TW201630905A - Compound - Google Patents

Abstract

The present invention provides a colored resin composition suitably for easily synthesizing a colored agent, and therefore, to form a color filter capable of inhibiting the sublimation of the colored agent. The compound of the present invention is represented by formula (I) and is applicable to dye being used for color display on the color filter and liquid crystal panel.

Description

Compound

The present invention relates to a compound or the like which can be used as a dye (for example, a colored resin composition, a color filter, a liquid crystal display device).

The dye is used, for example, for color display using reflected light or transmitted light in the fields of fiber materials, liquid crystal display devices, inkjet, and the like. As the dye, coumarin 6 is known (Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-154740 (Embodiment 8)

An object of the present invention is to provide a coloring resin composition which is easy to synthesize a coloring agent and which can form a color filter in which sublimation of a coloring agent is suppressed.

The invention includes the following invention.

[1] A compound represented by the formula (I), [Chemical 1]

[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; and 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 or different from each other; L ¹ represents a divalent hydrocarbon group having 1 to 60 carbon atoms; and -CH = which constitutes the divalent hydrocarbon group may be Substituting -N=, -CH ₂ - constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N(R ³ )-, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the divalent hydrocarbon group may be Substituted as a halogen atom, a cyano group, a nitro group, an amine carbenyl group, an amine sulfonyl group, -SO ₃ M ³ , -CO ₂ M ³ , a hydroxyl group, a decyl group or an amine group; R ³ represents a hydrogen atom, carbon a monovalent hydrocarbon group of 1 to 20 or a group represented by the formula (z); the hydrogen atom contained in the monovalent hydrocarbon group may be substituted with a halogen atom, a hydroxyl group or a carboxyl group, and -CH ₂ - constituting the monovalent hydrocarbon group may be Substituted as a carbonyl group; when a plurality of R ³ are present, they may be the same or different from each other;

In the formula (z), L ²² and L ³³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms; -CH = which may constitute a divalent hydrocarbon group may be substituted with -N=, and -CH ₂ constituting the divalent hydrocarbon group _; It may be substituted with 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 may be substituted with a halogen atom, a cyano group, a nitro group or an amine carbamic group. Aminesulfonyl, -SO ₃ M ³ , -CO ₂ M ³ , hydroxy, methoxyl or amine; M ¹ represents a hydrogen atom or an alkali metal atom; in the case where a plurality of M ¹ are present, may be the same or different; substituents L ^1, -SO ^₃ M ₃ or -CO ₂ M ³ hydrogen atoms contained in L ²² or L ³³ of the divalent hydrocarbon group contained in the M ³ represents a hydrogen atom or an alkali metal atom; in the presence of In the case of a plurality of M ³ , the same or different from each other; R ⁴⁴ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; and in the case where a plurality of R ⁴⁴ are present, they may be the same or different from each other] .

[2] The compound according to [1], wherein the above A is -SO ₂ -OL ^a -OM, -SO ₂ -NR ³ -L ^b -OM or -SO ₂ -NR ³ -L ² -OCO-L ³ -CO-OM, [wherein R ³ and M each have the same meaning as described above; each of L ^a and L ^{b is} independently a divalent hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ - constituting the divalent hydrocarbon group may be Is substituted with an oxygen atom or a carbonyl group; the hydrogen atom contained in the divalent hydrocarbon group may be substituted with a halogen atom or a carboxyl group; and L ² and L ³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms; and the divalent hydrocarbon group is constituted. -CH= may be substituted with -N=, and -CH ₂ - constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N(R ⁵⁵ )-, a sulfonyl group or a carbonyl group, and the divalent hydrocarbon group containing the hydrogen atom may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl acyl, acyl amine ^{_{sulfo, -SO 3 M 3, -CO 2}} M 3, hydroxy, methyl or acyl group; M ³ Indicates the same meaning as above; in the case where a plurality of M ³ are present, they may be the same or different from each other; R ⁵⁵ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; in the case where a plurality of R ⁵⁵ are present , etc. may be the same or different from each other].

[3] The compound according to [2], wherein each of L ^a and L ^{b is} independently a phenyl group, a methylene group, an ethyl group, a methyl group or a propyl group.

[4] The compound according to [1], [2] or [3], which is represented by the formula (II), [In the formula (II), n, X, R ¹ , R ² , L ² and L ^{3 have} the same meanings as described above; R ³³ represents a hydrogen atom or -L ²² -OCO-L ³³ -CO ₂ M ² ; ²² and L ³³ each have the same meaning as described above; M ² represents a hydrogen atom or an alkali metal atom; and in the case where a plurality of M ² are present, they may be the same or different from each other].

[5] The compound according to [1] or [4] wherein the above L ²² is a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the above L ³³ is a divalent aliphatic hydrocarbon group which may be substituted by a carboxyl group or a halogen atom. Or an aromatic hydrocarbon group.

[6] The compound according to any one of [2] to [4] wherein the above L ² is a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the above L ³ is a group which may be substituted by a carboxyl group or a halogen atom. A valence aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[7] The compound according to any one of [1] to [6] wherein R ¹ and R ² are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[8] A colored resin composition containing a coloring agent, a resin, a polymerizable compound, a polymerization initiator, and a solvent, which comprises the compound according to any one of [1] to [7].

[9] A color filter formed from the colored resin composition as described in [8].

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

According to the present invention, it is possible to provide a coloring resin composition which is easy to synthesize a coloring agent and which can form a color filter in which sublimation of a coloring agent is suppressed.

The compound of the present invention may be a compound represented by the formula (I), and may be a compound represented by the formula (II) (hereinafter sometimes referred to as a compound (I) and a compound (II)). The compounds of the invention also include tautomers or 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 from 1 to 4.

A represents -SO ₂ -L ¹ -OM.

M represents a hydrogen atom or an alkali metal atom. When there are a plurality of Ms, they may be the same or different from each other.

L ¹ represents a divalent hydrocarbon group having 1 to 60 carbon atoms. -CH= constituting the divalent hydrocarbon group may be substituted with -N=, and -CH ₂ - constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N(R ³ )-, a sulfonyl group or a carbonyl group The hydrogen atom contained in the divalent hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, an amine carbenyl group, an amine sulfonyl group, -SO ₃ M ³ , -CO ₂ M ³ , a hydroxyl group, a methyl group. Or an amine 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 substituted with a halogen atom, a hydroxyl group or a carboxyl group, and -CH ₂ - constituting the monovalent hydrocarbon group may be substituted with a carbonyl group.

In the case where a plurality of R ³ are present, they may be the same or different from each other.

In the formula (z), L ²² and L ³³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms. -CH= constituting the divalent hydrocarbon group may be substituted with -N=, and -CH ₂ - constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N(R ⁴⁴ )-, a sulfonyl group or a carbonyl group. The hydrogen atom contained in the divalent hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, an amine carbenyl group, an amine sulfonyl group, -SO ₃ M ³ , -CO ₂ M ³ , a hydroxyl group, a methyl group or Amine.

M ¹ represents a hydrogen atom or an alkali metal atom. In the case where there are a plurality of M ¹ , they may be the same or different from each other.

Substituent L ^1, -SO hydrogen atom of L ²² or L ³³ of the divalent hydrocarbon group contained in _{it. 3} or -CO ₂ M ³ M ³ M ³ contained in the hydrogen atom or alkali metal atom. In the case where a plurality of M ³ are present, they may be the same or different from each other.

R ⁴⁴ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. In the case where there are a plurality of R ⁴⁴ , they may be the same or different from each other]

In the formula (II), n, X, R ¹ , R ² , L ² and L ³ each have 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 each have the same meaning as described above.

M ² represents a hydrogen atom or an alkali metal atom. In the case where there are a plurality of M ² , they may be the same or different from each other]

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 second butyl group, and a third butyl group. , (2-ethyl)butyl, pentyl, isopentyl, 3-pentyl, neopentyl, third amyl, 1-methylpentyl, 2-methylpentyl, (3-ethyl) Pentyl, hexyl, isohexyl, 5-methylhexyl, (2-ethyl)hexyl, heptyl, (3-ethyl)heptyl, octyl, decyl, decyl, undecyl, a saturated aliphatic hydrocarbon group such as dodecyl or octadecyl, isopropenyl, 1-propenyl, 2-propenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, etc. An aliphatic hydrocarbon group such as an unsaturated aliphatic hydrocarbon group; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 1-methylcyclohexyl group, a 2-methylcyclohexyl group, a 3-methylcyclohexyl group, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4 - dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,2 - dimethylcyclohexyl, 3,3-di Cyclohexyl, 4,4-dimethylcyclohexyl, 2,4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl, 3,3,5,5-tetramethyl a saturated alicyclic hydrocarbon group such as a cyclohexyl group, an unsaturated alicyclic hydrocarbon group such as a cyclohexenyl group; a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,3-dimethylphenyl group, and 2,4 - dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4 , an aromatic hydrocarbon group such as 6-tricresyl, o-isopropylphenyl, m-isopropylphenyl, p-cumyl or 2,6-bis(2-propyl)phenyl; Illustrative are aralkyl groups such as benzyl, phenethyl, biphenyl, 1-naphthyl and 2-naphthyl, and the combinations thereof.

R ¹ and R ² are each independently a monovalent hydrocarbon group having 1 to 10 carbon atoms. The carbon number is preferably from 1 to 8, more preferably from 1 to 6, more preferably from 1 to 3. The above monovalent hydrocarbon group is more preferably a monovalent saturated or unsaturated aliphatic hydrocarbon group, and further preferably a monovalent saturated aliphatic hydrocarbon group.

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

X represents an oxygen atom or a sulfur atom.

n represents an integer from 1 to 4. n is preferably from 1 to 3, more preferably 1 or 2, and still more preferably 1.

A represents -SO ₂ -L ¹ -OM. A is preferably -SO ₂ -OL ^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, more preferably a divalent hydrocarbon group having 1 to 20 carbon atoms.

In L ¹ , the above divalent hydrocarbon group may be methylene, ethyl, propane-1,3-diyl (propyl), propane-1,2-diyl (propyl), butane-1 ,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, decane-1 , 9-diyl, decane-1,10-diyl, undecane-1,11-diyl, dodecane-1,12-diyl, tridecane-1,13-diyl, ten Tetralin-1,14-diyl, pentadecane-1,15-diyl, hexadecane-1,16-diyl, heptadecane-1,17-diyl, octadecan-1,18 -diyl, nonadecane-1,19-diyl, eicosane-1,20-diyl, triacontan-1,30-diyl, tetradecane-1,40-diyl, fifty a linear alkanediyl group such as alkane-1,50-diyl, hexadecane-1,60-diyl, methyl-ethyl-1,2-diyl (methylethylidene), butane- 1,3-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane- An aliphatic hydrocarbon group such as a branched alkanediyl group such as a 1,4-diyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group or a propane-2,2-diyl group.

