TWI716505B - Compound, coloring composition, color filter and display device - Google Patents

Abstract

The subject of the present invention is to provide a color filter having excellent solvent resistance, a display device including the color filter, a compound capable of providing them, and a coloring composition. The compound of the present invention is represented by formula (A-I).

Description

Compound, coloring composition, color filter and display device Invention field

The present invention relates to compounds and coloring compositions containing them.

Background of the invention

The coloring composition is used in the production of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays. As such a coloring composition, a coloring composition containing a compound represented by the following formula and the like is known.

[Prior Art Literature] [Patent Literature]

Patent Document 1: WO2012/053211

Patent Document 2: Japanese Patent Application Publication No. 2015-38201

Summary of the invention

In the conventionally known compounds, the absorbance and voltage holding ratio are not sufficiently satisfactory, and a color filter formed from a coloring composition containing the compound may not sufficiently satisfy solvent resistance.

The present invention includes the following inventions.

[1] A compound represented by formula (A-I).

[In formula (AI), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbons, or a substituted carbon number The aralkyl group of 7-30, the aromatic hydrocarbon group and the substituent that the aralkyl group may have may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , the saturated carbon number of 1-20 In the hydrocarbon group, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a substituted or unsubstituted amine group or halogen atom. When the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group Can be replaced by oxygen atom or -CO-. However, in this saturated hydrocarbon group with 2 to 20 carbon atoms, the adjacent methylene groups are not simultaneously replaced with oxygen atoms, and the terminal methylene groups are not replaced with oxygen atoms or -CO-. R ⁴¹ and R ⁴² may be combined with the nitrogen atom to which they are combined to form a ring, and R ⁴³ and R ⁴⁴ may be combined with the nitrogen atom to which they are combined to form a ring.

R ⁴⁷ ~ R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl _{^{group, -SO 3 -, -SO 2 -N}} - -SO 2 -R f, or an alkyl group having 1 to 8 carbon atoms constituting the The methylene group of the alkyl group can be replaced with an oxygen atom or -CO-, and R ⁴⁸ and R ⁵² can be combined with each other to form -NH-, -S-, or -SO ₂ -. However, in this alkyl group, adjacent methylene groups are not simultaneously replaced with oxygen atoms, and terminal methylene groups are not replaced with oxygen atoms or -CO-.

Ring T ¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms. The aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted amine group, or a substituted or unsubstituted amine group having 6 to 20 carbon atoms. Aromatic hydrocarbon group. The substituent that the aromatic hydrocarbon group may have may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f .

M ^r+ represents hydrogen ion, r-valent metal ion, or substituted or unsubstituted ammonium ion.

k represents the sum of the number of -SO ₃ ^-and the number of -SO ₂ -N ^-- SO ₂ -R ^f that the compound represented by formula (AI) has.

r represents an integer of 1 or more.

R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms.

However, the compound represented by the formula (AI) has at least one -SO ₂ -N ^-- SO ₂ -R ^f . ]

[2] The compound according to [1], wherein Mr ⁺ is a metal ion.

[3] The compound according to [1] or [2], wherein the aromatic heterocyclic ring represented by the above T ^{1 is} a ring represented by the following formula (A-t1).

[In formula (A-t1), ring T ² represents an aromatic heterocyclic ring having 3 to 10 carbon atoms.

R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted carbon number 7 to In an aralkyl group of 30, when the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or -CO-. However, in this saturated hydrocarbon group with 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced with oxygen atoms, and the terminal methylene groups are not replaced with oxygen atoms or -CO-. R ⁴⁵ and R ⁴⁶ may be combined to form a ring together with the nitrogen atom to which they are bonded.

R ⁵⁵ represents a saturated hydrocarbon group having 1 to 20 carbons, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbons.

k1 represents 0 or 1.

* Indicates the bonding end with the carbocation. ]

[4] A coloring composition containing the compound described in any one of [1] to [3].

[5] A color filter formed from the coloring composition described in [4].

[6] A display device including the color filter described in [5].

The compound of the present invention has excellent absorbance and voltage retention, and a coloring composition containing the compound can form a color filter having excellent solvent resistance.

Detailed ways

The compound of the present invention is represented by formula (A-I). Hereinafter, the compound represented by formula (A-I) is also referred to as compound (A-I). The compounds of the present invention are also Including its tautomers and their salts.

