JP6943558B2 - Color curable resin composition, color filter, and display device - Google Patents

Description

The present invention relates to a colored curable resin composition containing a xanthene compound.

Xanthene compounds are used as colorants for color filters contained in various display devices such as liquid crystal displays and solid-state image sensors. For example, Patent Document 1 describes a compound represented by the formula (A1).

Japanese Unexamined Patent Publication No. 2014-88558

When the above-mentioned compounds known conventionally are used, the heat resistance of the obtained color filter is not sufficiently satisfactory.

The present invention includes the following inventions.
[1] A color curable resin composition containing a xanthene compound (A-1), a resin (B), a polymerizable compound (C) and a polymerization initiator (D).
The xanthene compound (A-1) contains a cation (AXa) having a xanthene skeleton having a substituted or unsubstituted sulfamoyl group, at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and oxygen. It is a compound having an anion (AXb) containing as an essential element.
A colored curable resin composition in which the xanthene skeleton is a xanthene skeleton having a substituted or unsubstituted sulfamoyl group.
[2] The colored curable resin composition according to [1], wherein the cation (AXa) having a xanthene skeleton is a cation represented by the formula (I).

[In the formula (I), R ^{1a to} R ^4a may have a hydrogen atom and a substituent, and may have an aromatic hydrocarbon group or a substituent having 6 to 10 carbon atoms independently of each other. It represents a good saturated hydrocarbon group having 1 to 20 carbon atoms, and the methylene group (−CH ₂₋ ) contained in the saturated hydrocarbon group is −O−, −CO−, −NR ^11a −, −OCO−, −. It may be substituted with COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-, and R ^1a and R ^2a may be combined to form a ring containing a nitrogen atom, R. ^3a and R ^4a may be combined to form a ring containing a nitrogen atom. However, adjacent methylene groups are not substituted with the same substituent at the same time, and the terminal methylene group is not substituted. R ^6a and R ^7a independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ma represents an integer of 1-5. R ^9a and R ^10a represent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have hydrogen atoms or substituents independently of each other, and methylene groups (-CH _{2) contained in the saturated hydrocarbon groups.} -) is, -O -, - CO -, - NR 11a -, - OCO -, - COO -, - OCONH -, - NHCOO -, - CONH- or -NHCO- may be substituted by, R ^9a And R ^10a may be bonded to each other to form a 3- to 10-membered heterocycle containing a nitrogen atom. However, adjacent methylene groups are not substituted with the same substituent at the same time, and the terminal methylene group is not substituted. R ^11a represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]
[3] The colored curable resin composition according to [1] or [2], wherein the anion (AXb) is an anion of a heteropolyacid or an isopolyacid containing tungsten as an essential element.
[4] The colored curable resin composition according to any one of [1] to [3], wherein the anion (AXb) is any of a phosphotungstic acid anion, a siliceous tungstic acid anion, or a tungsten-based isopolyacid anion. thing.
[5] A color filter formed from the colored curable resin composition according to any one of [1] to [4].
[6] A display device including the color filter according to [5].

Since the color curable resin composition of the present invention contains a specific xanthene compound, it is possible to provide a color filter having excellent heat resistance.

The colored curable resin composition of the present invention contains a xanthene compound (A-1), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

<Colorant (A)>
The xanthene compound (A-1) in the present invention is an anion containing a cation having a xanthene skeleton (AXa), at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and oxygen as essential elements. It has (AXb), and the xanthene skeleton has a substituted or unsubstituted sulfamoyl group. By having a cation (AXa) having a xanthene skeleton and an anion (AXb), the heat resistance of the xanthene compound can be improved.

The cation (AXa) having a xanthene skeleton preferably has a substituted or unsubstituted sulfamoyl group, and more preferably a cation represented by the formula (I).

[In formula (I),
R ^{1a to} R ^4a have a hydrogen atom, an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, or a substituent having 1 to 20 carbon atoms, which may have a substituent. refers to a saturated hydrocarbon group, a methylene group contained in the saturated hydrocarbon group (-CH ₂ -) is, -O -, - CO -, - NR 11a -, - OCO -, - COO -, - OCONH-, It may be substituted with −NHCOO−, −CONH− or −NHCO−, R ^1a and R ^2a may be combined to form a ring containing a nitrogen atom, and R ^3a and R ^4a may be together. May form a ring containing a nitrogen atom. However, adjacent methylene groups are not substituted with the same substituent at the same time, and the terminal methylene group is not substituted.
R ^6a and R ^7a independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
ma represents an integer of 1-5.
R ^9a and R ^10a represent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have hydrogen atoms or substituents independently of each other, and methylene groups (-CH _{2) contained in the saturated hydrocarbon groups.} -) is, -O -, - CO -, - NR 11a -, - OCO -, - COO -, - OCONH -, - NHCOO -, - CONH- or -NHCO- may be substituted by, R ^9a And R ^10a may be bonded to each other to form a 3- to 10-membered heterocycle containing a nitrogen atom. However, adjacent methylene groups are not substituted with the same substituent at the same time, and the terminal methylene group is not substituted.
R ^11a represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]

In the formula (I), -SO ₃ ^- if there is, the number is one.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{1a to} R ^4a and R ^{9a to} R ^11a include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. , Nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group and other linear alkyl groups; isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and other branched chain alkyl groups; cyclopropyl group , Cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, tricyclodecyl group and other alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms.
Methylene group contained in the saturated hydrocarbon group (-CH ₂ -) is, -O -, - CO -, - NR 11a -, - OCO -, - COO -, - OCONH -, - NHCOO -, - CONH- Alternatively, it may be replaced with −NHCO−. However, adjacent methylene groups are not substituted with the same substituent at the same time, and the terminal methylene group is not substituted.

Examples of the group in which the methylene group (−CH ₂₋ ) contained in the saturated hydrocarbon group is substituted with −O− include the following (* indicates a bond).

Examples of the group in which the methylene group (−CH ₂₋ ) contained in the saturated hydrocarbon group is substituted with −CO− include the following (* indicates a bond).

Examples of the group in which the methylene group (−CH ₂₋ ) ^{contained in the saturated hydrocarbon group is substituted with −NR 11a} − include the following (* indicates a bond).

Examples of the group in which the methylene group (-CH _2- ) contained in the saturated hydrocarbon group is substituted with -OCO- include the following (* indicates a bond).

Examples of the group in which the methylene group (−CH ₂₋ ) contained in the saturated hydrocarbon group is substituted with −COO− include the following (* indicates a bond).

Examples of the group in which the methylene group (-CH _2- ) contained in the saturated hydrocarbon group is substituted with -OCONH- include the following (* indicates a bond).