In L ¹ , the above divalent hydrocarbon group may be a monocyclic or polycyclic alicyclic hydrocarbon group, and may be cyclobutane-1,3-diyl, cyclopentane-1,3-diyl or cyclohexane. -1,2-diyl, 1-methylcyclohexane-1,2-diyl, cyclohexane-1,4-diyl, cyclooctane-1,2-diyl, cyclooctane-1 , 5-diyl, etc., monocyclic cycloalkanediyl, etc. Alkane-2,3-diyl, descending Alkane-1,4-diyl, descending Alicyclic-2,5-diyl, adamantane-1,2-diyl, adamantane-1,5-diyl, adamantane-2,6-diyl, etc., polycyclic cycloalkanediyl, etc. Hydrocarbyl group.

In L ¹ , the divalent hydrocarbon group may be a monocyclic or polycyclic aromatic hydrocarbon group, and may be a polycyclic aromatic group such as a monocyclic aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a cophenyl group or a bisphenyl group. Hydrocarbyl group.

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

In L ¹ , -CH= constituting the divalent hydrocarbon group may be substituted with -N=, and -CH ₂ - constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N(R ³ )-, sulfonate. a mercapto group or a carbonyl group, the hydrogen atom contained in the divalent hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, an amine methyl group, an amine sulfonyl group, -SO ₃ M ³ , -CO ₂ M ³ , a hydroxyl group , a methyl group or an amine group.

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

[化8]

[化10]

[11]

The group represented by L ¹ is preferably a group represented by the formula (L1-9) to the formula (L1-19) and the formula (L1-25) to the formula (L1-43), more preferably a formula (L1- 9) the base represented by the formula (L1-12), the formula (L1-14), the formula (L1-17)~ the formula (L1-19), and the formula (L1-25)~the formula (L1-43), and further Preferably, it is a formula (L1-31)~(L1-34). If the group represented by L ¹ is such a group, it is easy to synthesize. Further, the aromatic ring system in the above chemical formula is exemplified as a compound having a bonding bond at the 1st position and the 4th position, or the 1st position and the 2nd position, and the bond bond of the 1st position and the 4th position may be changed to 1 position. And the 2-position keying button, the 1-digit and 2-digit bonding keys can be changed to the 1-digit and 4-digit bonding keys.

L ^a and L ^{b are} preferably a divalent hydrocarbon group each independently having a carbon number of 1 to 20, more preferably a carbon number of 1 to 20 selected from the group consisting of a divalent aromatic hydrocarbon group and a divalent saturated aliphatic hydrocarbon group. a hydrocarbon group, further preferably a phenyl group, a methylene group, an ethyl group, a methyl group or a propyl group, and more preferably a methylene group, an ethyl group or a methyl group. Ethyl or methyl extended ethyl.

In L ^a and L ^b , -CH ₂ - constituting the divalent hydrocarbon group may be substituted with an oxygen atom or a carbonyl group. The hydrogen atom contained in the divalent hydrocarbon group may be substituted with a halogen atom or a carboxyl 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 having 1 to 30 carbon atoms and a divalent aromatic hydrocarbon group, and preferably a linear or branched chain having 1 to 20 carbon atoms. One or more of the divalent aliphatic hydrocarbon group and the aromatic hydrocarbon group, and more preferably one or more of a linear or branched divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms and an aromatic hydrocarbon group. Specific examples of L ² and L ³ include the groups described as the divalent hydrocarbon group described in the specification.

In L ² and L ³ , -CH= constituting the divalent hydrocarbon group may be substituted with -N=, and -CH ₂ - constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N(R ⁵⁵ ) - a sulfonyl group or a carbonyl group, the hydrogen atom contained in the divalent hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, an amine methyl group, an amine sulfonyl group, -SO ₃ M ³ , -CO ₂ M ³ , hydroxyl, formazan or amine.

Examples of L ² and L ³ include a group represented by the formula (L23-1) to the formula (L23-22). ● indicates the key combination.

[化12]

L ^{2 is} preferably a group represented by the formula (L23-1) to the formula (L23-4), more preferably a group represented by the formula (L23-1) and the formula (L23-2), and particularly preferably The base represented by (L23-2). If L ^{2 is} such a group, it is easy to synthesize.

L ^{3 is} preferably a group represented by the formula (L23-1), the formula (L23-2), and the formula (L23-5) to the formula (L23-20), more preferably a formula (L23-1) or a formula. (L23-2), formula (L23-5), formula (L23-7) to formula (L23-10), and formula (L23-13) to formula (L23-20). If L ^{3 is} such a group, it is easy to synthesize.

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 the 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 have the same meanings as the above L ² and L ³ , respectively.

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

In R ³ , the hydrogen atom contained in the monovalent hydrocarbon group may be substituted with a halogen atom, a hydroxyl group or a carboxyl group, and -CH ₂ - constituting the monovalent hydrocarbon group may be substituted with a carbonyl group. In the case where a plurality of R ³ are present, they may be the same or different from each other.

L ^{22 is} preferably a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and further preferably an ethyl group or a methyl group.

L ^{33 is} preferably a divalent aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be substituted by a carboxyl group or a halogen atom, more preferably a linear or branched alkyl group having a carbon number of 1 to 8 which may be substituted by a carboxyl group or a halogen atom. The phenyl group is further preferably an ethyl group or a phenyl group which may be substituted by a carboxyl group or a halogen atom.

L ^{2 is} preferably a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and further preferably an ethyl group or a methyl group.

L ^{3 is} preferably a divalent aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be substituted by a carboxyl group or a halogen atom, more preferably a linear or branched alkyl group having a carbon number of 1 to 8 which may be substituted by a carboxyl group or a halogen atom. The phenyl group is further preferably an ethyl group or a phenyl group which may be substituted by a carboxyl group or a halogen atom.

In L ²² and L ³³ , -CH= constituting the divalent hydrocarbon group may be substituted with -N=, and -CH ₂ - constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N(R ⁴⁴ ) - a sulfonyl group or a carbonyl group, the hydrogen atom contained in the divalent hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, an amine methyl group, an amine sulfonyl group, -SO ₃ M ³ , -CO ₂ M ³ , hydroxyl, formazan or amine.

M ¹ represents a hydrogen atom or an alkali metal atom. In the case where there are a plurality of M ¹ , they may be the same or different from each other.

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 there are a plurality of R ⁴⁴ and R ⁵⁵ , they may be the same or different from each other. R ⁴⁴ and R ⁵⁵ may be one or more hydrocarbon groups selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group exemplified in the above R ¹ and R ² .

M, M ² and M ³ represent a hydrogen atom or an alkali metal atom, preferably a hydrogen atom, a sodium atom or a potassium atom, more preferably a hydrogen atom. When there are a plurality of such cases, they may be the same 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 respectively represent the above-exemplified formula (L1-1) to (L1-43). The basis.

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

The method for producing the compound (I) can be produced by reacting a compound represented by the formula (pa1) with chlorosulfonic acid to produce a compound represented by the formula (pa2), and then making the formula (pa2) The compound represented by the formula (p3) is reacted in the presence of a solvent.

The reaction temperature of the compound represented by the formula (pa1) with chlorosulfonic acid is preferably from 0 ° C to 200 ° C, more preferably from 30 ° C to 150 ° C, and further preferably from 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 further preferably 0 ° C to 60 ° C. °C.

The solvent used for the reaction of the compound represented by the formula (pa2) with the compound represented by the formula (pa3) includes methanol, ethanol, isopropanol, acetonitrile, tetrahydrofuran, acetone, and 3-methyl-2-pentane. Ketone, ethyl acetate, hexane, toluene, dichloromethane, chloroform, N,N-dimethylformaldehyde and N-methylpyrrolidone, etc., preferably acetonitrile, N,N-dimethylformaldehyde and N - Methyl pyrrolidone.

The compound represented by the formula (pa2) may be reacted with a compound represented by the formula (pa3) in the presence of a base or an alkali metal. The above-mentioned base is preferably a tertiary amine, a compound having a pyridine skeleton, and an organometallic compound, and specific examples thereof include triethylamine, pyridine, 4-dimethylaminopyridine, methyllithium, and phenyl. Lithium, butyllithium, a second butyllithium, a third butyllithium or the like are preferably pyridine, 4-dimethylaminopyridine and butyllithium. Examples of the alkali metal include sodium and lithium, and lithium is preferable.

[Chemistry 14]

In the formula (pa1), the formula (pa2), and the formula (pa3), R ¹ to R ² , X, n, L ¹ and M have the same meanings as described above.

In the formula (pa3), XX represents a hydrogen atom, a halogen atom, *-O-toluenesulfonyl group or *-O-methylsulfonyl group. * indicates the key combination]

In the production of the compound (pa2), the amount of the chlorosulfonic acid used is usually from 1 mol to 100 mol, preferably from 5 mol to 60 mol, based on the compound 1 mol expressed by the formula (pa1). More preferably 10 moles ~ 40 moles.

In the production of the compound (I), the amount of the compound represented by the formula (pa3) is usually from 1 mol to 100 mol, preferably 1 mol, based on the compound 1 mol expressed by the formula (pa2). Ears ~80 moles, more preferably 1~60 moles.

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

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

The above-mentioned base is preferably a tertiary amine and a compound having a pyridine skeleton, specifically For example, triethylamine, pyridine, 4-dimethylaminopyridine or the like may be mentioned, and pyridine and 4-dimethylaminopyridine are preferred.

Examples of the solvent include acetonitrile, tetrahydrofuran, acetone, 3-methyl-2-pentanone, ethyl acetate, hexane, toluene, dichloromethane, chloroform, N,N-dimethylformaldehyde, and N-methyl. The pyrrolidone or the like is preferably N,N-dimethylformaldehyde or N-methylpyrrolidone.

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

In the production of the compound (II), the amount of the compound represented by the formula (pa5) is usually 1 mol to 200 mol, preferably 1 mol, based on the compound 1 mol expressed by the formula (pa4). Ears ~160 moles, more preferably 1 mole to 140 moles.

In the production of the compound (II), the amount of the tertiary amine and the compound having a pyridine skeleton is usually 0.1 mol to 80 mol, preferably 0.1, based on the compound 1 mol represented by the formula (pa4). Moer ~ 60 moles, more preferably 0.1 to 45 moles.

The method for producing the formula (pa4) can be produced by reacting a compound represented by the formula (pa2) with a compound represented by the formula (pa6) in the presence of a solvent.

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

The solvent used for the reaction of the compound represented by the formula (pa2) with the compound represented by the formula (pa6) includes methanol, ethanol, isopropanol, acetonitrile, tetrahydrofuran, acetone, and 3-methyl-2-pentane. Ketone, ethyl acetate, hexane, toluene, dichloromethane, chloroform, N,N-dimethylformaldehyde and N-methylpyrrolidone, etc., preferably acetonitrile, N,N-dimethylformaldehyde and N - Methyl pyrrolidone.

