.

In the resin [K2], the ratio of the structural units derived from each of the structural units constituting the resin [K2]
Structural unit derived from (a): 2 to 45 mol%
Structural unit derived from (b): 2 to 95 mol%
Structural unit derived from (c): 1 to 65 mol%
It is preferable that
Structural unit derived from (a): 5 to 40 mol%
Structural unit derived from (b): 5 to 80 mol%
Structural unit derived from (c): 5 to 60 mol%
It is more preferable that

  When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter, Heat resistance and mechanical strength tend to be more excellent.

  Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].

In the resin [K3], the proportion of structural units derived from each of the structural units constituting the resin [K3]
Structural unit derived from (a): 2 to 60 mol%
Structural unit derived from (c): 40 to 98 mol%
It is preferable that
Structural unit derived from (a): 10 to 50 mol%
Structural unit derived from (c): 50 to 90 mol%
It is more preferable that

  Resin [K3] can be produced, for example, in the same manner as described for the production method of resin [K1].

  Resin [K4] obtains a copolymer of (a) and (c), and (b) has a carboxylic acid and / or carboxylic acid anhydride having (a) a C2-C4 cyclic ether moiety. It can be manufactured by adding to a product. Specifically, it can be produced as follows. First, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of the resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as that described for the resin [K3]. Next, the C2-C4 cyclic ether compound which (b) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer. Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a catalyst for the reaction of the carboxylic acid or carboxylic anhydride with the cyclic ether compound (for example, A resin [K4] is produced by placing tris (dimethylaminomethyl) phenol and the like) and a polymerization inhibitor (such as hydroquinone) in a flask and reacting at 60 to 130 ° C. for 1 to 10 hours, for example. be able to.

  The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). The colored curable resin composition containing a resin obtained by adjusting the amount of (b) used in this range is storage stability, developability when forming a pattern, solvent resistance of the resulting pattern, heat resistance Tend to have a better balance of properties, mechanical strength and sensitivity. Since the reactivity of the cyclic ether moiety is high and unreacted (b) hardly remains, (b) used in the resin [K4] is preferably (b1) and more preferably (b1-1).

  The amount of the catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c).

  The reaction conditions such as the charging method of each reagent, the reaction temperature, and the reaction time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

When the resin [K5] is produced, as a first step, a copolymer of (b) and (c) is obtained in the same manner as in the method for producing the resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as. In the first stage, the ratio of the structural units derived from (b) and (c) is relative to the total number of moles of all structural units constituting the copolymer of (b) and (c), respectively.
Structural unit derived from (b): 5 to 95 mol%
Structural unit derived from (c): 5 to 95 mol%
It is preferable that
Structural unit derived from (b): 10 to 90 mol%
Structural unit derived from (c): 10 to 90 mol%
It is more preferable that

  Furthermore, as a second step, the carboxylic acid of (a) is added to the cyclic ether moiety derived from (b) of the copolymer of (b) and (c) under the same conditions as in the resin [K4] production method. Resin [K5] can be obtained by reacting an acid or carboxylic anhydride.

  In the second stage, the amount of (a) to be reacted with the copolymer of (b) and (c) is preferably 5 to 80 mol per 100 mol of (b). Since the reactivity of the cyclic ether moiety is high and unreacted (b) hardly remains, (b) used in the resin [K5] is preferably (b1) and more preferably (b1-1).

  Resin [K6] is a resin obtained by further reacting resin [K5] with a carboxylic anhydride, and specifically, a cyclic ether moiety derived from (b) and a carboxylic acid of (a) or It can be produced by reacting a carboxylic acid anhydride with a hydroxy group generated by the reaction with the carboxylic acid anhydride.

  Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride. As for the usage-amount of carboxylic acid anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amount of (a).

Examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meta ) Resin such as acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxy tricyclo [5.2.1.0 ^{2, 6]} decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl-3- (meth) acrylate Resin [K2] such as luroyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl Resin [K3] such as (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer; glycidyl (meth) acrylate is added to benzyl (meth) acrylate / (meth) acrylic acid copolymer Added resin, resin obtained by adding glycidyl (meth) acrylate to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / ( Glycidyl (meth) acrylate was added to a (meth) acrylic acid copolymer Resins such as fat [K4]; resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, tricyclodecyl (meth) acrylate / styrene / glycidyl (meta ) Resin such as resin obtained by reacting (meth) acrylic acid with acrylate copolymer [K5]; (meth) acrylic acid reacted with tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer Resin [K6] such as a resin obtained by further reacting tetrahydrophthalic anhydride with the resin.