Examples of the group in which the methylene group (-CH _2- ) contained in the saturated hydrocarbon group is substituted with -NHCOO- include the following (* indicates a bond).

Examples of the group in which the methylene group (-CH _2- ) contained in the saturated hydrocarbon group is substituted with -CONH- include the following (* indicates a bond).

Examples of the group in which the methylene group (-CH _2- ) contained in the saturated hydrocarbon group is substituted with -NHCO- include the following (* indicates a bond).

The saturated hydrocarbon groups in R ^{1a to} R ^4a may have a substituent, and examples of the substituent include an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms that the saturated hydrocarbon groups of R ^{1a to} R ^4a may have are exemplified as the aromatic hydrocarbon group having 6 to 10 carbon atoms in ^{R 1a to} R ^4a. The same group as the group to be used can be mentioned.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The saturated hydrocarbon group in R ^9a and R ^10a may have a substituent, and the substituent includes, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, or a hydroxy group. Can be mentioned.

Examples of the ring formed by R ^1a and R ^2a together and the ring formed by R ^3a and R ^{4a together include the following.} In the formula, * represents a bond.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{1a to} R ^4a include a phenyl group, a toluyl group, a xsilyl group, a mesityl group, a propylphenyl group and a butylphenyl group.
The aromatic hydrocarbon group having 6 to 10 carbon atoms may have a substituent. The aromatic hydrocarbon group substituent which may have a halogen ^{atom, -R 8a, -OH, -OR 8a} , -SO 3 -, -SO 3 H, -SO 3 - Z +, - Examples thereof include CO ₂ H, -CO ₂ R ^8a , -SR ^8a , -SO ₂ R ^8a , -SO ₃ R ^8a and -SO ₂ NR ^12a R ^13a. Among them, as the _{^{substituent, -R 8a, -SO 3 -,}} -SO 3 H, -SO 3 - Z + and -SO ₂ NR ^12a R ^13a is _{^{preferably, -R 8a, -SO 3 - Z}} + And -SO ₂ NR ^12a R ^13a are more preferred. In this case, as −R ^8a , a saturated hydrocarbon group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 1 to 5 carbon atoms is further preferable. The -SO ₃ in this case ^- as Z ^{+ _{is, -SO 3 - N + (R}} 11a) 4 are preferred.
Z ⁺ represents ⁺ N (R ^11a ) ₄ , Na ⁺ or K ⁺ , and the four R ^11a may be the same or different.
R ^8a represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom.
R ^12a and R ^13a represent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have hydrogen atoms or substituents independently of each other, and methylene groups (-CH _{2) contained in the saturated hydrocarbon groups.} -) is, -O -, - CO -, - NR 11a -, - OCO -, - COO -, - OCONH -, - NHCOO -, - CONH- or -NHCO- may be substituted by, R ^12a And R ^13a may be bonded to each other to form a 3- to 10-membered heterocycle containing a nitrogen atom. However, adjacent methylene groups are not substituted with the same substituent at the same time, and the terminal methylene group is not substituted.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^8a , R ^12a and R ^13a include the same saturated hydrocarbon group having 1 to 20 carbon atoms represented by ^{R 1a to} R ^4a. ..
Saturated hydrocarbon groups having 1 to 20 carbon atoms represented by R ^12a and R ^13a may have a substituent, and the substituents include halogens such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Atoms or hydroxy groups can be mentioned.

Examples of −OR ^8a include alkyloxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and icosyloxy group. Can be mentioned.

Examples of -CO ₂ R ⁸ include alkyloxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, tert-butoxycarbonyl group, hexyloxycarbonyl group and icosyloxycarbonyl group.

Examples of −SR ^8a include alkyl sulfanyl groups such as methyl sulfanyl group, ethyl sulfanyl group, butyl sulfanyl group, hexyl sulfanyl group, decyl sulfanyl group and icosyl sulfanyl group.
Examples of −SO ₂ R ^8a include alkylsulfonyl groups such as methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, decylsulfonyl group and icosylsulfonyl group.
Examples of -SO ₃ R ^8a include alkyloxysulfonyl groups such as methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyloxysulfonyl group and icosyloxysulfonyl group.

-SO ₂ NR ^12a R ^13a includes, for example, a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butyl sulfamoyl group, N-tert-butyl sulfamoyl group, N-pentyl sulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3) -Methylbutyl) sulfamoyl group, N-cyclopentyl sulfamoyl group, N-hexyl sulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N- Heptyl sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octyl sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- N-1-substituted sulfamoyl groups such as (1,5-dimethylhexyl) sulfamoyl group and N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group and N, N-heptylmethylsulfamoyl Examples thereof include N, N-2 substituted sulfamoyl groups such as groups.

The ma is preferably 1 to 4, more preferably 1 or 2.

Examples of the alkyl group having 1 to 6 carbon atoms in R ^6a and R ^7a include those having 1 to 6 carbon atoms among the alkyl groups listed above.

R ^12a and R ^13a may represent a 3- to 10-membered nitrogen-containing heterocycle together with a nitrogen atom. Examples of the heterocycle include the following. In the formula, * represents a bond.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ^11a include a benzyl group, a phenylethyl group and a phenylbutyl group.

Z ⁺ is ^{preferably +} N (R ^11a ) ₄ , Na ⁺ or K ⁺ , and more preferably ⁺ N (R ^11a ) ₄ .
As the ⁺ N (R ^11a ) ₄ , ^{it is preferable that at least two of the four R 11a} are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ^11a is preferably 20 to 80, and more preferably 20 to 60.

Examples of the −SO ₂ NR ^9a R ^10a include groups similar to those exemplified as _{−SO 2} NR ^12a R ^13a. Further, as a 3- to 10-membered heterocycle containing a nitrogen atom in which ^{R 9a} and R ^{10a may be formed by bonding with each other, R 12a} and R ^13a may be formed together with a nitrogen atom. A ring similar to a good 3- to 10-membered nitrogen-containing heterocycle can be mentioned.

Among them, as R ^1a and R ^4a , a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent and an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent may be used. Is preferable, and an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent is more preferable. The ^{number of carbon atoms of the saturated hydrocarbon in R 1a} and R ^4a is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and having no substituent. Is preferable. The substituent of the aromatic hydrocarbon group is preferably ^{−R 8a.}
As R ^2a and R ^3a , saturated hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent are preferable. The ^{number of carbon atoms of the saturated hydrocarbon group in R 2a} and R ^3a is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and having no substituent. Is preferable.
As R ^6a and R ^7a , a hydrogen atom is preferable.
The ^{number of carbon atoms of the saturated hydrocarbon group in R 8a} is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
As R ^9a , R ^10a , R ^12a and R ^13a , a hydrogen atom and a saturated hydrocarbon group having 1 to 12 carbon atoms are preferable. Further, it is preferable that at least one of R ^9a and R ^10a is a saturated hydrocarbon group, more preferably both of R ^9a and R ^10a is a saturated hydrocarbon group. Further, it is preferable that at least one of R ^12a and R ^13a is a saturated hydrocarbon group, more preferably both R ^12a and R ^13a is a saturated hydrocarbon group.
As the −SO ₂ NR ^9a R ^10a and −SO ₂ NR ^12a R ^13a , an N-1-substituted sulfamoyl group and an N-2 substituted sulfamoyl group are preferable.
As R ^11a , a saturated hydrocarbon group having 1 to 20 carbon atoms is preferable.