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

In the production of the compound (pa4), the amount of the compound represented by the formula (pa6) is usually from 1 mol to 100 mol, preferably 1 mol, based on the compound 1 mol expressed by the formula (pa2). Ears ~80 moles, more preferably 1~60 moles.

The compound represented by the formula (pa2) is a Vilsmeier which is used in the presence of a solvent by using N,N-dimethylformamide and sulfinium chloride, phosphorus oxychloride, phosphorus pentachloride or ethylenedichloride. The reaction is synthesized from a compound represented by the formula (pa7).

In the formula (pa7), R ¹ to R ² , X and n have the same meanings as described above.

M' represents a hydrogen atom, an alkali metal atom or NH ₄ . When there are multiple M's, they may be the same or different from each other]

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

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

Examples of the solvent include acetonitrile, tetrahydrofuran, acetone, 3-methyl-2-pentanone, ethyl acetate, hexane, toluene, dichloromethane, chloroform, and 1,4-diene. Alkane, N,N-dimethylformaldehyde and N-methylpyrrolidone, etc., preferably acetonitrile, 1,4-two Alkane, N,N-dimethylformaldehyde and N-methylpyrrolidone.

In the production of the compound represented by the formula (pa2), the amount of N,N-dimethylformamide used is usually 1 mole to 50 moles per mole of the compound represented by the formula (pa7). Preferably, it is 1 mole to 40 moles, more preferably 1 mole to 30 moles.

In the production of the compound represented by the formula (pa2), the use amount of sulfinium chloride, phosphorus oxychloride, phosphorus pentachloride or ethanedichloride is relative to the compound 1 represented by the formula (pa7). Usually 1 mole to 50 moles, preferably 1 mole to 41 moles, more preferably 1 mole to 30 moles.

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

For example, a method may be mentioned in which a reaction mixture is added to a solvent represented by the compound (I), the compound (II), the compound represented by the formula (pa2) or the compound represented by the formula (pa4), and the crystal is crystallized by the method. After the precipitation, the crystal is taken out by filtration; the reaction mixture is dissolved in tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, toluene, chloroform or a mixed solution thereof, and then water, aqueous sodium hydroxide solution, aqueous acetic acid solution, hydrochloric acid, Sodium chloride water The solution, sodium hydrogencarbonate aqueous solution or sodium carbonate aqueous solution or the like is washed and then dried; or the solvent of the reaction mixture is distilled off, and then purified by column chromatography.

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

<Coloring agent of the present invention>

The coloring agent of the present invention (hereinafter sometimes referred to as "coloring agent (A)") contains, for example, the compound (I) or the compound (II) as an active ingredient. The colorant (A) may contain only the compound (I) or the compound (II), and may also 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 from 1 to 100% by mass, preferably from 3 to 100% by mass, more preferably from 3 to 70% by mass, still more preferably 3 ~60% by mass.

The colorant (A) can be used as a coloring agent contained in the colored resin composition used for the color filter of a display device such as a liquid crystal display device.

Examples of the dye other than the compound (I) or the compound (II) include a solvent index (Solvent), an acidity (Acid), and a basicity (Basic) in the Colour Index (published by The Society of Dyers and Colourists). ), a reactive, direct, disperse or reduced (Vat) compound, or a well-known dye as described in Dyeing note. Further, according to the chemical structure, an azo dye, an anthraquinone dye, a triphenylmethane dye, Dyes and phthalocyanine dyes, etc. These dyes may be used alone or in combination of two or more.

Specifically, a dye having the following color index (C.I.) number can be cited. CI Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; CI 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; CI reaction yellow 2, 76, 116; CI 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; CI Disperse Yellow 51 , 54, 76; CI solvent orange 2, 7, 11, 15, 26, 41, 54, 56, 99; CI 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; CI reaction orange 16; CI direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57 , 61, 64, 65, 68, 70, 96, 97, 106, 107; CI 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; CI Acid Red 73, 80, 91, 92, 97, 138 , 151, 211, 274, 289; CI Acid Violet 34, 102; CI Disperse Violet 26, 27; CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59. 60; CI 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; CI Acid Blue 25, 27, 40, 45, 78, 80, 112; CI Direct Blue 40; CI 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. Reduction Green 1 and the like.

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

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

Among the green pigments and blue pigments, a phthalocyanine pigment is preferred, and at least one selected from the group consisting of a copper halide phthalocyanine pigment and a zinc halide phthalocyanine pigment is preferred, and is preferably selected from the group consisting of CI Pigment Green 7 At least one of the group consisting of 36, 58 and 59. These pigments are suitable as green colorants, and by using a coloring agent containing these pigments, it is possible to form a color filter which is easy to optimize in transmission spectrum and which is excellent in light resistance or chemical resistance.

The pigment may be subjected to a rosin treatment, a surface treatment by using a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment on the surface of the pigment by a polymer compound or the like, or a method of sulfuric acid micronization or the like. The micronization treatment, the cleaning treatment for removing impurities by an organic solvent or water, the removal treatment for ionic impurities by an ion exchange method, or the like. The particle size of the pigment is preferably substantially uniform. By dispersing the pigment by containing a pigment dispersant, it is possible to prepare a pigment dispersion in which the pigment is uniformly dispersed in the pigment dispersant solution. The pigments may be separately subjected to dispersion treatment, or a plurality of types may be mixed and then subjected to dispersion treatment.

The pigment dispersant may, for example, be a surfactant, or the like, and may be any of a cationic, an anionic, a nonionic or an amphoteric surfactant. Specifically, a surfactant such as a polyester-based, polyamine-based or acrylic-based surfactant can be used. These pigment dispersants may be used singly or in combination of two or more. As a pigment dispersing agent, KP (Shin-Etsu Chemical Co., Ltd.), Flowlen (Kyoeisha Chemical Co., Ltd.), and Solsperse (registered trademark) (manufactured by Zeneca) are listed. EFKA (registered trademark) (manufactured by BASF Corporation), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), and the like.

In the case of using a pigment dispersant, the amount thereof to be used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, there is a tendency to obtain a pigment dispersion liquid which is more uniformly dispersed.

<Colored resin composition of the present invention>

The colored resin composition of the present invention contains a coloring agent (A), a resin (hereinafter sometimes referred to as "resin (B)"), a polymerizable compound (hereinafter sometimes referred to as "polymerizable compound (C)"), and polymerization. The starting agent (hereinafter sometimes referred to as "polymerization initiator (D)") and the solvent (hereinafter sometimes referred to as "solvent (E)"). The colored resin composition of the present invention may contain a leveling agent in addition to the components. The colored resin composition of the present invention may contain a polymerization initiation aid in addition to the components. Agent. In another aspect of the invention, the colored resin composition may comprise a colorant (A), a resin (B), a solvent (E), and optionally a surfactant.

The content ratio of the coloring agent (A) in the colored resin composition is usually 1% by mass or more and 70% by mass or less, and preferably 1% by mass or more and 60% by mass or less based on the total amount of the solid content component. It is more preferably 5% by mass or more and 60% by mass or less, and particularly preferably 5% by mass or more and 50% by mass or less. When the content of the colorant (A) is within the above range, it is easier to obtain a desired spectral or color density. In the present specification, the "total amount of the solid content component" means the total amount of the components remaining after the solvent is removed from the colored resin composition of the present invention. The total amount of the solid content component and the content of each component relative thereto can be measured, for example, by a known analytical method such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) contained in the colored resin composition of the present invention is preferably an alkali-soluble resin, more preferably having a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. Addition polymer. Examples of such a resin include the following resins [K1] to [K6].

Resin [K1]: at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter sometimes referred to as "(a)"), and a ring having a carbon number of 2 to 4 a copolymer of an ether structure and an ethylenically unsaturated bond monomer (b) (hereinafter sometimes referred to as "(b)")

Resin [K2]: (a), (b), and a monomer (c) capable of copolymerizing with (a) (wherein, unlike (a) and (b)) (hereinafter sometimes referred to as "(c) Copolymer

Resin [K3]: copolymer of (a) and (c)

Resin [K4]: a resin obtained by reacting the copolymer of (a) and (c) and (b)

Resin [K5]: a resin obtained by reacting the copolymer of (b) with (c) and (a)

Resin [K6]: a resin obtained by reacting the copolymer of (b) and (c) with (a) and further reacting with a carboxylic anhydride.

Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-/m-/p-vinylbenzoic acid, maleic acid, fumaric acid, and citraconic acid. Sinocanic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrobenzene Unsaturated dicarboxylic acid such as formic acid, dimethyltetrahydrophthalic acid or 1,4-cyclohexene dicarboxylic acid; methyl-5-lower Alkene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]-2-heptene, 5,6-dicarboxybicyclo[2.2.1]-2-heptene, 5-carboxy-5 -Methylbicyclo[2.2.1]-2-heptene, 5-carboxy-5-ethylbicyclo[2.2.1]-2-heptene, 5-carboxy-6-methylbicyclo[2.2. 1]-2-heptene, 5-carboxy-6-ethylbicyclo[2.2.1]-2-heptene and other bicyclic unsaturated compounds containing a carboxyl group; maleic anhydride, citraconic anhydride, and ykang Anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, Unsaturated dicarboxylic anhydride such as dimethyltetrahydrophthalic anhydride or 5,6-dicarboxybicyclo[2.2.1]-2-heptene anhydrate; succinic acid mono[2-(methyl)propene oxime Unsaturated mono[(meth)propenyloxyalkyl]ester of divalent or higher polycarboxylic acid such as phenylethyl ester, phthalic acid mono [2-(methyl) propylene methoxyethyl] ester The α-(hydroxymethyl) acrylate is equal to the unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule.

Among them, acrylic acid, methacrylic acid, and maleic anhydride are preferred from the viewpoint of copolymerization reactivity or solubility of the obtained resin in an aqueous alkaline solution.

(b) means a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, an oxirane ring, an oxetane ring, a tetrahydrofuran ring or the like) and an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether structure of 2 to 4 carbon atoms and a (meth)acryloxy group. In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid, "(meth)acryloyl group" and "(meth)acrylic acid. The expression "ester" also means the same meaning.

(b): a monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), having an oxetanyl group and an ethylenic unsaturated group The monomer (b2) of the bond (hereinafter sometimes referred to as "(b2)")) and the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)").

(b1): a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes 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)").

As (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferred. Specific examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and shrinkage. Glyceryl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinyl vinyl glycidyl ether, α-methyl - m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxy) Methyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidyloxy) Methyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tri ( Glycidoxymethyl)styrene and 2,4,6-tris(glycidoxymethyl)styrene.