  The resin (B) is preferably one kind selected from the group consisting of resin [K1], resin [K2] and resin [K3], more preferably from the group consisting of resin [K1] and resin [K2]. It is the kind chosen. When these resins are used, the colored curable resin composition is excellent in developability. Resin [K2] is more preferable from the viewpoint of adhesion between the coloring pattern and the substrate.

  The weight average molecular weight in terms of polystyrene of the resin (B) is usually from 3,000 to 100,000, preferably from 5,000 to 50,000, more preferably from 5,000 to 35,000, Preferably it is 5,000-30,000, Most preferably, it is 6,000-30,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution of the colored pattern tends to be improved.

  The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4, and still more preferably 1. 3 to 3.

  The acid value of the resin (B) is preferably 20 to 170 mg-KOH / g, more preferably 30 to 170 mg-KOH / g, of which 40 to 170 mg-KOH / g is preferred, of which 50 to 170 mg-KOH / g is preferable, 150 mg-KOH / g or less is more preferable, and 135 mg-KOH / g or less is more preferable.

  Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example.

  The content of the resin (B) is preferably 7 to 65% by mass, preferably 10 to 60% by mass, and more preferably 13 to 60% by mass, based on the total amount of solids. Of these, the content is preferably 17 to 55% by mass. When the content of the resin (B) is in the above range, a colored pattern can be easily formed, and the resolution of the colored pattern and the remaining film rate tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from a polymerization initiator, and examples thereof include a polymerizable compound having an ethylenically unsaturated bond, and a (meth) acrylic acid ester. Compounds having a structure are preferred. The polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having 5 to 6 ethylenically unsaturated bonds.

  Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, (A), (b) and (c). Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meta). ) Acrylate, bis (acryloyloxyethyl) ether of bisphenol A and 3-methylpentanediol di (meth) acrylate. Examples of the polymerizable compound having three or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- ( (Meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified di Intererythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate and caprolactone modified dipentaerythritol hexa (meth) An acrylate is mentioned.

  Among these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

  The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less.

  Content of the polymeric compound (C) in the colored curable resin composition of this invention is 5-65 mass% normally with respect to the total amount of solid content, Preferably it is 7-65 mass%, More Preferably it is 10-60 mass%, More preferably, it is 13-60 mass%, Most preferably, it is 17-55 mass%. The content ratio of the resin (B) and the polymerizable compound (C) (resin (B): polymerizable compound (C)) is usually 20:80 to 80:20, preferably 35:65, based on mass. ~ 80: 20. When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.

  Examples of the polymerization initiator (D) include O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, and biimidazole compounds.

  The O-acyl oxime compound is a compound having a structure represented by the formula (d1). Hereinafter, * represents a bond.

  Examples of O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1- On-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-di) Oxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl 6- (2-Methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used. Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine And at least one selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, and N-benzoyloxy-1- (4- More preferred is phenylsulfanylphenyl) octane-1-one-2-imine.

  The alkylphenone compound is a compound having a structure represented by the formula (d2) or a structure represented by the formula (d3). In addition, the benzene ring in these structures may have a substituent.

  Examples of the compound having the structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) ) -2-benzylbutan-1-one and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one. . Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.

  Examples of the compound having a structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy ) Phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxyacetophenone and benzyl Examples include dimethyl ketal.

  In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (d2).

  As triazine compounds, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl)- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methyl) Phenyl) ethenyl -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acyl phosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of the biimidazole compound include a compound represented by the formula (d4).

(In the formula, R ^{51 to} R ⁵⁶ represent an aryl group having 6 to 10 carbon atoms which may have a substituent.)

  Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and a phenyl group is preferable. Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example, Preferably it is a chlorine atom. As a C1-C4 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are mentioned, Preferably it is a methoxy group.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl). ) -4,4 ′, 5,5′-tetraphenylbiimidazole (for example, see JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2 ' -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (Trial Xylphenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.) and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (for example, see JP-A-07-010913). Of these, compounds represented by the following formula and mixtures thereof are preferred.

  Other polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ′. -Benzophenone compounds such as methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2- Examples include quinone compounds such as ethyl anthraquinone and camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant described below (particularly an amine polymerization initiation assistant).

  Examples of the polymerization initiator that generates an acid include 4-hydroxyphenyldimethylsulfonium-p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium-p-toluenesulfonate, 4 Onium salts such as acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitro Examples include benzyl tosylate and benzoin tosylate.

  The polymerization initiator (D) is preferably a polymerization initiator that generates active radicals, and more preferably selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds. At least 1 type is included, More preferably, an O-acyl oxime compound is included.

  Content of a polymerization initiator (D) is 0.1-40 mass parts normally with respect to 100 mass parts of total amounts of resin (B) and polymeric compound (C), Preferably it is 0.1-30. It is a mass part, More preferably, it is 1-30 mass parts, Most preferably, it is 1-20 mass parts.