[In formula (AI), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbons, or a substituted carbon number The aralkyl group of 7-30, the aromatic hydrocarbon group and the substituent that the aralkyl group may have may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , the saturated carbon number of 1-20 In the hydrocarbon group, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a substituted or unsubstituted amine group or halogen atom. When the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group Can be replaced by oxygen atom or -CO-. However, in this saturated hydrocarbon group with 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced with oxygen atoms, and the terminal methylene groups are not replaced with oxygen atoms or -CO-. R ⁴¹ and R ⁴² may be combined with the nitrogen atom to which they are combined to form a ring, and R ⁴³ and R ⁴⁴ may be combined with the nitrogen atom to which they are combined to form a ring.

R ⁴⁷ ~ R ⁵⁴ each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl _{^{group, -SO 3 -, -SO 2 -N}} - -SO 2 -R f, or an alkyl group having 1 to 8 carbon atoms constituting the The methylene group of the alkyl group can be replaced with an oxygen atom or -CO-, and R ⁴⁸ and R ⁵² can be combined with each other to form -NH-, -S-, or -SO ₂ -. However, in this alkyl group, adjacent methylene groups are not simultaneously replaced with oxygen atoms, and terminal methylene groups are not replaced with oxygen atoms or -CO-.

The ring T ¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. The substituent that the aromatic hydrocarbon group may have may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f .

M ^r+ represents hydrogen ion, r-valent metal ion, or substituted or unsubstituted ammonium ion.

k represents the sum of the number of -SO ₃ ^-and the number of -SO ₂ -N ^-- SO ₂ -R ^f that the compound represented by formula (AI) has.

r represents an integer of 1 or more.

R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms.

However, the compound represented by the formula (AI) has at least one -SO ₂ -N ^-- SO ₂ -R ^f . ]

The aromatic heterocyclic ring represented by ring T ¹ may be a monocyclic ring or a condensed ring. T by the ring carbon atoms of the aromatic heterocyclic ring ^represented 3 to 10, preferably 3 to 8. In addition, the aromatic heterocyclic ring is preferably a 5- to 10-membered ring, and more preferably a 5- to 9-membered ring. Examples of monocyclic aromatic heterocycles include 5-membered rings containing nitrogen atoms such as pyrrole ring, oxazole ring, pyrazole ring, imidazole ring, and thiazole ring; and 5 membered rings containing no nitrogen atom such as furan ring and thiophene ring. 6-membered ring containing nitrogen atoms such as pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, etc. As the aromatic heterocyclic ring of the condensed ring, indole ring, benzimidazole ring, benzo Condensed rings containing nitrogen atoms such as thiazole rings and quinoline rings; condensed rings containing no nitrogen atoms such as benzofuran rings.

Examples of substituents that the aromatic heterocyclic ring of ring T ¹ may have include halogen atoms, cyano groups, and optionally substituted saturated hydrocarbon groups having 1 to 20 carbons (preferably alkyl groups having 1 to 20 carbons), A substituted or unsubstituted amine group or an aromatic hydrocarbon group having 6 to 20 carbons which may have a substituent, etc. Preferably, a saturated hydrocarbon group having 1 to 20 carbons (preferably an alkyl group having 1 to 20 carbons) is mentioned , A substituted or unsubstituted amine group or an optionally substituted aromatic hydrocarbon group with 6 to 20 carbons.

Among them, as the aromatic heterocyclic ring of ring T ¹ , a nitrogen atom-containing aromatic heterocyclic ring is preferable, and a nitrogen atom-containing 5-membered aromatic heterocyclic ring is more preferable.

In addition, the ring T ^{1 is} more preferably a ring represented by formula (A-t1).

[In formula (A-t1), ring T ² represents an aromatic heterocyclic ring having 3 to 10 carbon atoms.

R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms, or an optionally substituted carbon number 7 to In an aralkyl group of 30, when the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or -CO-. However, in this saturated hydrocarbon group with 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced with oxygen atoms, and the terminal methylene groups are not replaced with oxygen atoms or -CO-. R ⁴⁵ and R ⁴⁶ may be combined to form a ring together with the nitrogen atom to which they are bonded.

R ⁵⁵ represents a saturated hydrocarbon group having 1 to 20 carbons, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbons.

k1 represents 0 or 1.