As the cation having a xanthene skeleton (AXa), a cation having a xanthene skeleton represented by the formula (I-1) is preferable. The cation represented by the formula (I-1) may be a tautomer thereof.

[In formula (I-1),
R ^{1b to} R ^4b represent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have substituents independently of each other, and the methylene group (−CH ₂ −) contained in the saturated hydrocarbon group is , -O -, - CO -, - NR 11b -, - OCO -, - COO -, - OCONH -, - NHCOO -, - CONH- or -NHCO- may be substituted by, R ^1b and R ^2b May be combined to form a ring containing a nitrogen atom, and R ^3b and R ^4b may be combined to form a ring containing a nitrogen atom. However, adjacent methylene groups are not substituted with the same substituent at the same time, and the terminal methylene group is not substituted.
R ^6b and R ^7b independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
mb represents an integer from 0 to 5. When mb is 2 or more, a plurality of −SO ₂ NR ^9b R ^10b may be the same or different.
R ^9b and R ^10b represent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have hydrogen atoms or substituents independently of each other, and methylene groups (-CH _{2) contained in the saturated hydrocarbon groups.} -) is, -O -, - CO -, - NR 11b -, - OCO -, - COO -, - OCONH -, - NHCOO -, - CONH- or -NHCO- may be substituted by, R ^9b And R ^10b may be bonded to each other to form a 3- to 10-membered heterocycle containing a nitrogen atom. However, adjacent methylene groups are not substituted with the same substituent at the same time, and the terminal methylene group is not substituted.
R ^11b represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]

A preferred embodiment of R ^1b to R ^11b and mb, respectively, from the preferred embodiments of the R ^1a to R ^11a and ma, is selected within a range that does not exceed the concept of R ^1b to R ^11b and mb.

The cation having a xanthene skeleton (AXa) is preferably a cation having a xanthene skeleton represented by the formula (I-2). The cation represented by the formula (I-2) may be a tautomer thereof.

[In formula (I-2),
R ^1c and R ^4c independently represent an alkyl group having 1 to 4 carbon atoms, an alkyl sulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
p and q represent integers 0 to 5 independently of each other. When p is 2 or more, the plurality of R ^1c may be the same or different, and when q is 2 or more, the plurality of R ^4c may be the same or different.
R ^2c and R ^3c represent monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have hydrogen atoms and substituents independently of each other, and methylene groups contained in the saturated hydrocarbon groups (R 2c and R 3c). -CH ₂ -) is, -O -, - CO -, - NR 11c -, - OCO -, - COO -, - OCONH -, - NHCOO -, - CONH- or may be substituted by -NHCO- .. However, adjacent methylene groups are not substituted with the same substituent at the same time, and the terminal methylene group is not substituted.
R ^1c and R ^2c may be combined to form a ring containing a nitrogen atom, and R ^3c and R ^4c may be combined to form a ring containing a nitrogen atom.
R ^6c and R ^7c independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
mc represents an integer from 0 to 5. When mc is 2 or more, a plurality of −SO ₂ NR ^9c R ^10c may be the same or different.
R ^9c and R ^10c represent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have hydrogen atoms or substituents independently of each other, and methylene groups (-CH _{2) contained in the saturated hydrocarbon groups.} -) is, -O -, - CO -, - NR 11c -, - OCO -, - COO -, - OCONH -, - NHCOO -, - CONH- or -NHCO- may be substituted by, R ^9c And R ^10c may be bonded to each other to form a 3- to 10-membered heterocycle containing a nitrogen atom. However, adjacent methylene groups are not substituted with the same substituent at the same time, and the terminal methylene group is not substituted.
R ^11c represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]

Preferred embodiments of R ^{1c to} R ^4c , R ^{6c to} R ^7c , R ^{9c to} R ^11c and mc are contained in the aromatic hydrocarbon groups represented by ^{R 1a to} R ^11a , ma and R ^{1a, respectively.} From the preferred embodiments of the substituents which may be used, they are selected within a range not exceeding the concepts of ^{R 1c to} R ^4c , R ^{6c to} R ^7c , R ^{9c to} R ^{11c and mc.}

Examples of the cation (AXa) include a cation represented by the following formula (AXa-I). In Table 1, R ⁴⁰ represented as ^{R 2A} , R ^3A , and R ^10A represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and preferably a branched chain alkyl group having 6 to 12 carbon atoms. , And more preferably a 2-ethylhexyl group.

In Table 1, Me represents a methyl group, Et represents an ethyl group, Pr represents an n-propyl group, and iPr represents an isopropyl group. Ph1 to Ph10 mean a group represented by the following formula, and Hc1 to Hc4 are cases where R ^1A and R ^2A , R ^3A and R ^4A are combined to form a ring containing a nitrogen atom, respectively. The rings corresponding to each of Hc1 to Hc4 are represented by the following formulas.

Among them, as the cation (AXa), cations (AXa-1) to (AXa-4) and (AXa-27) to (AXa-30) are preferable.

The cation (AXa) can be produced, for example, by sulfonamide-forming the compound represented by the formula (II).

［式（ＩＩ）中、Ｒ^1a〜Ｒ^4a、Ｒ^6a〜Ｒ^7a及びｍａは、上記と同義である。］

[In formula (II), R ^{1a to} R ^4a , R ^{6a to} R ^7a, and ma are synonymous with the above. ]

The anion (AXb) used in combination with the cation (AXa) having a xanthene skeleton contains at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements, preferably tungsten. And oxygen are contained as essential elements. These anions are preferable from the viewpoint of heat resistance.
As the anion (AXb), an anion of a heteropolyacid or an isopolyacid containing tungsten as an essential element is preferable, and an anions of phosphotungsten acid, silicotungic acid and tungsten-based isopolyacid are more preferable.