<Polymerization initiation aid>
The polymerization initiation assistant is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound (C) whose polymerization has been initiated by the polymerization initiator (D). When the colored curable resin composition of the present invention contains a polymerization initiation assistant, it is usually used in combination with a polymerization initiator (D).

  Examples of the polymerization initiation assistant include amine polymerization initiation assistants, alkoxyanthracene polymerization initiation assistants, thioxanthone polymerization initiation assistants, and carboxylic acid polymerization initiation assistants.

  Examples of the amine polymerization initiation aid include alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid Aminobenzoic acid esters such as 2-dimethylaminoethyl and 2-dimethylhexyl 4-dimethylaminobenzoate; N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4 ′ -Bis (diethylamino) benzophenone and 4,4'-bis (ethylmethylamino) benzophenone are mentioned, and alkylaminobenzophenone such as 4,4'-bis (diethylamino) benzophenone is preferred. Among these, alkylaminobenzophenone is preferable, and 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

  As an alkoxyanthracene polymerization initiation assistant, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9, Examples include 10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

  Examples of the thioxanthone polymerization initiation assistant include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

  Carboxylic acid polymerization initiators include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenyl And sulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

  When using a polymerization initiation aid, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass. When the content of the polymerization initiation assistant is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>
A solvent (E) is not limited, The solvent normally used in the said field | area can be used individually or in combination of 2 or more types. Specifically, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O -, -CO- and -COO- free solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfoxide.

  Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, pyruvin Examples include methyl acid, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

  Ether solvents include 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, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, include phenetol and methyl anisole.

  Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. Is mentioned.

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

  Aromatic hydrocarbon solvents include benzene, toluene, xylene and mesitylene.

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

  Two or more of these solvents may be combined.

  Among the above solvents, an organic solvent having a boiling point of 120 ° C. or more and 210 ° C. or less at 1 atm is preferable from the viewpoints of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3 -Methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide and N-methylpyrrolidone are preferred, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, di- Propylene glycol methyl ether acetate, ethyl lactate, 3-metho Shi butyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N, N- dimethylformamide and N- methylpyrrolidone is more preferred.

  Content of a solvent (E) is 70-95 mass% normally with respect to the total amount of colored curable resin composition, Preferably it is 75-92 mass%, More preferably, it is 75-90 mass%. . When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good. .

<Leveling agent>
Examples of the leveling agent include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.

  Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) are listed.

  Examples of the fluorosurfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Laboratory Co., Ltd.).

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation) can be mentioned.

  The content of the leveling agent is usually 0.0005% by mass or more and 0.6% by mass or less, preferably 0.001% by mass or more and 0.5% by mass or less, based on the total amount of the colored curable resin composition. More preferably 0.001% by mass to 0.2% by mass, still more preferably 0.002% by mass to 0.1% by mass, and particularly preferably 0.005% by mass to 0.07% by mass. It is below mass%. When the leveling agent content is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
The colored curable resin composition of the present invention includes additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., if necessary. May be included.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and, if necessary, It can be prepared by mixing a leveling agent, a polymerization initiation aid and other components. In addition to the colorant (A), pigments and dyes can also be mixed. The pigment is preferably mixed in advance with a part or all of the solvent (E) and used in the state of a pigment dispersion dispersed using a bead mill or the like until the average particle size of the pigment is about 0.2 μm or less. . Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed.

  It is preferable to prepare a solution by dissolving Compound (I) in part or all of the solvent (E) in advance. Furthermore, it is preferable to filter the solution with a filter having a pore size of about 0.01 to 1 μm.

  The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which a colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.

  The film thickness of the color filter to be produced can be appropriately adjusted according to the purpose and application, and is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.5 to 6 μm.

  As a substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate In addition, an aluminum, silver, silver / copper / palladium alloy thin film or the like is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

  The formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.

  First, a colored curable resin composition is applied on a substrate, dried by heating (prebaking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained. Examples of the coating method include a spin coating method, a slit coating method, and a slit and spin coating method. 30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa. The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

  Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used. The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp. Use an exposure device such as a mask aligner or stepper because it can irradiate parallel light uniformly over the entire exposure surface and perform precise alignment between the photomask and the substrate on which the colored composition layer is formed. Is preferred. A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide. The concentration of the alkaline compound is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass. The developer may contain a surfactant. The development method may be any of paddle method, dipping method and spray method. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.

  It is preferable to further post-bake the resulting colored pattern. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes. The color filter having a colored pattern or a colored coating film thus obtained may be further subjected to surface coating treatment in order to impart various characteristics.