Examples of (b1-2) include vinylcyclohexene oxide and 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000; manufactured by Daicel). 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M100; Daicel) (Production), a compound represented by the formula (1) and a compound represented by the formula (2).

[化18]

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

Examples of the alkyl group having 1 to 4 carbon atoms of R ^a and R ^b include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, and a third butyl group. Examples of the alkyl group in which the hydrogen atom of R ^a and R ^b is substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, and 3- Hydroxypropyl, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl and 4-hydroxybutyl.

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 group having 1 to 4 carbon atoms, specifically It is preferably a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group having 1 to 6 carbon atoms of R ^c include a linear or branched alkanediyl group, and specific examples thereof include a methylene group, an ethylidene group, and a propane-1,3-two group. a linear alkanediyl group such as a butane-1,4-diyl group, a pentane-1,5-diyl group and a hexane-1,6-diyl group; a propane-1,2-diyl group or the like Alkanediyl.

X ^a and X ^b are each independently preferably a single bond, * - R ^c - or * -R ^c -O-, more preferably a single bond or * -R ^c -O-, specifically, it is preferably a single bond Methylene, ethyl, *-CH ₂ -O- or *-CH ₂ CH ₂ -O-, more preferably a single bond or *-CH ₂ CH ₂ -O-. Further, in the above formula, * represents a bond with O.

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

[化23]

The compound represented by the formula (2) includes a compound represented by the formula (2-1) to the formula (2-15), and among them, a formula (2-1), a formula (2-3), and a formula are preferable. (2-5), a compound represented by the formula (2-7), the formula (2-9), and the formula (2-11) to the formula (2-15), more preferably a formula (2-1) or a formula (() 2-7), a compound represented by the formula (2-9) and the formula (2-15).

[化27]

[化32]

The compound represented by the formula (1) and the compound represented by the formula (2) may be used singly, and the compound represented by the formula (1) may be used in combination with the compound represented by the formula (2). When these are used in combination, the ratio of the compound represented by the formula (1) to the compound represented by the formula (2) (the compound represented by the formula (1): the compound represented by the formula (2)) is based on the molar standard. Preferably, it is 5:95 to 95:5, more preferably 10:90 to 90:10, and still more preferably 20:80 to 80:20.

As (b2), a monomer having an oxetanyl group and a (meth) acryloxy group is more preferable. Examples of (b2) include 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, and 3- Ethyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methylpropene oxime Ethyloxyoxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane and 3 -ethyl-3-propenyloxyethyl Oxetane.

As (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group is more preferable. Examples of (b3) include tetrahydrofuran methyl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofuranmethyl methacrylate.

(b) preferably (b1), in terms of reliability of heat resistance and chemical resistance of the obtained color filter, is excellent in storage stability of the colored resin composition. In other words, (b1) is preferably (b1-2).

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentane (meth)acrylate Ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, {tricyclo[5.2.1.0 ^2,6 ]decane-8-yl} In this technical field, it is called "dicyclopentyl (meth) acrylate" as a conventional name. It may also be called "tricyclodecyl (meth) acrylate) or (meth) acrylate. Ring [5.2.1.0 ^2,6 ]nonene-8-yl} ester (referred to as "dicyclopentenyl (meth) acrylate)" in the technical field, (meth)acrylic acid Dicyclopentyloxyethyl ester, (meth)acrylic acid Base ester, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (methyl) (meth) acrylate such as benzyl acrylate; hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate; maleic acid a dicarboxylic acid diester such as ethyl ester, diethyl fumarate or diethyl itaconate; bicyclo[2.2.1]-2-heptene, 5-methylbicyclo[2.2.1]- 2-heptene, 5-ethylbicyclo[2.2.1]-2-heptene, 5-hydroxybicyclo[2.2.1]-2-heptene, 5-hydroxymethylbicyclo[2.2.1] -2-heptene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]-2-heptene, 5-methoxybicyclo[2.2.11-2-heptene, 5-ethoxy Bicyclo[2.2.1]-2-heptene, 5,6-dihydroxybicyclo[2.2.1]-2-heptene, 5,6-di(hydroxymethyl)bicyclo[2.2.1] -2-heptene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]-2-heptene, 5,6-dimethoxybicyclo[2.2.1]-2- Heptene, 5,6-diethoxybicyclo[2.2.1]-2-heptene, 5-hydroxy-5-methylbicyclo[2.2.1]-2-heptene, 5-hydroxy-5 -ethylbicyclo[2.2.1]-2-heptene, 5-hydroxymethyl-5-methyl Bicyclo[2.2.11-2-heptene, 5-t-butoxycarbonylbicyclo[2.2.1]-2-heptene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]-2- Heptene, 5-phenoxycarbonylbicyclo[2.2.1]-2-heptene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]-2-heptene, 5, a bicyclic unsaturated compound such as 6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]-2-heptene; N-phenyl maleimide, N-cyclohexyl-n-butylene Imine, N-benzyl maleimide, N-butylenediamine-3-butyleneimine benzoate, N-butylenediamine-4-cis Butylenediamine butyrate, N-butylenediamine-6-methyleneimine hexanoate, N-butylimide-3-oximidine a dicarbonyl quinone imine compound such as propionate or N-(9-acridinyl) maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, Vinyl-containing aromatic compounds such as vinyl toluene and p-methoxystyrene; vinyl nitriles such as acrylonitrile and methacrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; acrylamide and methyl a vinyl-containing decylamine such as acrylamide; Vinyl esters like esters; 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like hexadiene.

Among these, from the viewpoint of copolymerization reactivity and heat resistance, a vinyl group-containing aromatic compound, a dicarbonyl quinone imine compound, and a bicyclic unsaturated compound are preferable. Specifically, styrene, vinyl toluene, benzyl (meth)acrylate, (meth)acrylic acid {tricyclo[5.2.1.0 ^2,6 ]decane-8-yl}ester, N-benzene is preferred. A cis-butenylene imine, N-cyclohexyl maleimide, N-benzyl maleimide, and bicyclo [2.2.1]-2-heptene.

In the resin [K1], the ratio of the structural unit derived from each of them is preferably among all the structural units constituting the resin [K1]. The structural unit derived from (a): 2 to 60 mol% derived from the structural unit of (b): 40 to 98 mol%, more preferably the structural unit derived from (a): 10 to 50 mol% of the source The structural unit from (b): 50~90 mol%.

When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability of the colored resin composition, the developability in forming a colored pattern, and the solvent resistance of the obtained color filter tend to be more excellent.

The resin [K1] can be, for example, the method described in the "Experimental Method for Polymer Synthesis" (Dazu Takashi, issue: Chemical Tongren (share), first edition, first print, March 1, 1972). The citations described in this document are made by reference.

Specifically, a method in which a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction container, for example, by replacing oxygen with nitrogen, thereby forming a deoxidizing environment and stirring Heat and keep warm. In addition, the polymerization initiator, solvent, and the like used herein are not particularly limited, and those generally used in the field can be used. For example, examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxidation. The solvent (such as benzamidine peroxide) may be any solvent as long as it dissolves each monomer, and examples thereof include a solvent of the colored resin composition of the present invention described below.

As the copolymer to be obtained, the solution after the reaction may be used as it is, or a solution obtained by concentration or dilution may be used, or a solid (powder) form extracted by a method such as reprecipitation may be used. In particular, by using the solvent contained in the colored resin composition of the present invention as a solvent in the polymerization, the solution after the reaction can be directly used for preparing the colored resin composition of the present invention, so that the colored resin composition of the present invention can be simplified. Manufacturing steps.

In the resin [K2], the ratio of the structural unit derived from each of them is among all the structural units constituting the resin [K2]. Preferably, the structural unit derived from (a): 2 to 45 mol% of the structural unit derived from (b): 2 to 95 mol% derived from the structural unit of (c): 1 to 65 mol%, more The structural unit derived from (a): 5 to 40 mol% derived from the structural unit of (b): 5 to 80 mol% derived from the structural unit of (c): 5 to 60 mol%.

When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored resin composition, the developability in forming a colored pattern, and the solvent resistance, heat resistance and mechanical properties of the obtained color filter are present. The tendency to be more excellent.

The resin [K2] can be produced, for example, in the same manner as the method described in the method for producing the resin [K1].

In the resin [K3], among the structural units derived from each, among all the structural units constituting the resin [K3], it is preferred that the structural unit derived from (a): 2 to 60 mol% is derived from ( c) The structural unit: 40 to 98 mol%, more preferably the structural unit derived from (a): 10 to 50 mol% derived from the structural unit of (c): 50 to 90 mol%.

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

The resin [K4] can be obtained by adding the copolymer of (a) and (c) and adding the cyclic ether having 2 to 4 carbon atoms (b) to the carboxylic acid (a) and/or Or a carboxylic anhydride. Specifically, it can be manufactured in the following manner. First, it is described in the manufacturing method of the resin [K1]. The copolymer of (a) and (c) was produced in the same manner. In this case, the ratio of the structural units derived from each of them is preferably the same as that exemplified for the resin [K3]. Then, a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the above copolymer is reacted with a cyclic ether compound having 2 to 4 carbon atoms which is contained in (b). After the copolymer of (a) and (c) is produced, the gas in the flask is replaced with nitrogen by air, and the catalyst (b), the catalyst of the reaction of the carboxylic acid or the carboxylic anhydride with the cyclic ether compound is charged into the flask ( For example, tris(dimethylaminomethyl)phenol or the like and a polymerization inhibitor (for example, hydroquinone) can be reacted at, for example, 60 to 130 ° C for 1 to 10 hours, whereby the resin [K4] can be produced.

The amount of use of (b) is preferably from 5 to 80 moles, more preferably from 10 to 75 moles, relative to (a) 100 moles. By adjusting the amount of use of (b) to the range, the colored resin composition containing the obtained resin has storage stability, developability in pattern formation, solvent resistance of the obtained pattern, heat resistance, and mechanical strength. And the tendency of the balance of sensitivity is better. The (b) for the resin [K4] is preferably (b1), more preferably (b1-1), in terms of high reactivity of the cyclic ether moiety and unreacted (b).

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

The reaction conditions such as the method of adding each reagent, the reaction temperature, and the reaction time can be appropriately adjusted in consideration of the production equipment, the amount of heat released during polymerization, and the like. In addition, the addition method or the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generation during polymerization, and the like in the same manner as the polymerization conditions.

When the resin [K5] was produced, the copolymer of (b) and (c) was obtained in the same manner as in the production method of the above resin [K1]. With respect to the obtained copolymer, the solution after the reaction may be used as it is, or a solution obtained by concentration or dilution may be used, or a solid (powder) form extracted by a method such as reprecipitation may be used. In the first stage, the ratio of the structural units derived from (b) and derived from (c) with respect to the copolymers constituting the above (b) and (c) The total number of moles of all structural units of the substance is preferably a structural unit derived from (b): 5 to 95 mol% of the structural unit derived from (c): 5 to 95 mol %, more preferably a source The structural unit from (b): 10 to 90 mol% derived from the structural unit of (c): 10 to 90 mol%.