Examples of anions of heteropolyacids and isopolyacids containing tungsten as essential elements include kegin-type phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ^3- and Dawson-type phosphotungstate ion α- [P ₂ W ₁₈ O. ₆₂ ] ^6- , β- [P ₂ W ₁₈ O ₆₂ ] ^6- , Kegin-type heteropolymetalate α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^4- , and other examples are [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ^{] 12-} , [NaP ₅ ]. W ₃₀ O ₁₁₀ ] ^14- , α- [SiW ₉ O ₃₄ ] ^10- , γ- [SiW ₁₀ O ₃₆ ] ^8- , α- [SiW ₁₁ O ₃₉ ] ^8- , β- [SiW ₁₁ O ₃₉ ] ^{8 -} , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- and mixtures thereof.

Further, an anion composed of oxygen and at least one element selected from the group consisting of silicon and phosphorus is also preferable.
Examples of the anion composed of oxygen and at least one element selected from the group consisting of silicon and phosphorus include SiO ₃ ^2- and PO ₄ ^3- .

Anion as the (AXb), Keggin phosphotungstic acid ion, phosphotungstic acid anions such as Dawson-type phosphotungstic acid ion; Keggin silicotungstic acid anions such as silicotungstic acid ion, [W ₁₀ O _32] ^4-, etc. Tungstic acid anion is preferred. Of these, phosphotungstic acid anion and tungsten-based isopolyacid anion are particularly preferable.

As the anion (AXb), an anion of a heteropolyacid and an isopolic acid containing tungsten as an essential element is more preferable, an anion of phosphotoxynic acid, an anion of silicotoxy acid and an anion of a tungsten-based isopolyacid are further preferable, and [PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , [SiW ₁₂ O ₄₀ ] ^4- and [W ₁₀ O ₃₂ ] ^4- are even more preferable, and [PW ₁₂ O ₄₀ ] ^3- and [P] ₂ W ₁₈ O ₆₂ ] ^6- is particularly preferred. From the viewpoint of heat resistance, it is preferable to use an anion of a heteropolyacid or an isopolyacid containing tungsten as an essential element.

As compound (AI),
Any three of the cations (AXa-1) to (AXa-52), preferably any of the cations (AXa-1) to (AXa-4) and (AXa-27) to (AXa-30). Combination of the three cations of the above and the anion α- [PW ₁₂ O ₄₀ ] ^3-,
Any of the six cations (AXa-1) to (AXa-52), preferably any of the cations (AXa-1) to (AXa-4) and (AXa-27) to (AXa-30). 6 cations and anion α- [P ₂ W ₁₈ O ₆₂ ] ^6-
Any of the four cations (AXa-1) to (AXa-52), preferably any of the cations (AXa-1) to (AXa-4) and (AXa-27) to (AXa-30). Examples thereof include a combination of the four cations of the above and anions α- [SiW ₁₂ O ₄₀ ] ^4- and [W ₁₀ O ₃₂ ] ^4-.

Specifically, it is preferably a compound (Xa) composed of the following cation (AXa) and anion (AXb).

The xanthene compound (A-1) can be produced, for example, by mixing the compound represented by the formula (III) and the alkali metal salt of the anion (Axb) in a solvent. Alkali metals include lithium, sodium and potassium.

[In formula (III), R ^{1a to} R ^4a , R ^{6a to} R ^7a , R ^{9a to} R ^10a and ma are synonymous with the above. ]

Solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, acetone, tetrahydrofuran, dioxane, water and chloroform. Can be mentioned.
The compound represented by the formula (III) can be produced by a known method.

In the present invention, a colored dispersion containing the xanthene compound (A-1) and a solvent may be prepared, and the obtained colored dispersion may be used in the colored curable resin composition. As the solvent used for the coloring dispersion, the same solvent as the solvent (E) described later can be used. Further, it is preferable to use a pigment dispersant as the coloring dispersion liquid, and if necessary, a part or all (preferably a part) of the resin (B) used in the coloring curable resin composition can be used. It may be included in advance.

The xanthene compound (A-1) may be contained alone as the colorant (A), but other dyes (A1) and pigments are used for color matching, that is, for adjusting the spectral characteristics. (P) may be included.

Examples of the dye (A1) include dyes such as oil-soluble dyes, acidic dyes, basic dyes, direct dyes, medium dyes, amine salts of acidic dyes and sulfonamide derivatives of acidic dyes, and examples thereof include Color Index (The Society). Examples thereof include compounds classified as dyes in of Dyers and Colorists (published by Colorists) and known dyes described in dyeing notes (color dyeing company). According to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acrydin dyes, styryl dyes, coumarin dyes, quinoline. Examples include dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferably used.

Specifically, C.I. I. Solvent Yellow 4 (Hereinafter, the description of CI Solvent Yellow is omitted and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99. , 162;
C. I. Solvent Red 45, 49, 125, 130, 218;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent Blue 4, 5, 37, 67, 70, 90;
C. I. Solvent Green 1, 4, 5, 7, 34, 35, etc. I. Solvent dye,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Violet 6B, 7, 9, 17, 19, 30, 102;
C. I. Acid Blue 1,7,9,15,18,22,29,42,59,60,62,70,72,74,82,83,86,87,90,92,93,100,102,103, 104, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;
C. I. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109 and the like. I. Acid dye,
C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C. I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like. I. Direct dye,
C. I. Disperse Yellow 54, 76, etc. I. Disperse dye,
C. I. Basic Red 1, 10;
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;
C. I. Basic Green 1; etc. I. Basic dye,
C. I. Reactive Yellow 2,76,116;
C. I. Reactive orange 16;
C. I. Reactive Red 36; etc. I. Reactive dye,
C. I. Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern tread 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43 , 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
C. I. Modant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modant Blue 1,2,3,7,9,12,13,15,16,19,20,21,22,26,30,31,39,40,41,43,44,49,53,61 , 74, 77, 83, 84;
C. I. Modant Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. I. Mordant dye,
C. I. Bat Green 1 etc. C.I. I. Vat dyes and the like can be mentioned.
Of these, blue dyes, violet dyes and red dyes are preferable.
These dyes may be used alone or in combination of two or more.

As the pigment (P), a known pigment can be used without particular limitation, and examples thereof include pigments classified as pigments by the Color Index (The Society of Dyers and Colorists Publishing).
Examples of the pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments;
C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments;
C. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments;
C. I. Pigment Green 7, 36, 58, 59 and other green pigments; and the like.

If necessary, the pigment is treated with a rosin, a surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a graft treatment on the pigment surface with a polymer compound or the like, and atomization by a sulfuric acid atomization method or the like. Treatment, cleaning treatment with an organic solvent, water, etc. for removing impurities, removal treatment of ionic impurities by an ion exchange method, or the like may be performed. It is preferable that the particle size of each pigment is uniform.