  The color filter formed from the colored curable resin composition of the present invention is useful as a color filter used for display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

  Next, the present invention will be described more specifically with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

  In the following synthesis examples, the structure of the compound was confirmed by NMR (JMM-ECA-500; manufactured by JEOL Ltd.) or mass spectrometry (LC; Agilent 1200 model, MASS; Agilent LC / MSD6130 model).

The polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Manufactured by Tosoh Corporation)

  The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

Synthesis example 1
25.3 parts of Coumarin 6 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 206 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C. for 4.5 hours. The mixture was cooled to 10 ° C. and added dropwise to a mixture of 750 parts of ice and 750 parts of water. During the dropping, the temperature of the mixture subjected to the dropping was kept at 10 ° C. Insoluble matter was obtained as a residue of suction filtration. To this residue, 1000 parts of water at 10 ° C. was added, and the mixture was stirred while maintaining the temperature at 10 ° C. to obtain an insoluble matter as a residue of suction filtration. 196 parts of residue were obtained. A mixture of 35.0 parts of DL-1-amino-2-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 502 parts of acetonitrile was added to 99.6 parts of the residue, and the mixture was stirred at room temperature for 3 hours. The mixture was then stirred at 40 ° C. for 1 hour. The mixture was cooled to room temperature, 2220 parts of chloroform and 1500 parts of a 2.5% aqueous sodium hydroxide solution were added, stirred and allowed to stand. The chloroform solution layer was taken out, 1500 parts of a 10% aqueous acetic acid solution was added, and the mixture was stirred and allowed to stand. The chloroform solution layer was taken out, dried over magnesium sulfate, and filtered. After the solvent was distilled off from the filtrate with a rotary evaporator, the filtrate was dried under reduced pressure at 60 ° C. to obtain 12.0 parts of a compound represented by the formula (I-96).

<Identification of Compound Represented by Formula (I-96)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 488
Exact Mass: 487

Synthesis example 2
1.03 parts of the compound represented by the formula (I-96) obtained above, 0.238 parts of succinic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 0.0370 parts and 35.0 parts of 1-methyl-2-pyrrolidone (manufactured by Nacalai Tesque) were mixed and stirred at 70 ° C. for 2.5 hours. To this mixture, 1.07 part of succinic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.287 part of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at 70 ° C. for 18 hours. To this mixture, 300 parts of 1N hydrochloric acid and 444 parts of chloroform were added, stirred and allowed to stand. The chloroform solution layer was taken out and washed twice with 300 parts of 1N hydrochloric acid and once with 300 parts of a 10% aqueous acetic acid solution. The chloroform solution layer was dried over magnesium sulfate and then filtered. After the filtrate was distilled off with a rotary evaporator, the obtained residue was added to 200 parts of water. To this mixture, 444 parts of chloroform was added, stirred and allowed to stand. The chloroform solution layer was taken out, dried over magnesium sulfate, and filtered. The filtrate was evaporated under reduced pressure with a rotary evaporator and then dried under reduced pressure at 60 ° C. To the resulting residue, 5.00 parts of N, N-dimethylformamide was added and stirred, and then added dropwise to 200 parts of an 18% aqueous sodium chloride solution. To this mixture, 444 parts of chloroform was added, stirred and allowed to stand. The chloroform solution layer was taken out, dried over magnesium sulfate, and filtered. The filtrate was evaporated using a rotary evaporator. To the obtained residue, N, N-dimethylformamide (5.06 parts) was added and stirred, and the mixture was added dropwise to 300 parts of an 18% aqueous sodium chloride solution. Insoluble matter was obtained as a residue of suction filtration. This residue was dried under reduced pressure at 60 ° C. to obtain 1.21 parts of a compound represented by the formula (I-117).
.

<Compound represented by Formula (I-117)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 588
Exact Mass: 587

Synthesis example 3
1.07 parts of the compound represented by the formula (I-96) obtained above, 3.28 parts of phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 4-dimethylaminopyridine (Tokyo Chemical Industry Co., Ltd.) 0.556 parts) and 17.0 parts of 1-methyl-2-pyrrolidone (manufactured by Nacalai Tesque) were mixed and stirred at 100 ° C. for 17.5 hours. To this mixture, 1.68 parts of phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.277 part of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added and stirred at 100 ° C. for 4 hours. . The mixture was stirred at 120 ° C. for 4 hours. The mixture was stirred at 100 ° C. for 1 hour. The mixture was cooled to room temperature, 444 parts of chloroform and 300 parts of 1N hydrochloric acid were added, stirred and allowed to stand. The chloroform solution layer was taken out and washed twice with 300 parts of 1N hydrochloric acid, three times with 300 parts of a 15% aqueous sodium carbonate solution and once with 300 parts of a 10% aqueous acetic acid solution. The chloroform solution layer was dried over magnesium sulfate and then filtered. The filtrate was evaporated under reduced pressure with a rotary evaporator and then dried under reduced pressure at 60 ° C. To the resulting residue, 10.6 parts of acetone was added and stirred, and then added dropwise to a mixture of 240 parts of water and 60 parts of methanol. To this mixture, 888 parts of chloroform was added and stirred, and then allowed to stand. The chloroform solution layer was taken out, dried over magnesium sulfate, and filtered. The filtrate was evaporated using a rotary evaporator. To the obtained residue, 22.3 parts of N, N-dimethylformamide was added and stirred, and then added dropwise to 610 parts of an 18% aqueous sodium chloride solution. Insoluble matter was obtained as a residue of suction filtration. This residue was dried under reduced pressure at 60 ° C. to obtain 1.55 parts of a compound represented by the formula (I-118).