Further, as a second step, the copolymer of (b) and (c) has a cyclic ether moiety derived from (b) and (a) under the same conditions as in the production method of the resin [K4]. The carboxylic acid or a carboxylic acid anhydride is reacted, whereby the resin [K5] can be obtained.

In the second stage, the amount of (a) used for the reaction with the copolymers of (b) and (c) above is preferably from 5 to 80 moles per 100 moles of (b). The (b) for the resin [K5] is preferably (b1), more preferably (b1-1), in terms of high reactivity of the cyclic ether moiety and unreacted (b).

The resin [K6] is a resin obtained by further reacting a resin [K5] with a carboxylic anhydride, and specifically, a carboxylic acid or a carboxy group derived from the cyclic ether moiety derived from (b) and (a) It is produced by reacting a hydroxyl group produced by an acid anhydride reaction with a carboxylic acid anhydride.

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, and 3,4,5,6-tetrahydrobenzene. Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]-2-heptene anhydrate. The amount of the carboxylic anhydride used is 1 mol, preferably 0.5 to 1 mol, based on the amount used in (a).

Examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer and 3,4-epoxytricyclo(methyl)acrylate [5.2.1.0]. Resin such as ^2,6 ]nonyl ester/(meth)acrylic copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (meth)acrylic acid Glycidyl ester/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.4.1.0 ^2,6 ]decyl (meth)acrylic acid/N-cyclohexyl cis (meth)acrylate Butylenediamine copolymer, 3,4-epoxytricyclo(5.sup.2-epoxy)[5.2.1.0 ^2,6 ]decyl ester / (meth)acrylic / vinyl toluene copolymer, 3-methyl- a resin such as 3-(meth)acryloxymethyloxybutane/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth)acrylate/(meth)acrylic acid copolymer, Resin such as styrene/(meth)acrylic acid copolymer, benzyl (meth)acrylate/tricyclodecyl (meth)acrylate/(meth)acrylic acid copolymer [K3]; glycidol (meth)acrylate a resin obtained by adding an ester to a benzyl (meth) acrylate/(meth)acrylic acid copolymer to make (meth) propylene Addition of glycidyl ester to a resin obtained from a tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, and addition of glycidyl (meth)acrylate to a tricyclo(meth)acrylate a resin such as a resin obtained by decyl ester/benzyl (meth)acrylate/(meth)acrylic acid copolymer [K4]; a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate a resin obtained by reacting with (meth)acrylic acid, a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate with (meth)acrylic acid a resin [K5]; a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid and further reacting with tetrahydrophthalic anhydride A resin such as a resin obtained [K6].

The resin (B) is preferably one selected from the group consisting of a resin [K1], a resin [K2], and a resin [K3], and more preferably selected from the group consisting of a resin [K1] and a resin [K2]. One of them. When it is such a resin, the colored resin composition is excellent in developability. From the viewpoint of the adhesion between the colored pattern and the substrate, the resin [K1] is further preferable.

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

Molecular weight distribution of resin (B) [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably from 1.1 to 6, more preferably from 1.2 to 4, still more preferably from 1.3 to 3.

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

Here, the acid value is a value measured by the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be obtained, for example, by titration using a potassium hydroxide aqueous solution.

The content of the resin (B) is preferably from 7 to 65% by mass, more preferably from 10 to 60% by mass, and particularly preferably from 13 to 60% by mass, based on the total amount of the solid content. It is preferably 17 to 55 mass%. When the content of the resin (B) is in the above range, there is a tendency that the colored pattern is easily formed, the resolution of the colored pattern, and the residual film ratio are improved.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound which can be polymerized by the action of an active radical and/or an acid generated by a polymerization initiator, and examples thereof include a polymerizable compound having an ethylenically unsaturated bond, and preferably have ( A compound of a methyl acrylate structure. The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds, more preferably a polymerizable compound having five to six ethylenically unsaturated bonds.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexyl carbitol acrylate. 2-hydroxyethyl acrylate, N-vinylpyrrolidone, (a), (b) and (c) above. Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, and neopentyl glycol di(a). Acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl)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, and pentaerythritol tetra(meth)acrylate. Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, three quarters Alcohol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol 九 (meth) acrylate, isocyanuric acid tris (2-(methyl) Propylene methoxyethyl ester, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol 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) acrylate.

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.

The content of the polymerizable compound (C) in the colored resin composition of the present invention is usually 5 to 65% by mass, preferably 7 to 65% by mass, more preferably 10%, based on the total amount of the solid content component. 60% by mass, further preferably 13 to 60% by mass, particularly preferably 17 to 55% by mass. The content ratio of the resin (B) to the polymerizable compound (C) (resin (B): polymerizable compound (C)) is usually 20:80 to 80:20, preferably 35:65 by mass. ~80:20. When the content of the polymerizable compound (C) is in the above range, the residual film ratio at the time of formation of 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 initiating polymerization by generating active radicals, acids, or the like under the action of light or heat, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include an O-indenyl hydrazine compound, an alkyl phenone compound, and three. A compound, a mercaptophosphine oxide compound, and a biimidazole compound.

The O-indenyl compound is a compound having a structure represented by the formula (d1). Hereinafter, * indicates a keying key.

The O-indenyl hydrazine compound may, for example, be N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine or N-benzylideneoxy group. 1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclopentyl Propane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]B Alkan-1-amine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxol Methyloxy)benzhydryl}-9H-indazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-A Benzobenzhydryl)-9H-oxazol-3-yl]-3-cyclopentylpropane-1-imine and N-benzylideneoxy-1-[9-ethyl-6-(2- Methyl benzhydryl)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (the above is manufactured by BASF Corporation), and N-1919 (made by ADEKA Co., Ltd.) can also be used. Wherein, it is preferably selected from the group consisting of N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzylideneoxy-1-( 4-phenylthiophenyl)octane-1-one-2-imine and N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1 At least one of the group consisting of -keto-2-imine, more preferably N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-ya amine.

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

The compound having a structure represented by the formula (d2) includes 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propan-1-one and 2-dimethyl group. Amino-1-(4-morpholinylphenyl)-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, and 379 (the above are manufactured by BASF Corporation) can also be used.

The compound having a structure represented by the formula (d3) includes 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4-( 2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one Oligomers, α,α-diethoxyacetophenone and benzoin dimethyl ketal.

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

As three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-sunflower-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three And 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri .

The fluorenylphosphine oxide compound is exemplified by 2,4,6-trimethylbenzimidyldiphenylphosphine oxide.

The biimidazole compound may, for example, be a compound represented by the formula (d4).

[化37]

(wherein 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 preferred. Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group is preferred.

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 Japanese Patent Laid-Open No. Hei 6-75372, Japanese Patent Laid-Open No. Hei 6-75373, etc.), 2 , 2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5, 5'-tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. Sho 48-38403, Japanese Patent An imidazole compound in which a phenyl group at the 4,4', 5, 5'-position is substituted with an alkoxycarbonyl group is disclosed in JP-A-62-174204 (for example, Japanese Patent Laid-Open Publication No. Hei 07-010913, etc.). Among them, preferred are compounds represented by the following formulas and mixtures thereof.

[化38]

As other polymerization initiators, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-benzene Benzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)benzophenone, 2, a benzophenone compound such as 4,6-trimethylbenzophenone; a quinone compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine, camphorquinone; 10-butyl-2-chloroacridone; Benzene oxime, methyl phenylglyoxylate, titanium titanate compound, and the like. These are preferably used in combination with a polymerization initiation aid (particularly an amine polymerization initiation aid) to be described later.

Examples of the polymerization initiator which generates an acid include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylhydrazine hexafluoroantimonate, and 4-ethyloxiranium p-toluenesulfonate. Phenyl dimethyl hydrazine, hexafluoroantimonic acid 4-ethenyloxyphenyl methyl benzyl hydrazine, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium hexafluoroantimonate, diphenyl p-toluene sulfonate An anthracene salt such as hydrazine or diphenylphosphonium hexafluoroantimonate, or a nitrobenzyl tosylate or a benzoin tosylate.

The polymerization initiator (D) is preferably a polymerization initiator which produces a living radical, more preferably contains an alkylbenzene compound selected from three, At least one of the group consisting of the compound, the fluorenylphosphine oxide compound, the O-mercapto fluorene compound, and the biimidazole compound further preferably contains an O-fluorenyl hydrazine compound.

The content of the polymerization initiator (D) is usually 0.1 to 40 parts by mass, preferably 0.1 to 30 parts by mass, more preferably 100 parts by mass based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). It is 1 to 30 parts by mass, preferably 1 to 20 parts by mass.

<Polymerization starter>

The polymerization initiation aid is used to promote the initiation of polymerization under the action of the polymerization initiator (D). A polymerized compound or sensitizer of the polymerizable compound (C). In the case where the colored resin composition of the present invention contains a polymerization initiator, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiation aid include an amine polymerization initiation aid, an alkoxy fluorene polymerization initiation aid, and 9-oxosulfuric acid. It is a polymerization start aid and a carboxylic acid polymerization start aid.

Examples of the amine-based polymerization initiator include alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate and 4-dimethylaminobenzene. Aminobenzoic acid, ethyl 4-dimethylaminobenzoate, isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate Ester; N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michlerone), 4,4'-bis(diethylamino) a benzophenone and a 4,4'-bis(ethylmethylamino)benzophenone, wherein an alkyl group such as 4,4'-bis(diethylamino)benzophenone is preferred. Aminobenzophenone. Among them, an alkylaminobenzophenone is preferred, and 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

Examples of the alkoxy oxime-based polymerization initiator include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, and 9,10-diethoxyanthracene. 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

9-oxosulfur As a polymerization starter, it can be exemplified by 2-isopropyl-9-oxosulfur 4-isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro 9-oxosulfur And 1-chloro-4-propoxy-9-oxosulfur .

Examples of the carboxylic acid-based polymerization initiator include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, and dimethylphenyl group. Thioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid , naphthylthioacetic acid, N-naphthylglycine, and naphthyloxyacetic acid.

When the polymerization initiator is used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 100 to 30 parts by mass, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). It is 1 to 20 parts by mass. When the content of the polymerization initiation aid is within this range, the coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>

The solvent (E) is not limited, and the solvent which is usually used in the field may be used singly or in combination of two or more kinds. Specific examples thereof include an ester solvent (a solvent containing -COO- in the molecule but not containing -O-), an ether solvent (a solvent containing -O- in the molecule but not containing -COO-), and an ether ester solvent. (a solvent containing -COO- and -O- in the molecule), a ketone solvent (a solvent containing -CO- in the molecule but not containing -COO-), an alcohol solvent (containing OH in the molecule, but not containing -O-, - a solvent of -CO- and -COO-), an aromatic hydrocarbon solvent, a guanamine solvent, and dimethyl hydrazine.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclohexane Alcohol acetate and γ-butyrolactone.