The pigment can be made into a pigment dispersion liquid in which the pigment dispersant is uniformly dispersed in the solution by carrying out the dispersion treatment by containing the pigment dispersant. The pigments may be individually dispersed or a plurality of types may be mixed and dispersed.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants may be used alone or in combination of two or more. Pigment dispersants include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solspers (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by BASF), and Ajinomoto Fine (Ajinomoto Fine). Examples thereof include Techno Co., Ltd. and Disperbyk (manufactured by Big Chemie).

The content of the xanthene compound (A-1) is usually 1% by mass or more and 100% by mass or less, preferably 10% by mass or more and 100% by mass or less, based on the total amount of the colorant (A). Further, it may be 30% by mass or more, preferably 50% by mass or more, and more preferably 70% by mass or more.
When the dye (A1) is contained, the content of the dye (A1) is preferably 0.5% by mass or more and 90% by mass or less, and more preferably 40% by mass or more, based on the total amount of the colorant (A). It is 80% by mass or less. When the pigment (P) is contained, the content of the pigment (P) is preferably 1% by mass or more and 99% by mass or less, and more preferably 1% by mass or more and 70% by mass with respect to the total amount of the colorant (A). % Or less, more preferably 1% by mass or more and 50% by mass or less.

The content of the colorant (A) is preferably 0.1% by mass or more and 70% by mass or less, more preferably 0.5% by mass or more and 60% by mass or less, and further, with respect to the total amount of solid content. It is preferably 1% by mass or more and 50% by mass or less. When the content of the colorant (A) is within the above range, desired spectroscopy and color density can be obtained.
In the present specification, the "total amount of solids" means the total amount of the components excluding the solvent (E) from the colored curable resin composition of the present invention. The total amount of solids and the content of each component relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and is derived from at least one monomer (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. It is preferably a polymer having a structural unit.
The resin (B) is a monomer (b) having a structural unit derived from the monomer (a), a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond, and a monomer ( A copolymer having a structural unit derived from at least one of the monomer (c) copolymerizable with a) is preferable.
The reaction order is not limited, and the monomer (a) and at least one of the monomers (b) and (c) may be copolymerized at one time. When any of the monomers (a) to (c) is used, the monomer (a) and the monomer (b) may be copolymerized and then the monomer (c) may be reacted. , The monomer (a) and the monomer (c) may be copolymerized and then the monomer (b) may be reacted. Further, the monomer (a) may be reacted with the copolymer of the monomer (b) and the monomer (c), and the carboxylic acid anhydride may be further reacted.

As (a), for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexendicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, Bicyclounsaturated compounds containing carboxy groups such as 5-carboxymethylbicyclo [2.2.1] hept-2-ene, 5-carboxyethylbicyclo [2.2.1] hept-2-ene;
Examples thereof include carboxylic acid anhydrides such as the anhydrides of the unsaturated dicarboxylic acids excluding fumaric acid and mesaconic acid.
Unsaturated mono [(meth) acryloyloxyalkyl] ester of a polyvalent carboxylic acid having a divalent value or higher, such as monooxalate [2- (meth) acryloyloxyethyl] and mono [2- (meth) acryloyloxyethyl] phthalate. Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an alkaline aqueous solution.

(B) refers to a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxylan ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. In (b), a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group is preferable.

Examples of (b) include a monomer (b1) having an oxylanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a simple monomer having an oxetanyl group and an ethylenically unsaturated bond. A metric (b2) (hereinafter sometimes referred to as "(b2)"), a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (b3) (hereinafter sometimes referred to as "(b3)"), etc. Can be mentioned.

As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)” may be used. (There is), a monomer (b1-2) having an epoxidized structure of an alicyclic unsaturated hydrocarbon (hereinafter, may be referred to as “(b1-2)”) can be mentioned.

As (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Specific examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, vinylbenzyl glycidyl ether, and α-methylvinylbenzyl. Glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene , 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris Examples thereof include (glycidyloxymethyl) styrene and 2,4,6-tris (glycidyloxymethyl) styrene.

Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, celloxide (registered trademark) 2000; manufactured by Daicel Corporation), and 3,4-epoxycyclohexylmethyl (meth). Acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer (registered trademark) M100; manufactured by Daicel Corporation), formula ( Examples thereof include a compound represented by BI) and a compound represented by the formula (BII).

[In the formula (BI) and the formula (BII), ^Ra and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group. It may be replaced.
X ^a and X ^b are each independently a single ^{bond, * - R c -, *} - R c -O -, * - represents the R ^c -S- or * -R ^c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Examples of the compound represented by the formula (BI) include compounds represented by any of the formulas (BI-1) to (BI-15), preferably the formulas (BI-1) and the formula (BI-15). -3), formula (BI-5), formula (BI-7), formula (BI-9) or compounds represented by formulas (BI-11) to formulas (BI-15) are mentioned, and more preferably. Examples thereof include compounds represented by the formula (BI-1), the formula (BI-7), the formula (BI-9) or the formula (BI-15).

Examples of the compound represented by the formula (BII) include compounds represented by any of the formulas (BII-1) to (BII-15), preferably the formulas (BII-1) and the formula (BII-15). -3), formulas (BII-5), formulas (BII-7), formulas (BII-9) and compounds represented by formulas (BII-11) to formulas (BII-15) are more preferable. Examples thereof include compounds represented by the formula (BII-1), the formula (BII-7), the formula (BII-9) and the formula (BII-15).

The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone or in combination with the compound represented by the formula (BI) and the compound represented by the formula (BII). You may. When these are used in combination, the content ratio of the compound represented by the formula (BI) and the compound represented by the formula (BII) is preferably 5:95 to 95: 5, and more preferably 10 on a molar basis. : 90 to 90:10, more preferably 20:80 to 80:20.

As the (b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, 3-methyl-3- (meth) acryloyloxyethyloxetane and 3-. Ethyl-3- (meth) acryloyloxyethyl oxetane and the like can be mentioned.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (corresponding to In the technical field, it is commonly referred to as "dicyclopentanyl (meth) acrylate", and may be referred to as "tricyclodecyl (meth) acrylate"), tricyclo [5.2.1.0 ^{2]. , 6} ] Decane-9-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate ) Acrylate ”), tricyclo [5.2.1.0 ^2,6 ] decene-9-yl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, (Meta) acrylic acid esters such as adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2] .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] Hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2. 1] Hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy -5-Methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2] .2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-Phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-bis (cyclohexyl) Bicyclounsaturated compounds such as oxycarbonyl) bicyclo [2.2.1] hept-2-ene;
N-Phenylmaleimide, N-Cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3 -Maleimide propionate and dicarbonylimide derivatives such as N- (9-acridinyl) maleimide;
Vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and p-methoxystyrene; vinyl group-containing nitriles such as (meth) acrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; (meth) acrylamide. Such as vinyl group-containing amides; esters such as vinyl acetate; dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene; and the like.
Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are selected from the viewpoint of copolymerization reactivity and heat resistance. preferable.