<Identification of Compound Represented by Formula (I-118)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 636
Exact Mass: 635

Synthesis example 4
1.03 parts of the compound represented by the formula (I-96) obtained above, trimellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.09 parts, 4-dimethylaminopyridine (Tokyo Chemical Industry Co., Ltd.) )) 0.797 parts and 1-methyl-2-pyrrolidone (Nacalai Tesque) 35.5 parts were mixed and stirred at 100 ° C. for 6 hours. To this mixture, 2.08 parts of trimellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.406 parts of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) are added, and 2.5% at 100 ° C. Stir for hours. The mixture was cooled to room temperature, 444 parts of chloroform and 300 parts of 1N hydrochloric acid were added, stirred and allowed to stand. The chloroform solution layer was taken out and washed 4 times with 300 parts of 1N hydrochloric acid. The chloroform solution was evaporated using a rotary evaporator. To the obtained residue, 269 parts of ethyl acetate and 300 parts of 1N hydrochloric acid were added and stirred, and then allowed to stand, and the ethyl acetate solution layer was taken out. To this ethyl acetate solution, 300 parts of 15% aqueous sodium carbonate solution was added and stirred, and then allowed to stand to take out the aqueous solution layer. To this aqueous solution, 100 parts of a 15% aqueous sodium carbonate solution was added. To this aqueous solution, 105 parts of 35% hydrochloric acid and 269 parts of ethyl acetate were added and stirred, and then allowed to stand, and the ethyl acetate solution layer was taken out. To this ethyl acetate solution, 300 parts of a 10% aqueous acetic acid solution was added and stirred, and then allowed to stand to take out the ethyl acetate solution layer. The ethyl acetate solution was dried over magnesium sulfate and then filtered. The filtrate was evaporated using a rotary evaporator. The residue was purified by column chromatography to obtain 0.354 part of a mixture of the compound represented by formula (I-119) and the compound represented by formula (I-120).

<Identification of Compound Represented by Formula (I-119)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 680
Exact Mass: 679
<Identification of Compound Represented by Formula (I-120)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 680
Exact Mass: 679

Synthesis example 5
3-Amino-4-hydroxybenzenesulfonic acid hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) 45.4 parts, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.50 parts, 4- (diethylamino) salicylaldehyde 44.1 parts (manufactured by Tokyo Chemical Industry Co., Ltd.), 25.8 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 547 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed, The mixture was stirred at 125 ° C. for 2 hours.

  To this mixture, 9.50 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 44.1 parts of 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) )) 25.8 parts and 1-pentanol (Tokyo Chemical Industry Co., Ltd.) 30.3 parts were mixed and stirred at 125 ° C. for 12 hours.

  After cooling the above mixture to room temperature, a solid was obtained as a residue of suction filtration. To this residue, 967 parts of N, N-dimethylformamide was added and stirred at 90 ° C. for 2 hours. The mixture was suction filtered while maintaining the temperature at 80 ° C. to obtain a solid as a residue of suction filtration. To this residue, 126 parts of N, N-dimethylformamide was added to obtain a solid as a residue of suction filtration.

  To this residue, 967 parts of N, N-dimethylformamide was added and stirred at 90 ° C. for 4 hours. The mixture was stirred at room temperature for 12 hours to give a solid as a residue of suction filtration. To this residue, 126 parts of N, N-dimethylformamide was added to obtain a solid as a residue of suction filtration.

  To this residue, 2000 parts of water was added and heated to 80 ° C. to prepare a solution. After this solution was cooled to 30 ° C., 1580 parts of methanol was added and stirred for 12 hours. The precipitated solid was obtained as a residue of suction filtration. To this residue, 2000 parts of water was added and heated to 80 ° C. to prepare a solution. The solvent of this solution was distilled off to obtain a solid.

  To this solid, 148 parts of chloroform was added and stirred. The solvent of this mixture was distilled off to obtain 75.3 parts of a compound represented by the formula (1PAT).