Examples of the ether solvent 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, and two. Ethylene 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-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether and Methyl anisole.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethoxygen Ethyl 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 Ether acetate.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone and isophorone.

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

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

The guanamine solvent may, for example, be N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone.

These solvents may be used in combination of two or more.

Among the above solvents, in terms of coatability and drying property, an organic solvent having a boiling point of 1 atm of 120 ° C or more and 210 ° C or less is preferable. Among them, preferred are 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-di Methylformamide and N-methylpyrrolidone, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, acetic acid 3-methoxybutyl ester, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N,N-dimethylformamide and N-methylpyrrolidone.

The content of the solvent (E) is usually 70 to 95% by mass, preferably 75 to 92% by mass, and more preferably 75 to 90% by mass based on the total amount of the colored resin composition. When the content of the solvent (E) is in the above range, the flatness at the time of coating becomes good, and the color density is not insufficient when the color filter is formed. Therefore, the display characteristics tend to be good.

<leveling agent>

Examples of the leveling agent include a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

The polyoxo-based surfactant is exemplified by a surfactant having a decane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (Dow Corning Toray), 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 (manufactured by Momentive Performance Materials Japan Co., Ltd.).

The fluorine-based surfactant is exemplified by a surfactant having a fluorocarbon chain in the molecule. Specific examples include Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, and MEGAFAC F554. MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (made by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Institute of Precision Chemistry).

Examples of the polyfluorene-based surfactant having a fluorine atom include a surfactant having a decane bond and a fluorocarbon chain in the molecule. Specific examples include MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, and MEGAFAC F443 (manufactured by DIC).

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

<Other ingredients>

The colored resin composition of the present invention may optionally contain additives such as a filler, other polymer compound, adhesion promoter, antioxidant, light stabilizer, chain transfer agent, and the like as known in the art.

<Method for Producing Colored Resin Composition>

The colored resin composition of the present invention can be, for example, a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and optionally a leveling agent. The polymerization starting assistant and other components are prepared by mixing. In addition to the colorant (A), a pigment or a dye may be further mixed. The pigment is preferably mixed with a part or all of the solvent (E) in advance, and is dispersed in a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less, and is used in the form of a pigment dispersion liquid. At this time, part or all of the above-mentioned pigment dispersant and resin (B) may be blended as needed.

With respect to the compound (I), it is preferred to prepare a solution by partially dissolving it in part or all of the solvent (E). Further, it is preferred to filter the solution by a filter having a pore diameter of about 0.01 to 1 μm.

Preferably, the mixed colored resin composition is filtered by a filter having a pore diameter of about 0.01 to 10 μm.

<Method of Manufacturing Color Filter>

Examples of the method for producing a colored pattern from the colored resin composition of the present invention include a photolithography method, an inkjet method, a printing method, and the like. Among them, photolithography is preferred. Light lithography The method is a method in which a colored resin composition is applied onto a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask to be developed. In the photolithography method, a colored coating film which is a cured product of the coloring composition layer can be formed by not using a photomask during exposure and/or without developing. The colored pattern or colored coating film thus formed is the color filter of the present invention.

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

As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, or soda lime glass coated with cerium oxide, or polycarbonate, polymethyl methacrylate or polyterephthalic acid can be used. A resin plate such as ethylene glycol or the like, and an aluminum, silver, silver/copper/palladium alloy film or the like is formed on the substrate. Other color filter layers, resin layers, transistors, circuits, and the like may also be formed on the substrates.

The formation of pixels of various colors by photolithography can be carried out under known or conventional devices or conditions. For example, it can be produced as follows.

First, a colored resin composition is applied onto a substrate, and dried by heating (prebaking) and/or drying under reduced pressure, thereby removing volatile components such as a solvent and drying them, thereby obtaining a smooth colored composition layer. Examples of the coating method include a spin coating method, a slit coating method, and a slit + spin coating method. The temperature at the time of heat drying is preferably from 30 to 120 ° C, more preferably from 50 to 110 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes. In the case of drying under reduced pressure, it is preferably carried out at a temperature of from 50 to 150 Pa at a temperature ranging from 20 to 25 °C. The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected depending on the target film thickness of the color filter.

Then, the colored composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the reticle is not particularly limited, and a pattern corresponding to the intended use can be used. As the light source used for the exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, it is also possible to use a filter that cuts off the wavelength region for light that does not reach 350 nm. The cut-off, or selective use of a band pass filter that draws the wavelength regions is used for light near 436 nm, near 408 nm, and near 365 nm. Specific examples of the light source include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp. In order to uniformly illuminate the entire exposed surface with parallel rays or to accurately align the reticle with the substrate on which the colored composition layer is formed, it is preferred to use an exposure apparatus such as a reticle alignment machine and a stepper. . The colored composition layer after the exposure is brought into contact with the developing solution to develop, thereby forming a colored pattern on the substrate. The unexposed portion of the colored composition layer is dissolved in the developer by development to remove it. As the developer, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferred. The concentration of the basic compound is preferably from 0.01 to 10% by mass, more preferably from 0.02 to 5% by mass. The developer may also contain a surfactant. The developing method may be any of a liquid coating method, a dipping method, and a spraying method. Further, the substrate can be tilted at an arbitrary angle during development. It is preferred to carry out water washing after development.

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

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

[Examples]

Next, the present invention will be more specifically described by way of examples. In the examples, "%" and "parts" mean mass% and parts by mass unless otherwise stated.

In the following synthesis examples, the structure of the compound was carried out by NMR (JMM-ECA-500; manufactured by JEOL Ltd.) or mass spectrometry (LC; Model 1200 manufactured by Agilent, MASS; LC/MSD 6130 manufactured by Agilent). confirm.

The weight average molecular weight (Mw) and the number average molecular weight of the resin in terms of polystyrene The measurement of (Mn) was carried out by the GPC method under the following conditions.

Device: HLC-8120GPC (manufactured by Tosoh)

Column: TSK-GELG2000HXL

Column temperature: 40 ° C

Solvent: THF

Flow rate: 1.0mL/min

Solid content concentration of the solution to be tested: 0.001 to 0.01% by mass

Injection volume: 50μL

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh)

The ratio (Mw/Mn) of the weight average molecular weight to the number average molecular weight in terms of polystyrene obtained above was defined as a molecular weight distribution.

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 dropped into a mixture of 750 parts of ice and 750 parts of water. During the dropwise addition, the temperature of the mixture of ice and water to which the above mixture was added was maintained at 10 °C. A suction filtration was carried out to obtain an insoluble matter as a residue. To the residue, 1000 parts of water at 10 ° C was added, and the temperature of the mixture was kept at 10 ° C while stirring, and suction filtration was carried out to obtain an insoluble matter as a residue. 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. Thereafter, the mixture was stirred at 40 ° C for 1 hour. The mixture was cooled to room temperature, and 2,200 parts of chloroform and 1,500 parts of a 2.5% aqueous sodium hydroxide solution were added and stirred, and then allowed to stand. The chloroform solution layer was extracted, and 1500 parts of a 10% aqueous acetic acid solution was added thereto, and the mixture was stirred, and then allowed to stand. The chloroform solution layer was extracted, dried with magnesium sulfate, and filtered. Filtrate After the solvent was distilled off by a rotary evaporator, it was dried under reduced pressure at 60 ° C to obtain 12.0 parts of the compound of formula (I-96).

<Identification of the compound represented by formula (I-96)>

(mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 488

Exact Mass: 487

Example 2

1.03 parts of the compound represented by the above formula (I-96), 0.238 parts of succinic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.0370 A mixture of 35.0 parts of 1-methyl-2-pyrrolidone (manufactured by Nacalai Tesque Co., Ltd.) was mixed, and stirred at 70 ° C for 2.5 hours. 1.07 parts of succinic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.287 parts of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the mixture, and the mixture was stirred at 70 ° C for 18 hours. To the mixture, 300 parts of 1N hydrochloric acid and 444 parts of chloroform were added and stirred, and the mixture was allowed to stand. The chloroform solution layer was extracted, 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 with magnesium sulfate and filtered. After the solvent was distilled off by a rotary evaporator to remove the solvent, the obtained residue was added to 200 parts of water. After adding 444 parts of chloroform to the mixture, the mixture was stirred and allowed to stand. The chloroform solution layer was extracted, dried with magnesium sulfate, and filtered. After the solvent was distilled off by a rotary evaporator, the solvent was dried at 60 ° C under reduced pressure. dry. To the obtained residue, 5.00 parts of N,N-dimethylformamide was added and stirred, and then dropped into 200 parts of an 18% aqueous sodium chloride solution. After adding 444 parts of chloroform to the mixture, the mixture was stirred and allowed to stand. The chloroform solution layer was extracted, dried with magnesium sulfate, and filtered. The solvent was distilled off using a rotary evaporator to remove the solvent. To the obtained residue, 5.06 parts of N,N-dimethylformamide was added and stirred, and then dropped into 300 parts of an 18% aqueous sodium chloride solution. A suction filtration was carried out to obtain an insoluble matter as a residue. The residue was dried under reduced pressure at 60 ° C to obtain 1.21 parts of the compound of formula (I-117).

<Compound represented by formula (I-117)>

(mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 588

Accurate quality: 587

Example 3

1.07 parts of the compound represented by the above formula (I-96), 3.28 parts of phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), and 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.556 parts and 37.0 parts of 1-methyl-2-pyrrolidone (manufactured by Nacalai Tesque Co., Ltd.) were mixed, and stirred at 100 ° C for 17.5 hours. To the mixture, 1.68 parts of phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.277 parts of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 100 ° C for 4 hours. The mixture was stirred at 120 ° C for 4 hours. Time. The mixture was stirred at 100 ° C for 1 hour. The mixture was cooled to room temperature, and 444 parts of chloroform and 300 parts of 1N hydrochloric acid were added and stirred, and then allowed to stand. The chloroform solution layer was extracted, washed twice with 300 parts of 1N hydrochloric acid, washed three times with 300 parts of a 15% sodium carbonate aqueous solution, and washed once with 300 parts of a 10% aqueous acetic acid solution. The chloroform solution layer was dried with magnesium sulfate and filtered. The solvent was distilled off by a rotary evaporator, and then dried under reduced pressure at 60 °C. To the obtained residue, 10.6 parts of acetone was added and stirred, and then dropped into a mixture of 240 parts of water and 60 parts of methanol. To the mixture, 888 parts of chloroform was added and stirred, and then allowed to stand. The chloroform solution layer was extracted, dried with magnesium sulfate, and filtered. The solvent was distilled off using a rotary evaporator to remove the solvent. To the obtained residue, 22.3 parts of N,N-dimethylformamide was added and stirred, and then dropped into 610 parts of an 18% aqueous sodium chloride solution. A suction filtration was carried out to obtain an insoluble matter as a residue. The residue was dried under reduced pressure at 60 ° C to obtain 1.55 parts of the compound of formula (I-118).