The polymerization initiator, solvent and the like are not particularly limited, and those usually used in the art can be used. For example, as the polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl peroxide, etc.) As the solvent, any solvent may be used as long as it dissolves each monomer, and examples of the solvent (E) of the colored curable resin composition of the present invention include a solvent described later.

As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a copolymer taken out as a solid by a method such as reprecipitation is used. You may. In particular, by using the solvent contained in the color curable resin composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the color curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of the present invention can be simplified.
Further, if necessary, a reaction catalyst of a carboxylic acid or carboxylic acid anhydride and a cyclic ether (for example, tris (dimethylaminomethyl) phenol or the like), a polymerization inhibitor (for example, hydroquinone or the like) or the like may be used.
Examples of the carboxylic acid anhydride include maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 , 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride and the like. The amount of the carboxylic acid anhydride used is preferably 0.5 to 1 mol with respect to 1 mol of the amount used in (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.0 ^2,6. ] Resins such as decyl (meth) acrylate / (meth) acrylic acid copolymer; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexyl maleimide copolymer, 3,4- Epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl-3- (meth) acrylic loyloxymethyloxetane / (meth) ) Resins such as acrylic acid / styrene copolymer; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) Resins such as acrylate / (meth) acrylic acid copolymer; resin in which glycidyl (meth) acrylate is added to benzyl (meth) acrylate / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / styrene. / (Meta) Acrylate copolymer with glycidyl (meth) acrylate added, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer with glycidyl (meth) acrylate Resins such as added resins; resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, tricyclodecyl (meth) acrylate / styrene / glycidyl (meth). ) A resin such as a resin obtained by reacting an acrylate copolymer with (meth) acrylic acid; a resin obtained by reacting a tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer with (meth) acrylic acid. Further, a resin such as a resin obtained by reacting tetrahydrophthalic acid anhydride can be mentioned.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. .. When the molecular weight is in the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the unexposed portion in the developing solution is good, and the resolution of the colored pattern tends to be improved.
The dispersity [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value of the resin (B) in terms of solid content is preferably 50 to 170 mg-KOH / g, more preferably 50 to 150 mg-KOH / g, and even more preferably 50 to 135 mg-KOH / g. .. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of solids. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and residual film ratio of the colored pattern tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, which is preferable. Examples include (meth) acrylic acid ester compounds.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. Etc., and the above-mentioned (a), (b) and (c) can be mentioned.

Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di. Examples thereof include (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (dipentaerythritol hexa (). Meta) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl ) Isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, Examples thereof include caprolactone-modified pentaerythritol tetra (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate, and preferably dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

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

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and 17 to 55% by mass with respect to the total amount of solids. Is even more preferable.
The content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] is preferably 20:80 to 80:20 on a mass basis. It is preferably 35: 65-80: 20.
When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming the coloring pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat to initiate polymerization, and a known polymerization initiator can be used. ..
Examples of the polymerization initiator (D) include an O-acyloxime compound, an alkylphenone compound, a biimidazole compound, a triazine compound, an acylphosphine oxide compound and the like.

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

Examples of the O-acyloxym compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6-] (2-Methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,, 3-dimethyl-2,) 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole] -3-yl] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane- 1-on-2-imine and the like can be mentioned. Commercially available products such as Irgacure OXE01 and OXE02 (all manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. Among them, the O-acyloxym compounds are N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1. It is preferably at least one selected from the group consisting of −on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, preferably N. More preferably, it is −benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine.
The content of the O-acyloxime compound is preferably 5 parts by mass or more, more preferably 50 parts by mass or more, and further preferably 70 parts by mass or more in 100 parts by mass of the polymerization initiator. It is more preferably 80 parts by mass or more, and more preferably 100 parts by mass or less.

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

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4). -Morphorinophenyl) -2-benzylbutane-1-one and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one And so on. Commercially available products such as Irgacure 369, 907, 379 (all manufactured by BASF) may be used.
Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2). -Hydroxyethoxy) phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α-diethoxy Examples thereof include acetophenone and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

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 (see, for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4, 4', 5,5'-Tetraphenyl biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole 2-Chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxy) Phenyl) Biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.) and the phenyl group at the 4,4', 5,5'-position are substituted with a carboalkoxy group. Examples thereof include imidazole compounds (see, for example, Japanese Patent Application Laid-Open No. 7-10913). Of these, compounds represented by the following formulas and mixtures thereof are preferable.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-). Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy) Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-) 2-Methylphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. Can be mentioned.

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

Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone; 9,10-phenanthrene quinone, Kinone compounds such as 2-ethylanthraquinone and benzophenone; examples include 10-butyl-2-chloroacrydone, benzyl, methyl phenylglioxylate and titanosen compounds.
These are preferably used in combination with the polymerization initiation aid (D1) described later.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound and a biimidazole compound, and more preferably. A polymerization initiator containing an O-acyloxime compound.

The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is a mass part.

<Polymerization initiation aid (D1)>
The polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by the polymerization initiator. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4 -Dimethylaminobenzoate 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone and 4,4'-bis Examples thereof include (ethylmethylamino) benzophenone, and preferably 4,4'-bis (diethylamino) benzophenone. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-di. Butoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene and the like can be mentioned.

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

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, and dichlorophenylsulfanyl acetic acid. Examples thereof include N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

When these polymerization initiators (D1) are used, the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). , More preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a 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 particularly limited, and a solvent usually used in the art can be used. For example, ester solvent (solvent containing -COO- in the molecule and not containing -O-), ether solvent (solvent containing -O- in the molecule and not containing -COO-), ether ester solvent (solvent in the molecule). Solvent containing -COO- and -O-), Ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule, -O-,- CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

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, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. , Propropylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Examples thereof include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyletol, methyl anisole and the like.

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

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. And so on.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.
Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

These solvents may be used alone or in combination of two or more.
Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3- Preference is given to methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone and the like, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether and di. More preferred are propylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and N-methylpyrrolidone.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and the display characteristics tend to be good because the color density is not insufficient when the color filter is formed.

<Leveling agent (F)>
Examples of the leveling agent (F) include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan GK) and the like. ..

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

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

When the leveling agent (F) is contained, the content thereof is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002, based on the total amount of the colored curable resin composition. It is mass% or more and 0.1 mass% or less, more preferably 0.005 mass% or more and 0.07 mass% or less. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
The color-curable resin composition of the present invention is an additive known in the art, such as a filler, other polymer compounds, an adhesion accelerator, an antioxidant, a light stabilizer, and a chain transfer agent, if necessary. May include.