<Identification of Compound Represented by Formula (1PAT)>
¹ H-NMR (500 MHz, DMSO-d ₆ ): 1.14 (6H, t), 3.49 (4H, q), 6.60 (1H, d), 6.81 (1H, dd), 7 .09 (4H, s), 7.66 (1H, dd), 7.66 (1H, d), 7.70 (1H, d), 7.88 (1H, d), 8.83 (1H, s).

  4.3 parts of the compound represented by the formula (1PAT), 1.9 parts of N, N-dimethylformamide, and 21 parts of 1,4-dioxane were mixed, and the mixture was stirred at room temperature with phosphorus oxychloride 3. 1 part was added dropwise. To this mixture, 10 parts of 1,4-dioxane was added and stirred at 70 ° C. for 3 hours. To this mixture, 3.1 parts of phosphorus oxychloride and 0.94 part of N, N-dimethylformamide were added and stirred at 70 ° C. for 1 hour. The mixture was allowed to cool to room temperature. Insoluble matter was obtained as a residue of suction filtration. The residue was washed with 16 parts of acetonitrile and air dried. 5.6 parts of residue were obtained.

  2.1 parts of this residue and 5.2 parts of 1,4-dioxane were mixed. This mixture was stirred while being cooled using a water bath, and 0.37 part of DL-1-amino-2-propanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.0 part of triethylamine were added to the mixture. The mixture was stirred at room temperature for 2 hours. This mixture was added to 25 parts of water. Insoluble matter was obtained as a residue of suction filtration. This residue was dissolved in a mixed solution of 24 parts of N, N-dimethylformamide and 20 parts of methanol. The solvent of this solution was distilled off with a rotary evaporator. The obtained residue was purified by column chromatography. 16 parts of hexane was added to the obtained crystals and stirred. This mixture was subjected to suction filtration, and the obtained residue was air-dried to obtain 1.3 parts of a compound represented by the formula (I-10-1).

<Identification of Compound Represented by Formula (I-10-1)>
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 472
Exact Mass: 471

Synthesis Example 6
4.7 parts of the compound represented by the formula (I-10-1), 9.6 parts of trimellitic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 3.7 parts and 51 parts of 1-methyl-2-pyrrolidone (manufactured by Nacalai Tesque) were mixed and stirred at 100 ° C. for 1 hour in a nitrogen atmosphere.

  The mixture was allowed to cool to room temperature and then filtered. After 90 parts of ethyl acetate and 160 parts of 10% hydrochloric acid were added to the filtrate and stirred, the ethyl acetate solution layer was taken out. To this ethyl acetate solution, 160 parts of 10% hydrochloric acid was added, stirred and allowed to stand, and then the ethyl acetate solution layer was taken out. To this ethyl acetate solution, 120 parts of a 15% aqueous sodium carbonate solution was added, stirred and allowed to stand, and then the aqueous solution layer was taken out. To this aqueous solution, 90 parts of ethyl acetate was added, stirred while cooling using an ice bath, and 35% hydrochloric acid was added to adjust the pH of the aqueous solution layer to less than 1. This mixture was allowed to stand, and the ethyl acetate solution layer was taken out. To this ethyl acetate solution, 150 parts of a 10% aqueous acetic acid solution was added and stirred, and then allowed to stand to take out the ethyl acetate solution layer. The ethyl acetate solution was dried over magnesium sulfate and then filtered. The filtrate was evaporated using a rotary evaporator. The residue was purified by column chromatography to obtain 4.9 parts of a mixture of the compound represented by formula (I-33-1) and the compound represented by formula (I-34-1).

<Identification of Compound Represented by Formula (I-33-1)>
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 664
Exact Mass: 663
<Identification of Compound Represented by Formula (I-34-1)>
(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 664
Exact Mass: 663

Synthesis example 7
An appropriate amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to make a nitrogen atmosphere, 100 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 ° C. with stirring. Next, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] decan-9-yl acrylate mixture (content ratio is 50:50 in molar ratio) 171 parts dissolved in propylene glycol monomethyl ether acetate 40 parts using a dropping pump over about 5 hours And dripped. On the other hand, a solution prepared by dissolving 26 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was placed in a flask over about 5 hours using another dropping pump. It was dripped. After completion of dropping of the polymerization initiator, the temperature was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a copolymer (resin B1) solution having a solid content of 43.5%. The obtained resin B1 had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value in terms of solid content of 53 mgKOH / g.