* Indicates the bonding end with the carbocation. ]

Examples of the aromatic heterocyclic ring of the ring T ² include the same rings as the aromatic heterocyclic ring exemplified in the ring T ¹ .

Furthermore, the ring T ^{1 is} particularly preferably a ring represented by formula (A-t1-1).

[In formula (A-t1-1), R ⁵⁶ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbons.

X2 represents an oxygen atom, -N(R ⁵⁷ )- or a sulfur atom.

R ⁵⁷ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ⁴⁵ and R ⁴⁶ have the same meaning as above.

* Indicates the bonding end with the carbocation. ]

In addition, the ring T ^{1 is} also preferably a ring represented by formula (A-t2).

[In formula (A-t2), ring T ³ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms and having a nitrogen atom.

R ⁵⁸ represents a saturated hydrocarbon group having a carbon number of 1 to 20 carbon atoms may have a substituent, an aromatic hydrocarbon group having 6 to 20, -SO ₃ ^-, or _{^{-SO 2 -N - -SO 2 -R f}} .

R ⁵⁹ represents a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbons, or an optionally substituted aralkyl group having 7 to 30 carbons.

k2 represents 0 or 1.

* Indicates the bonding end with the carbocation. ]

The ring T ^{1 is} also more preferably a ring represented by formula (A-t2-1).

[In the formula (A-t2-1), R ⁶⁰ represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbons.

R ⁶¹ represents a hydrogen atom, -SO ₃ ^-, or _{^{-SO 2 -N - -SO 2 -R f}} .

R ⁵⁹ is synonymous with the above.

* Indicates the bonding end with the carbocation. ]

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ may be any of linear, branched and cyclic. Examples of linear or branched saturated hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, and decyl groups. Straight-chain alkyl such as hexaalkyl and eicosyl; branched alkyl such as isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl, etc. The carbon number of the saturated hydrocarbon group is preferably 1-10, more preferably 1-8, and still more preferably 1-6.

The cyclic saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ may be monocyclic or polycyclic. Examples of the cyclic saturated hydrocarbon group include alicyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. The carbon number of the cyclic saturated hydrocarbon group is preferably 3-10, and more preferably 6-10.

Specific examples of saturated hydrocarbon groups represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ include groups represented by the following formulas. In the following formula, * represents a bonding end.

The saturated hydrocarbon groups represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ may be substituted with substituted or unsubstituted amine groups or halogen atoms. Examples of substituted amino groups include alkylamino groups such as dimethylamino and diethylamino. In addition, examples of the halogen atom include fluorine, chlorine, bromine, and iodine. In addition, when the halogen atom is a fluorine atom, the saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ substituted with a halogen atom (fluorine atom) is preferably a trifluoromethyl, five Perfluoroalkyl groups such as fluoroethyl and heptafluoropropyl.

As a saturated hydrocarbon group having 1 to 20 carbon atoms having a substituent, for example, a group represented by the following formula can be cited. In the following formula, * means that with nitrogen atom etc. Bonded end.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ include groups having 1 to 8 carbon atoms in the linear or branched saturated hydrocarbon groups exemplified by the saturated hydrocarbon group represented by R ⁴¹ group.

In addition, examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁵⁷ include groups having 1 to 10 carbon atoms in the linear or branched saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ⁴¹ .

When the saturated hydrocarbon group represented by R ⁴¹ to R ⁴⁶ has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or -CO-. However, in this saturated hydrocarbon group with 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced with oxygen atoms, and the terminal methylene groups are not replaced with oxygen atoms or -CO-. In this case, the saturated hydrocarbon group is preferably a linear or branched saturated hydrocarbon group (that is, a linear or branched alkyl group), and a linear saturated hydrocarbon group (that is, a linear alkyl group) is more preferable. The preferable carbon number of the saturated hydrocarbon group in which a methylene group can be substituted with an oxygen atom or -CO- is 2-10, More preferably, it is 2-8. When the methylene group is replaced with an oxygen atom or -CO-, the number of carbons between the terminal and the oxygen atom or -CO-, or between the oxygen atom or -CO- and the oxygen atom or -CO- is 1 or more, preferably It is 1 to 5, more preferably 2 to 3, and even more preferably 2. In the group in which the methylene group of the saturated hydrocarbon group is replaced with an oxygen atom or -CO-, for example, an alkoxyalkyl group; or (alkoxyalkoxy)alkyl group, (alkoxyalkoxyalkoxy group) Group) alkyl, (alkoxy alkoxy alkoxy alkoxy) alkyl, (alkoxy alkoxy alkoxy alkoxy alkoxy) alkyl, (alkoxy alkoxy alkoxy) The number of repetitions of the alkoxy unit is, for example, 1 to 6, preferably 1 to 4, and more preferably 1 to 2, such as polyalkoxyalkyl groups such as oxyalkoxyalkoxyalkyloxy) alkyl. In a more preferable specific example, a group represented by the following formula can be mentioned. In the following formula, * represents the bonding terminal to the nitrogen atom.