<Manufacturing method of colored curable resin composition>
The color curable resin composition of the present invention is, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) used as necessary. , Leveling agent (F), polymerization initiator (D1) and other components can be mixed.
When the colorant (A) other than the xanthene compound (A-1) contains the pigment (P), the pigment (P) is mixed with a part or all of the solvent (E) in advance, and the average particle size of the pigment is increased. It is preferable to disperse using a bead mill or the like until the thickness becomes about 0.2 μm or less. At this time, if necessary, a part or all of the pigment dispersant and the resin (B) may be blended.
It is preferable to filter the colored curable resin composition after mixing with a filter having a pore size of about 0.01 to 10 μm.

<Manufacturing method of color filter>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, a printing method and the like. Above all, the photolithography method is preferable. The photolithography method is a method in which the colored curable resin composition is applied to a substrate and dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film which is a cured product of the coloring composition layer can be formed by not using a photomask at the time of exposure and / or not developing. The colored pattern or colored coating film thus formed can be used as the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited and can be appropriately adjusted according to the purpose, application and the like. For example, 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.5. It is ~ 6 μm.

As the substrate, a glass plate, a resin plate, silicon, or a substrate obtained by forming an aluminum, silver, silver / copper / palladium alloy thin film, or the like on a substrate of the above material is used. Another color filter layer, resin layer, transistor, circuit, or the like may be formed on these substrates.

The formation of each color pixel by the photolithography method can be performed by a known or conventional device or condition. For example, it can be produced as follows. First, a color curable resin composition is applied onto a substrate and dried by heat drying (prebaking) and / or vacuum drying to remove volatile components such as a solvent to obtain a smooth colored composition layer. Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like.

The coloring composition layer is then exposed via a photomask to form the desired coloring pattern. An exposure device such as a mask aligner and a stepper is used because it is possible to uniformly irradiate the entire exposed surface with parallel rays and accurately align the photomask with the substrate on which the coloring composition layer is formed. Is preferable.

A coloring pattern is formed on the substrate by developing the coloring composition layer after exposure by bringing it into contact with a developing solution. By development, the unexposed portion of the coloring composition layer is dissolved in a developing solution and removed. As the developing solution, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate and tetramethylammonium hydroxide is preferable. The developing method may be any of a paddle method, a dipping method, a spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.
Further, it is preferable to post-bake the obtained coloring pattern.
The obtained coloring pattern can be configured as a color filter.

The color curable resin composition of the present invention can produce a color filter having particularly excellent heat resistance. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image sensor.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples as well as the present invention, and appropriate modifications are made to the extent that it can be adapted to the gist of the above and the following. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention. In the following, unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".

(Synthesis Example 1)
10 parts of the compound represented by the formula (AXa-1), 300 parts of chloroform and 5.7 parts of N, N-dimethylformamide were put into a flask equipped with a cooling tube and a stirrer, and the temperature was kept at 20 ° C. or lower under stirring. While maintaining, 12.6 parts of thionyl chloride was added dropwise, and the reaction was carried out by maintaining for 5 hours. Then, while maintaining the temperature below 20 ° C. with stirring, a mixed solution of 6.7 parts of N-ethylmethylamine and 11.5 parts of triethylamine was added dropwise. Then, the reaction was carried out by stirring at the same temperature for 5 hours. Then, the obtained reaction mixture was distilled off with a rotary evaporator, and then a small amount of methanol was added and the mixture was vigorously stirred. This mixture was added to a mixed solution of 375 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C. to obtain 10.7 parts of the compound represented by the formula (AXa-1a).

Identification of the compound represented by the formula (AXa-1a) (mass spectrometry) Ionization mode = ESI +: m / z = 701.9 [M-Cl] ⁺
Exact Mass: 736.4

400 parts of methanol was added to 7.3 parts of the compound represented by the formula (AXa-1a), and the mixture was stirred at 20 ° C. to 30 ° C. for 1 hour to obtain a solution. To this solution, 400 parts of ion-exchanged water was added, and the mixture was stirred for 2 hours to obtain a solution (AXa-1aKA).
On the other hand, 28.8 parts of ion-exchanged water was added to 9.6 parts of trihydrogen of phospho12 tungstic acid, and the mixture was stirred at 20 ° C. to 30 ° C. for 1 hour, then 28.8 parts of methanol was added, and the mixture was stirred for 2 hours. (AXa-1aKB) was obtained. The solution (AXa-1aKB) was added to the solution (AXa-1aKA), and the mixture was stirred at 20 ° C. to 30 ° C. for 12 hours. The resulting precipitate was collected by filtration and washed twice with 200 parts of ion-exchanged water and then twice with 200 parts of methanol. The crystals collected by filtration were dried at 60 ° C. for 24 hours to obtain 10.2 parts of the compound represented by the formula (AXa-1A).

(Synthesis Example 2)
In Synthesis Example 1, 10.2 parts of the compound represented by the formula (AXa-2A) was obtained by synthesizing in the same manner as in Synthesis Example 1 except that 2-ethylhexylamine was used instead of N-ethylmethylamine. rice field.

(Synthesis Example 3)
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 100 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 ° C. with stirring. Then, in the flask, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] Mixture of decane-9-ylacrylate (content ratio is 50:50 in molar ratio) (trade name "E-DCPA", manufactured by Daicel Co., Ltd.) 171 parts propylene glycol monomethyl ether acetate 40 parts The solution dissolved in was added dropwise over about 5 hours using a dropping pump. On the other hand, a solution prepared by dissolving 26 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was placed in the flask over about 5 hours using another dropping pump. Dropped. After the addition of the polymerization initiator was completed, the mixture was kept at the same temperature for about 3 hours and then cooled to room temperature to obtain a solution of a copolymer and resin (B-1) having a solid content of 43.5%. The weight average molecular weight of the obtained resin (B-1) was 8000, the dispersity was 1.98, and the acid value in terms of solid content was 53 mg-KOH / g.

(Synthesis Example 4)
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 ° C. with stirring. Then, in the flask, 38 parts of acrylic acid, ^{a mixture of 3,4-epoxytricyclo [5.2.1.0 2,6} ] decane-8 and 9-yl acrylate (content ratio is 50 in molar ratio: 50: 50) A solution prepared by dissolving 289 parts (trade name "E-DCPA", manufactured by Daicel Co., Ltd.) in 125 parts of propylene glycol monomethyl ether acetate was added dropwise using a dropping pump over about 5 hours. On the other hand, a solution prepared by dissolving 33 parts of the polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise into the flask over about 6 hours using another dropping pump. bottom. After the addition of the polymerization initiator was completed, the mixture was kept at the same temperature for about 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-2)) having a solid content of 35.1%. The weight average molecular weight of the obtained resin (B-2) was 9,200, the dispersity was 2.08, and the acid value in terms of solid content was 77 mg-KOH / g.