[Film thickness measurement]
The film thickness was measured using DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.
[Preparation of resin composition for sublimation test (SJS)]
Resin: Methacrylic acid / benzyl methacrylate (molar ratio: 30/70) copolymer (manufactured by Taoka Chemical Co., Ltd., average molecular weight 10700, acid value 70 mg KOH / g) 33.8% propylene glycol monomethyl ether acetate solution 40 parts;
Polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 5.8 parts;
Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF Japan Ltd.) 0.58 parts;
Leveling agent: polyether-modified silicone (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.010 parts;
Solvent: 47 parts of propylene glycol monomethyl ether;
Solvent: 6.8 parts of propylene glycol monomethyl ether acetate were mixed to obtain a resin composition for sublimation test (SJS).

[Formation of resin coating film for sublimation test (SJSM)]
On a 2-inch square glass substrate (Eagle XG; manufactured by Corning), the resin composition for sublimation test (SJS) obtained above was applied by spin coating, and volatile components were volatilized at 100 ° C. for 3 minutes. . After cooling, it was irradiated with light using an exposure machine (TME-150RSK; manufactured by Topcon Corporation) at an exposure amount of 150 mJ / cm ² (based on 365 nm) in an air atmosphere. A resin coating film for sublimation test (SJSM) (thickness: 2.2 μm) was formed by heating in an oven at 220 ° C. for 2 hours.

Example 1
Colorant (A): 14 parts of a compound represented by formula (I-96);
Resin (B): Resin (B1) (solid content conversion) 170 parts;
Solvent (E): 220 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 600 parts of N, N-dimethylformamide;
And surfactant: Polyether modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.063 parts was mixed to obtain a colored curable resin composition.

Example 2
Colorant (A): 20 parts of a compound represented by formula (I-117);
Resin (B): Resin (B1) (solid content conversion) 160 parts;
Solvent (E): 210 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 610 parts of N, N-dimethylformamide;
And surfactant: Polyether modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.063 parts was mixed to obtain a colored curable resin composition.

Example 3
Colorant (A): 22 parts of a compound represented by formula (I-118);
Resin (B): Resin (B1) (solid content conversion) 160 parts;
Solvent (E): 210 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 610 parts of N, N-dimethylformamide;
And surfactant: Polyether modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.063 parts was mixed to obtain a colored curable resin composition.

Comparative Example 1
Colorant (A): Coumarin 6 11 parts;
Resin (B): Resin (B1) (solid content conversion) 170 parts;
Solvent (E): 190 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 630 parts of N, N-dimethylformamide;
And surfactant: Polyether modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.063 parts was mixed to obtain a colored curable resin composition.

[Sublimation evaluation]
Example 4
The colored curable resin composition obtained in Example 1 was applied by spin coating on a 2 inch square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes for colored curable properties. A resin composition layer was formed. The film thickness was measured using DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd. This colored coating film and the resin coating film for sublimation test (SJSM) obtained above were opposed to each other with a space of 70 μm between them, and post-baked at 220 ° C. for 40 minutes. The color difference (ΔEab *) before and after heating of the resin coating film for sublimation test (SJSM) was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). A color difference (ΔEab *) of 5.0 or more indicates that the colorant has sublimability. The results are shown in Table 9. In Table 9, o indicates that the colorant does not have sublimability, and x indicates that the colorant has sublimability.

Example 5
Sublimation evaluation was performed in the same manner as in Example 4 except that the colored curable resin composition obtained in Example 1 was replaced with the colored curable resin composition obtained in Example 2. The results are shown in Table 9.

Example 6
Sublimation evaluation was performed in the same manner as in Example 4 except that the colored curable resin composition obtained in Example 1 was replaced with the colored curable resin composition obtained in Example 3. The results are shown in Table 9.

Comparative Example 2
Sublimation evaluation was performed in the same manner as in Example 4 except that the colored curable resin composition obtained in Example 1 was replaced with the colored curable resin composition obtained in Comparative Example 1. The results are shown in Table 9.

(Preparation of colored curable resin composition)
Example 7
Colorant (A): C.I. I. Pigment Green 7 (pigment) 27 parts,
12 parts acrylic pigment dispersant,
Resin (B): Resin B1 (solid content conversion) 9.5 parts, and Solvent (E): Propylene glycol monomethyl ether acetate 180 parts were mixed, and a pigment dispersion in which the pigment was sufficiently dispersed using a bead mill;
Colorant (A): 3.0 parts of a compound represented by formula (I-118);
Resin (B): Resin B1 (solid content conversion) 40 parts;
Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 49 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 9.8 parts;
Solvent (E): 670 parts of propylene glycol monomethyl ether acetate; and leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) A composition was obtained.

Example 8
C. of the colorant (A) I. Pigment Green 7 (pigment) is changed to C.I. I. A colored curable resin composition was obtained in the same manner as in Example 7 except that the pigment green 36 (pigment) was used.