<Identification of the compound represented by formula (I-118)>

(mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 636

Accurate quality: 635

Example 4

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

<Identification of the compound represented by the formula (I-119)>

(mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 680

Accurate quality: 679

<Identification of the compound represented by formula (I-120)>

(mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 680

Accurate quality: 679

Example 5

45.4 parts of 3-amino-4-hydroxybenzenesulfonic acid hydrate (manufactured by Tokyo Chemical Industry Co., Ltd.), 9.50 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 4-(diethylamino) willow 44.1 parts of aldehyde (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.) were mixed at 125 Stir at ° C for 2 hours.

To the mixture, 9.00 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.), and ethyl cyanoacetate (Tokyo Chemical Co., Ltd.) were mixed. 25.8 parts of 15.8 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 125 ° C for 12 hours.

After cooling the mixture to room temperature, suction filtration was carried out to obtain a solid form as a residue. Things. 967 parts of N,N-dimethylformamide was added to the residue, and the mixture was stirred at 90 ° C for 2 hours. The mixture was subjected to suction filtration while maintaining the mixture at 80 ° C to obtain a solid matter as a residue of the suction filtration. 126 parts of N,N-dimethylformamide was added to the residue, and suction filtration was carried out to obtain a solid matter as a residue.

967 parts of N,N-dimethylformamide was added to the residue, and the mixture was stirred at 90 ° C for 4 hours. The mixture was stirred at room temperature for 12 hours, and suction-filtered to obtain a solid material as a residue. 126 parts of N,N-dimethylformamide was added to the residue, and suction filtration was carried out to obtain a solid matter as a residue.

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

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

<Identification of the compound represented by the formula (1PAT)>

^{1 H-NMR (500MHz, 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 1,4-two 21 parts of the alkane were mixed, and while stirring the mixture, 3.1 parts of phosphorus oxychloride was added dropwise at room temperature. Add 1,4-two to the mixture 10 parts of alkane were stirred at 70 ° C for 3 hours. To the mixture, 3.1 parts of phosphorus oxychloride and 0.94 parts of N,N-dimethylformamide were added, and the mixture was stirred at 70 ° C for 1 hour. The mixture was allowed to stand to cool to room temperature. A suction filtration was carried out to obtain an insoluble matter as a residue. The residue was washed with 16 parts of acetonitrile and air-dried. A residue of 5.6 parts was obtained.

2.1 parts of the residue and 1,4-two The mixture of 5.2 parts of alkane was mixed. The mixture was stirred while cooling with a water bath, and 0.37 parts 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. A suction filtration was carried out to obtain an insoluble matter as a residue. The residue was dissolved in a mixture of 24 parts of N,N-dimethylformamide and 20 parts of methanol. The solution was distilled off using a rotary evaporator to remove the solvent. The obtained residue was purified by column chromatography. 16 parts of hexane was added to the obtained crystals and stirred. The mixture was subjected to suction filtration, and the obtained residue was air-dried to obtain 1.3 parts of the compound represented by the formula (I-10-1).

<Identification of the compound represented by formula (I-10-1)>

(mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 472

Accurate quality: 471

Example 6

4.7 parts of the compound represented by the formula (I-10-1), trimellitic anhydride (Tokyo Chemical Industry) (manufactured by the company) 9.6 parts, 3.4 parts of 4-dimethylaminopyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 51 parts of 1-methyl-2-pyrrolidone (manufactured by Nacalai Tesque Co., Ltd.) were mixed. The mixture was stirred at 100 ° C for 1 hour under a nitrogen atmosphere.

After the mixture was allowed to stand to cool to room temperature, it was filtered. After 90 parts of ethyl acetate and 160 parts of 10% hydrochloric acid were added to the filtrate and stirred, a layer of an ethyl acetate solution was extracted. To the ethyl acetate solution, 160 parts of 10% hydrochloric acid was added and stirred, and the mixture was allowed to stand, and then a layer of an ethyl acetate solution was extracted. To the ethyl acetate solution, 120 parts of a 15% aqueous sodium carbonate solution was added and stirred, and the mixture was allowed to stand, and then the aqueous layer was extracted. 90 parts of ethyl acetate was added to the aqueous solution, and the mixture was stirred while cooling with an ice bath, and 35% hydrochloric acid was added thereto so that the pH of the aqueous layer layer did not reach 1. The mixture was allowed to stand, and a layer of an ethyl acetate solution was extracted. After 150 parts of a 10% aqueous acetic acid solution was added to the ethyl acetate solution and stirred, the mixture was allowed to stand, and an ethyl acetate solution layer was extracted. The ethyl acetate solution was dried over magnesium sulfate and filtered. The solvent was distilled off using a rotary evaporator to remove the solvent. This residue was purified by column chromatography to obtain 4.9 parts of a mixture of a compound represented by formula (I-33-1) and a compound represented by formula (I-34-1).

[化47]

<Identification of the compound represented by formula (I-33-1)>

(mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 664

Accurate quality: 663

<Identification of the compound represented by formula (I-34-1)>

(mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 664

Accurate quality: 663

Synthesis Example 1

After introducing an appropriate amount of nitrogen into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to obtain a nitrogen atmosphere, 100 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 ° C while stirring. Then, 19 parts of methacrylic acid, acrylic acid {3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl} ester was added dropwise to the flask over a period of about 5 hours using a drip pump. a mixture of acrylic acid {3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl} ester (containing 50:50 by molar ratio) of 171 parts dissolved in propylene glycol monomethyl ether 40 parts of the obtained solution of the acid ester. On the other hand, using another drip pump, the mixture was sprayed into the flask for about 5 hours to dissolve 26 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in propylene glycol monomethyl ether. 120 parts of the obtained solution of acetate. After completion of the dropwise addition of the polymerization initiator, it was kept at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin B1) 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 of 53 mgKOH/g in terms of solid content.

[Measurement of film thickness]

The film thickness was measured using DEKTAK3 (manufactured by Nippon Vacuum Technology Co., Ltd.).

[Preparation of Sublimation Test Resin Composition (SJS)]

The following components were mixed to obtain a sublimation test resin composition (SJS).

Resin: methacrylic acid/benzyl methacrylate (Morby: 30/70) copolymer (manufactured by Tiangang Chemical Industry Co., Ltd., average molecular weight 10700, acid value 70 mgKOH/g) 33.8% propylene glycol monomethyl ether acetate 40 parts of ester solution; polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 5.8 parts; polymerization initiator: N-benzylideneoxy-1-(4) -Phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF JAPAN) 0.58 parts; leveling agent: polyether modified polyoxo (Toray Silicone SH8400) ; Dow Corning Toray (manufactured by the company) 0.010 parts; solvent: propylene glycol monomethyl ether 47 parts; solvent: propylene glycol monomethyl ether acetate 6.8 parts.

[Formation of resin coating film (SJSM) for sublimation test]

The above-mentioned sublimation test resin composition (SJS) was applied onto a glass substrate (EAGLE XG; manufactured by Corning Co., Ltd.) of 2 inches square by a spin coating method, and volatile components were obtained at 100 ° C for 3 minutes. Volatile. After cooling, light exposure was performed using an exposure machine (TME-150RSK; manufactured by TOPCON) at an exposure amount of 150 mJ/cm ² (365 nm basis) in an atmospheric environment. The film was heated at 220 ° C for 2 hours in an oven to form a resin coating film (SJSM) for sublimation test (film thickness: 2.2 μm).

Example 7

The following components were mixed to obtain a colored resin composition.

Coloring agent (A): 14 parts of the compound represented by the formula (I-96); resin (B): resin (B1) (in terms of solid content) 170 parts; solvent (E): propylene glycol monomethyl ether acetate 220 A solvent (E): 600 parts of N,N-dimethylformamide; and a surfactant: 0.063 parts of a polyether modified polysiloxane (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.).

Example 8

The following components were mixed to obtain a colored resin composition.

Coloring agent (A): 20 parts of the compound represented by the formula (I-117); resin (B): resin (B1) (in terms of solid content) 160 parts; solvent (E): propylene glycol monomethyl ether acetate 210 A solvent (E): 610 parts of N,N-dimethylformamide; and a surfactant: 0.063 parts of a polyether modified polysiloxane (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.).

Example 9

The following components were mixed to obtain a colored resin composition.

Coloring agent (A): 22 parts of the compound represented by the formula (I-118); resin (B): resin (B1) (in terms of solid content) 160 parts; solvent (E): propylene glycol monomethyl ether acetate 210 A solvent (E): 610 parts of N,N-dimethylformamide; and a surfactant: 0.063 parts of a polyether modified polysiloxane (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.).

Comparative example 1

The following components were mixed to obtain a colored resin composition.

Colorant (A): 611 parts of coumarin; resin (B): resin (B1) (converted solid content) 170 parts; solvent (E): propylene glycol monomethyl ether acetate 190 parts; solvent (E): 630 parts of N,N-dimethylformamide; and surfactant: 0.063 parts of polyether modified polyoxyxide oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.).

[sublimation evaluation]

Example 10

The colored resin composition obtained in Example 7 was applied onto a 2 inch square glass substrate (EAGLE XG; manufactured by Corning Co., Ltd.) by spin coating, and then prebaked at 100 ° C for 3 minutes to form a pre-baked resin composition. A layer of the resin composition is colored. The film thickness was measured using DEKTAK3 (manufactured by Nippon Vacuum Technology Co., Ltd.). The colored coating film was placed in a state of being separated from the above-mentioned sublimation test resin coating film (SJSM) at a distance of 70 μm, and baked at 220 ° C for 40 minutes. The color difference (ΔEab*) of the resin coating film (SJSM) for sublimation test before and after heating was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). If When the color difference (?Eab*) is 5.0 or more, it means that the coloring agent has sublimation property. The results are shown in Table 9. In Table 9, ○ indicates that the colorant does not have sublimation property, and × indicates that the colorant has sublimation property.

Example 11

The sublimation property evaluation was carried out in the same manner as in Example 10 except that the colored resin composition obtained in Example 7 was replaced with the colored resin composition obtained in Example 8. The results are shown in Table 9.

Example 12

Sublimation evaluation was performed in the same manner as in Example 10 except that the colored resin composition obtained in Example 7 was replaced with the colored resin composition obtained in Example 9. The results are shown in Table 9.