The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
Equipment; HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature; 40 ° C
Solvent; THF
Flow velocity; 1.0 mL / min
Test solution solid content concentration; 0.001 to 0.01% by mass
Injection volume; 50 μL
Detector; RI
Calibration standard material; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Made by Tosoh Corporation)
Ratio of polystyrene-equivalent weight average molecular weight and number average molecular weight obtained above (Mw / Mn)
) Was the degree of dispersion.

[Preparation of Color Curable Resin Composition]
Examples 1 and 2, Comparative Example 1
The components shown in the table below were mixed to obtain a colored curable resin composition.

In the table, each component is as follows.
Dye (A-1): Compound represented by formula (AXa-1A) Dye (A-2): Compound represented by formula (AXa-2A) Dye (A-3): Rhodamine B (Tokyo Chemical Industry (Tokyo Chemical Industry) Made by Co., Ltd.)
Resin (B): Resin (B-1) (in terms of solid content)
Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization Initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure® OXE-01; BASF; O-acyloxime compound)
Solvent (E-1): Propylene Glycol Monomethyl Ether Acetate Solvent (E-2): Propylene Glycol Monomethyl Ether Solvent (E-3): Ethyl Lactate Solvent (E-4): Dimethylformamide Leveling Agent (F): Megafuck ( Registered trademark) F554 (manufactured by DIC Co., Ltd.)

[Pattern formation]
A colored photosensitive composition was applied onto a 2-inch square glass substrate (Eagle XG; manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to obtain a composition layer. After cooling, the distance between the glass substrate on which the composition layer was formed and the quartz glass photomask was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used in an air atmosphere at 150 mJ / cm ² The light was irradiated at the exposure amount of (365 nm standard). As the photomask, a photomask having a 100 μm line-and-space pattern formed is used. After light irradiation, the coating film is immersed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 80 seconds, washed with water, and then in an oven at 220 ° C. After 20 minutes of post-baking, a pattern was obtained.

[Heat resistance evaluation]
In forming the above pattern, a coating film was obtained in the same manner as above except that a photomask was not used when irradiating with light. The chromaticity of the obtained coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). Then, after heating the same coating film at 230 ° C. for 20 minutes, the chromaticity was measured again using a colorimeter (OSP-SP-200; manufactured by OLYMPUS), and the color difference of the coating film before and after heating (ΔEab *). Asked. The color difference (ΔEab *) of the coating film formed from the colored curable resin compositions of Examples 1 and 2 was 4.5 and 3.8, respectively. The color difference (ΔEab *) of the coating film formed from the colored curable resin composition of Comparative Example 1 was 80.1. From this, it was found that the coating film and the pattern formed from the colored curable resin composition of the present invention have excellent heat resistance.

Comparative Example 2
(Preparation of dispersion)
10.0 parts of Pigment Red 81, 10.5 parts of dispersant DISPERBYK-LPN6919 (propylene glycol monomethyl ether acetate solution with 38% solid content), and propylene glycol monomethyl ether acetate solution (resin B-2) as a dispersion resin (resin B-2). Weigh 5.7 parts (solid content 35%) and 163.7 parts of propylene glycol monomethyl ether acetate, add 300 parts of 0.4 μm zirconia beads, and shake for 3 hours using a paint conditioner (manufactured by LAU). To prepare a dispersion.

(Preparation of Color Curable Resin Composition)
Dispersion: 15 parts;
Alkali-soluble resin (B): Resin (B-1) (solid content equivalent) 1.0 part;
Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 2.0 parts;
Polymerization Initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure® OXE-01; BASF; O-acyloxime compound) 0.3 copies;
Solvent (E): 18 parts of propylene glycol monomethyl ether acetate;
Leveling agent (H): Polyether-modified silicone oil (in terms of solid content)
(Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.09 parts were mixed to obtain a colored curable resin composition.

When the heat resistance was evaluated by the same method as in Examples 1 and 2 and Comparative Example 1, the color difference (ΔEab *) was 17.7.

By using the color curable resin composition of the present invention, it is possible to provide a color filter having good heat resistance. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image sensor.

Claims (5)

A color curable resin composition containing a xanthene compound (A-1), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).
The xanthene compound (A-1) contains a cation (AXa) having a xanthene skeleton having a substituted or unsubstituted sulfamoyl group, at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and oxygen. Ri compound der having an anion (AXb) which comprises, as essential elements,
It said cation having a xanthene skeleton (AXa) is colored curable resin composition Ru cations der represented by formula (I-2).

[In formula (I-2),
R ^1c and R ^4c independently represent an alkyl group having 1 to 4 carbon atoms, an alkyl sulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms.
p and q represent integers 0 to 5 independently of each other. When p is 2 or more, the plurality of R ^1c may be the same or different, and when q is 2 or more, the plurality of R ^4c may be the same or different.
R ^2c and R ^3c represent monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have substituents independently of each other, and the methylene group (-CH _{2) contained in the saturated hydrocarbon group.} -) is, -O -, - CO -, - NR 11c -, - OCO -, - COO -, - OCONH -, - NHCOO -, - CONH- or may be substituted by -NHCO-. However, adjacent methylene groups are not substituted with the same substituent at the same time, and the terminal methylene group is not substituted.
R ^1c and R ^2c may be combined to form a ring containing a nitrogen atom, and R ^3c and R ^4c may be combined to form a ring containing a nitrogen atom.
R ^6c and R ^7c independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
mc represents an integer of 1-5. When mc is 2 or more, a plurality of −SO ₂ NR ^9c R ^10c may be the same or different.
R ^9c and R ^10c represent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have hydrogen atoms or substituents independently of each other, and methylene groups (-CH _{2) contained in the saturated hydrocarbon groups.} -) is, -O -, - CO -, - NR 11c -, - OCO -, - COO -, - OCONH -, - NHCOO -, - CONH- or -NHCO- may be substituted by, R ^9c And R ^10c may be bonded to each other to form a 3- to 10-membered heterocycle containing a nitrogen atom. However, adjacent methylene groups are not substituted with the same substituent at the same time, and the terminal methylene group is not substituted.
R ^11c represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ] Anion (AXb) is an anion in which claim 1 Symbol placement colored curable resin composition of the heteropoly acid or isopolyacid containing tungsten as essential elements. The colored curable resin composition according to claim 1 or 2 , wherein the anion (AXb) is either a phosphotungstic acid anion, a silicotungstic acid anion, or a tungsten-based isopolyacid anion. A color filter formed from the colored curable resin composition according to any one of claims 1 to 3. A display device including the color filter according to claim 4.