Example 9
C. of the colorant (A) I. Pigment Green 7 (pigment) is changed to C.I. I. A colored curable resin composition was obtained in the same manner as in Example 7 except that it was replaced with CI Pigment Green 58 (pigment).

Example 10
[Preparation of colored pattern]
The colored curable resin composition obtained in Example 7 was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) by spin coating, and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. Formed. After cooling, the distance between the substrate on which the colored composition layer is formed and the photomask made of quartz glass is set to 200 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Corporation) is used, and 80 mJ / cm ^{2 in} an air atmosphere. The exposure amount (standard on 365 nm) was used. A photomask having a 100 μm line and space pattern was used. The colored composition layer after the exposure was developed by being immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 70 seconds, and washed with water.

  The colored coating film was post-baked at 230 ° C. for 30 minutes to obtain a colored pattern.

Example 11
A colored pattern was obtained in the same manner as in Example 10 except that the colored curable resin composition obtained in Example 7 was replaced with the colored curable resin composition obtained in Example 8.

Example 12
A colored pattern was obtained in the same manner as in Example 10 except that the colored curable resin composition obtained in Example 7 was replaced with the colored curable resin composition obtained in Example 9.

  From the above results, it was confirmed that according to the present invention, it is possible to provide a color curable resin composition technique that provides a color filter in which a colorant does not sublime.

  According to the present invention, since it is not necessary to dimerize the colorant, it is possible to provide a color curable resin composition technique that provides a color filter that facilitates the synthesis of the colorant and does not sublime the colorant. The filter is suitably used for a display device such as a liquid crystal display device.

Claims (7)

A compound represented by formula (I).
[In the formula (I),
X represents an oxygen atom or a sulfur atom.
R ¹ and R ² each independently represent a hydrocarbon group having 1 to 20 carbon atoms.
n represents an integer of 1 to 4.
A represents _{^{-SO 2 -NR 3 -L 2 -OCO-}} L 3 -CO-OM.
M represents a hydrogen atom or an alkali metal atom. When a plurality of M are present, they may be the same as or different from each other.
L ² and L ³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms. -CH ₂ -CH = is constituting the divalent hydrocarbon group, may be replaced in -N =, constituting the divalent hydrocarbon group - represents an oxygen atom, a sulfur atom, -N ( R ⁵⁵ ) —, a sulfonyl group or a carbonyl group may be substituted, and the hydrogen atom contained in the divalent hydrocarbon group is a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, —SO ₃ M , -CO ₂ M, hydroxy group, formyl group, an alkyl group, an alkynyl group or may be substituted with an amino group.
R ⁵⁵ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ⁵⁵ are present, they may be the same as or different from each other.
R ³ represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a group represented by the formula (z). The hydrogen atom contained in the monovalent hydrocarbon group may be replaced with a halogen atom, a hydroxy group or a carboxy group, and —CH ₂ — constituting the monovalent hydrocarbon group is replaced with a carbonyl group. May be. When a plurality of R ³ are present, they may be the same as or different from each other.
In formula (z), L ²² and L ³³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms. -CH ₂ -CH = is constituting the divalent hydrocarbon group, may be replaced in -N =, constituting the divalent hydrocarbon group - represents an oxygen atom, a sulfur atom, -N ( R ⁴⁴ ) —, a sulfonyl group or a carbonyl group may be substituted, and the hydrogen atom contained in the divalent hydrocarbon group is a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, —SO ₃ M , -CO ₂ M, hydroxy group, formyl group, an alkyl group, an alkynyl group or may be substituted with an amino group.
M ¹ represents a hydrogen atom or an alkali metal atom.
R ⁴⁴ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ⁴⁴ are present, they may be the same as or different from each other. ] A compound according to claim 1 of the formula (II).
[In the formula (II),
n, X, R ¹ , R ² , L ² , L ³ and R ⁵⁵ represent the same meaning as described above.
R ³³ represents a hydrogen atom or _{^{-L 22 -OCO-L 33 -CO 2}} M 2.
L ²² and L ³³ represent the same meaning as L ² and L ³ .
M ² represents a hydrogen atom or an alkali metal atom. ] L ² and L ²² are a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms,
The compound according to claim 1 or 2 , wherein L ³ and L ³³ are a divalent aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be substituted with a carboxy group or a halogen atom. Wherein R ¹ and R ^2, independently of one another, a compound according to any one of claims 1 to 3 which is a monovalent hydrocarbon group having 1 to 10 carbon atoms. Colorant comprising a compound according to any one of claims 1-4, resin, a polymerizable compound, a polymerization initiator and a colored curable resin composition containing a solvent. A color filter formed from the colored curable resin composition according to claim 5 . A liquid crystal display device comprising the color filter according to claim 6 .