Comparative example 2

Sublimation evaluation was performed in the same manner as in Example 10 except that the colored resin composition obtained in Example 7 was replaced with the colored resin composition obtained in Comparative Example 1. The results are shown in Table 9.

[Preparation of Colored Resin Composition]

Example 13

The following components were mixed to obtain a colored resin composition.

Colorant (A): C.I. Pigment Green 7 (pigment) 27 parts,

12 parts of acrylic pigment dispersant, resin (B): resin B1 (in terms of solid content) 9.5 parts, and solvent (E): 180 parts of propylene glycol monomethyl ether acetate were mixed, and the pigment was sufficiently made using a bead mill a dispersion of the pigment; a coloring agent (A): 3.0 parts of the compound represented by the formula (I-118); a resin (B): a resin B1 (in terms of solid content) 40 parts; a polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 49 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiobenzene) Octyl-1-keto-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 9.8 parts; solvent (E): propylene glycol monomethyl ether acetate 670 And leveling agent (F): Polyether modified polyoxyxide oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.) 0.15 parts.

Example 14

A colored resin composition was obtained in the same manner as in Example 13 except that C.I. Pigment Green 7 (pigment) of the colorant (A) was replaced with C.I. Pigment Green 36 (pigment).

Example 15

A colored resin composition was obtained in the same manner as in Example 13 except that C.I. Pigment Green 7 (pigment) of the colorant (A) was replaced with C.I. Pigment Green 58 (pigment).

Example 16

[Production of coloring patterns]

The colored resin composition obtained in Example 13 was applied onto a 2 inch square glass substrate (EAGLE XG; manufactured by Corning) by a spin coating method, and then prebaked at 100 ° C for 3 minutes to form a pre-baked resin composition. Coloring the composition layer. After cooling, the distance between the substrate on which the colored composition layer was formed and the mask made of quartz glass was set to 200 μm, and the exposure machine (TME-150RSK; manufactured by TOPCON) was used in an atmosphere of 80 mJ/cm ² . The exposure amount (365 nm reference) was exposed. Further, as the photomask, a pattern in which a line and a gap of 100 μm were formed was used. The exposed coloring composition layer was 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 developed, and washed with water.

The colored coating film was baked at 230 ° C for 30 minutes, thereby obtaining a colored pattern.

Example 17

A colored pattern was obtained in the same manner as in Example 16 except that the colored resin composition obtained in Example 13 was replaced with the colored resin composition obtained in Example 14.

Example 18

A colored pattern was obtained in the same manner as in Example 16 except that the colored resin composition obtained in Example 13 was replaced with the colored resin composition obtained in Example 15.

[Preparation of Colored Resin Composition]

Example 19

The compound represented by the formula (I-117) is replaced with a mixture of the compound represented by the formula (I-119) obtained in the embodiment 4 and the compound represented by the formula (I-120), and Example 8 was carried out in the same manner to obtain a colored resin composition.

Example 20

Substituting the compound represented by the formula (I-117) with the formula (I-10-1) obtained in the example 5 Other than the above, the compound shown was carried out in the same manner as in Example 8 to obtain a colored resin composition.

Example 21

The compound represented by the formula (I-117) is replaced by a mixture of the compound represented by the formula (I-33-1) obtained in the example 6 and the compound represented by the formula (I-34-1), and It was carried out in the same manner as in Example 8 to obtain a colored resin composition.

[sublimation evaluation]

Example 22

The sublimation property evaluation was carried out in the same manner as in Example 10 except that the colored resin composition obtained in Example 7 was replaced with the colored resin composition obtained in Example 19. The results are shown in Table 10.

Example 23

The sublimation property evaluation was carried out in the same manner as in Example 10 except that the colored resin composition obtained in Example 7 was replaced with the colored resin composition obtained in Example 20. The results are shown in Table 10.

Example 24

The sublimation property was evaluated in the same manner as in Example 10 except that the colored resin composition obtained in Example 7 was replaced with the colored resin composition obtained in Example 21. The results are shown in Table 10.

[Preparation of Colored Resin Composition]

Example 25

A colored resin composition was obtained in the same manner as in Example 13 except that C.I. Pigment Green 7 (pigment) of the colorant (A) was replaced with C.I. Pigment Green 59 (pigment).

Example 26

[Production of coloring patterns]

A colored pattern was obtained in the same manner as in Example 16 except that the colored resin composition obtained in Example 13 was replaced with the colored resin composition obtained in Example 25.

Example 27

In the same manner as in Example 3 except that phthalic anhydride was replaced with tetrachlorophthalic anhydride in the same manner as in Example 3, the compound represented by the formula (I-122) was obtained.

Example 28

In the same manner as in Example 6, except that the trimellitic anhydride was replaced with tetrachlorophthalic anhydride, the compound represented by the formula (I-36-1) was obtained.

Example 29

In the same manner as in Example 3, except that the phthalic anhydride was replaced with tetrafluorophthalic anhydride, the compound represented by the formula (I-121) was obtained.

Example 30

In the same manner as in Example 6, except that the trimellitic anhydride was replaced with tetrafluorophthalic anhydride, the compound represented by the formula (I-35-1) was obtained.

Example 31

In the same manner as in Example 5 except that 4-(diethylamino) salicylaldehyde was replaced by 4-(dioctylamino) sulphonaldehyde in Example 5, the formula (I) was obtained. -53-1) The compound represented.

Example 32

In the embodiment 6, the compound represented by the formula (I-10-1) is replaced with the compound represented by the formula (I-53-1), and the trimellitic anhydride is replaced with the phthalic acid, and The same procedure as in Example 6 was carried out to obtain a compound represented by the formula (I-75-1).

Based on the above results, it was confirmed that according to the present invention, it is possible to provide a colored resin composition capable of forming a color filter in which sublimation of a coloring agent is suppressed.

[Industrial availability]

According to the present invention, a compound which can be used as a coloring agent for a color filter can be obtained. The compound is easy to synthesize and can be produced without a dimerization step. A colored resin composition capable of forming a color filter in which sublimation of a coloring agent is suppressed can be provided, and the color filter is suitable for a display device such as a liquid crystal display device.

Claims (10)

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; and 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 or different from each other; L ¹ represents a divalent hydrocarbon group having 1 to 60 carbon atoms; and -CH = which constitutes the divalent hydrocarbon group may be Substituting -N=, -CH ₂ - constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N(R ³ )-, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the divalent hydrocarbon group may be Substituted as a halogen atom, a cyano group, a nitro group, an amine carbenyl group, an amine sulfonyl group, -SO ₃ M ³ , -CO ₂ M ³ , a hydroxyl group, a decyl group or an amine group; R ³ represents a hydrogen atom, carbon a monovalent hydrocarbon group of 1 to 20 or a group represented by the formula (z); the hydrogen atom contained in the monovalent hydrocarbon group may be substituted with a halogen atom, a hydroxyl group or a carboxyl group, and -CH ₂ - constituting the monovalent hydrocarbon group may be Substituted as a carbonyl group; when a plurality of R ³ are present, they may be the same or different from each other; In the formula (z), L ²² and L ³³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms; -CH= constituting the divalent hydrocarbon group may be substituted with -N=, and -CH ₂ constituting the divalent hydrocarbon group _; - may be substituted with 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 may be substituted with a halogen atom, a cyano group, a nitro group, an amine formamidine group a group, an amine sulfonyl group, -SO ₃ M ³ , -CO ₂ M ³ , a hydroxyl group, a methyl group or an amine group; M ¹ represents a hydrogen atom or an alkali metal atom; when a plurality of M ¹ are present, etc. may be the same or different from each other; substituents L ^1, -SO ^₃ M ₃ or -CO ₂ M ³ is hydrogen atom or L ²² L ³³ contained in the divalent hydrocarbon group of 2 ^represents a hydrogen atom or an alkali metal atom M contained in it; in In the case where a plurality of M ³ are present, they may be the same or different from each other; R ⁴⁴ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; and in the case where a plurality of R ⁴⁴ are present, they may be the same or different from each other ]. The compound of claim 1, wherein the above A is -SO ₂ -OL ^a -OM, -SO ₂ -NR ³ -L ^b -OM or -SO ₂ -NR ³ -L ² -OCO-L ³ -CO-OM Wherein R ³ and M each have the same meaning as defined above; L ^a and L ^b are each independently a divalent hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ - constituting the divalent hydrocarbon group may be substituted with oxygen. An atom or a carbonyl group; a hydrogen atom contained in the divalent hydrocarbon group may be substituted with a halogen atom or a carboxyl group; and L ² and L ³ each independently represent a divalent hydrocarbon group having 1 to 30 carbon atoms; and -CH = which may constitute the divalent hydrocarbon group; Substituted as -N=, -CH ₂ - constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N(R ⁵⁵ )-, a sulfonyl group or a carbonyl group, and a hydrogen atom contained in the divalent hydrocarbon group Can be substituted with a halogen atom, a cyano group, a nitro group, an amine carbaryl group, an amine sulfonyl group, -SO ₃ M ³ , -CO ₂ M ³ , a hydroxyl group, a decyl group or an amine group; M ³ represents the same as above Meaning; when there are a plurality of M ³ , they may be the same or different from each other; R ⁵⁵ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; in the case where a plurality of R ⁵⁵ are present, they are mutually Can be the same or different]. The compound of claim 2, wherein each of L ^a and L ^{b is} independently a phenyl, methylene, ethyl, methyl or ethyl propyl group. A compound according to claim 1, 2 or 3, which is represented by formula (II), [In the formula (II), n, X, R ¹ , R ² , L ² and L ³ each have the same meaning as defined above; R ³³ represents a hydrogen atom or -L ²² -OCO-L ³³ -CO ₂ M ² ; L ²² and L ³³ each have the same meaning as described above; M ² represents a hydrogen atom or an alkali metal atom; and in the case where a plurality of M ² are present, they may be the same or different from each other]. The compound of claim 1 or 4, wherein the L ²² is a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the above L ³³ is a divalent aliphatic hydrocarbon group or an aromatic hydrocarbon group which may be substituted by a carboxyl group or a halogen atom. The compound according to any one of claims 2 to 4, wherein the above L ² is a divalent saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the above L ³ is a divalent aliphatic hydrocarbon group or aromatic group which may be substituted by a carboxyl group or a halogen atom. A hydrocarbon group. The compound according to any one of claims 1 to 6, wherein each of R ¹ and R ^{2 is} independently a monovalent hydrocarbon group having 1 to 10 carbon atoms. A colored resin composition containing a coloring agent, a resin, a polymerizable compound, a polymerization initiator, and a solvent, which comprise the compound according to any one of claims 1 to 7. A color filter formed by the colored resin composition of claim 8. A liquid crystal display device comprising the color filter of claim 9.