In addition, the number of carbon atoms of the optionally substituted aromatic hydrocarbon group represented by R ⁴¹ to R ⁴⁶ , R ⁵⁵ , R ⁵⁶ and R ⁵⁸ to R ⁶⁰ is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6. ~12. Examples of the aromatic hydrocarbon group include phenyl, tolyl, xylyl, naphthyl, anthracenyl, phenanthryl, biphenyl, terphenyl, etc., preferably phenyl, naphthyl, tolyl, and xylene The group is particularly preferably a phenyl group. In addition, the aromatic hydrocarbon group may have 1 or 2 or more substituents. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; halogenated alkyl groups having 1 to 6 carbon atoms such as chloromethyl and trifluoromethyl; and carbon atoms such as methoxy and ethoxy. Alkoxy with 1~6; hydroxyl; sulfamsulfonyl; alkylsulfonyl with 1 to 6 carbons such as methylsulfonyl; methoxycarbonyl, ethoxycarbonyl and other carbon 1 to 6 alkoxycarbonyl _{^{group; -SO 3 -; -SO 2 -N}} - -SO 2 -R f , etc., may be -SO ₃ ^- or _{^{-SO 2 -N - -SO 2 -R f}} . However, -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f is preferably directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group, that is, the hydrogen atom bonded to the aromatic hydrocarbon ring is substituted.

As a specific example of the aromatic hydrocarbon group which may have a substituent, the group represented by the following formula is mentioned, for example. In the following formula, * represents the bonding terminal to the nitrogen atom.

Examples of the optionally substituted aralkyl groups represented by R ⁴¹ to R ⁴⁶ and R ⁵⁹ include the groups described as the above aromatic hydrocarbon groups bonded with carbons such as methylene, ethylene, and propylene. The number of 1 to 10 (preferably carbon number of 1 to 5) alkylene group and the like. The carbon number of the aralkyl group is preferably 7-30, more preferably 7-20, and even more preferably 7-17.

As the ring formed by combining R ⁴¹ and R ⁴² with the nitrogen atom to which they are bonded, the ring formed by combining R ⁴³ and R ⁴⁴ with the nitrogen atom to which they are bonded, and the nitrogen bonded to and bonded to R ⁴⁵ and R ⁴⁶ The ring formed by the atoms includes a pyrrolidine ring, a morpholine ring, a piperidine ring, a piperazine ring and other nitrogen-containing non-aromatic 4-7 membered rings. Preferably, a pyrrolidine ring, a piperidine ring, etc. A 4- to 7-membered ring with only one nitrogen atom as a heteroatom.

As R ⁵⁸ , a saturated hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable.

Among them, as R ⁴¹ to R ⁴⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁸ to R ⁶⁰ , a saturated hydrocarbon group having 1 to 20 carbons or an aromatic hydrocarbon group that may have a substituent is preferable, and each independently, more preferably a carbon number of 1 ~8 saturated hydrocarbon group or aromatic hydrocarbon group represented by the following formula. R ⁵⁵ , R ⁵⁶ , and R ⁵⁸ to R ^{60 are} more preferably aromatic hydrocarbon groups represented by the following formula. In the following formula, * represents the bonding terminal to the nitrogen atom.

R ⁴⁵ to R ^{46 are} preferably each independently a saturated hydrocarbon group having 1 to 20 carbons, a group in which the methylene group constituting an alkyl group having 2 to 20 carbons is replaced with an oxygen atom or -CO-, or may have a substituent Or R ⁴⁵ and R ⁴⁶ combine to form a ring with the nitrogen atom to which they are combined. More preferably, R ⁴⁵ to R ⁴⁶ are each independently a saturated hydrocarbon group having 1 to 8 carbons, an alkoxyalkyl group, or an aromatic hydrocarbon group represented by the following formula, or R ⁴⁵ and R ^{46 are} combined to form only one A 4- to 7-membered ring in which a nitrogen atom is a hetero atom is more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or an aromatic hydrocarbon group represented by the following formula. In the following formula, * represents the bonding terminal to the nitrogen atom.

In addition, examples of the alkyl group having 1 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ include linear or branched saturated hydrocarbon groups exemplified by the saturated hydrocarbon group represented by R ⁴¹ having carbon numbers of 1 to 8 The group. In addition, the methylene group that constitutes the alkyl group having 2 to 8 carbon atoms represented by R ⁴⁷ to R ⁵⁴ is replaced with an oxygen atom or -CO- group (however, in the alkyl group, the adjacent methylene group is not Will be replaced with an oxygen atom at the same time, and the methylene group at the terminal will not be replaced with an oxygen atom or -CO-). Examples include the alkylene groups represented by R ⁴¹ to R ⁴⁶ that constitute an alkyl group with 2 to 20 carbon atoms. The methyl group is replaced with a group with 8 or less carbon atoms selected from the group of oxygen atom or -CO-. As the C1-C8 alkyl group represented by R ⁴⁷ to R ⁵⁴ , more preferably, a group represented by the following formula can be cited. In the following formula, * represents a bonding terminal to a carbon atom.

R ⁴⁷ to R ⁵⁴ are each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, more preferably each independently a hydrogen atom, a methyl group, a fluorine atom, or Chlorine atom.

In addition, as R ⁵⁷ , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferable.

As R ⁶¹ , a hydrogen atom is preferable.

Examples of metal ions with r valence represented by Mr ⁺ include alkali metal ions such as lithium ion, sodium ion, and potassium ion; alkaline earth metal ions such as beryllium ion, magnesium ion, calcium ion, strontium ion, and barium ion; and titanium ion , Zirconium ion, chromium ion, manganese ion, iron ion, cobalt ion, nickel ion, copper ion and other transition metal ions; zinc ion, cadmium ion, aluminum ion, indium ion, tin ion, lead ion, bismuth ion and other typical metal ions Wait. r is 1 or more, preferably 2 or more, preferably 5 or less, more preferably 4 or less, and still more preferably 3 or less. In addition, examples of the substituted or unsubstituted ammonium ion represented by Mr ⁺ include quaternary ammonium ions such as tetraalkylammonium ions.

As Mr ⁺ , from the viewpoint of voltage retention, r-valent metal ions are preferable, alkaline earth metal ions, typical metal ions, etc. are more preferable, and magnesium ions, barium ions, and zinc ions are still more preferable. As Mr ⁺ , from the viewpoint of absorbance, a hydrogen ion or an alkali metal ion is preferable, and a hydrogen ion is more preferable.

In the formula (AI), the number of Mr ⁺ is more than the sum of the number of -SO ₃ ^-and the number of -SO ₂ -N ^-- SO ₂ -R ^f that the compound represented by the formula (AI) has (k ) One less number. Therefore, the compound (AI) has a valence of 0, that is, an electrically neutral compound. The case, -SO ₃ ^{- -} the number of -SO ₃ having preferably 6 or less, more preferably 3 or less, may be 1 or more. In addition, the number of -SO ₃ ^- is also preferably zero.

Examples of the fluoroalkyl group having 1 to 12 carbon atoms represented by R ^f include monofluoromethyl, difluoromethyl, trifluoromethyl (perfluoromethyl), monofluoroethyl, difluoroethyl, Trifluoroethyl, tetrafluoroethyl, pentafluoroethyl (perfluoroethyl), monofluoropropyl, difluoropropyl, trifluoropropyl, tetrafluoropropyl, pentafluoropropyl, hexafluoropropyl , Heptafluoropropyl (perfluoropropyl), monofluorobutyl, difluorobutyl, trifluorobutyl, tetrafluorobutyl, pentafluorobutyl, hexafluorobutyl, heptafluorobutyl, octafluorobutyl Base, nonafluorobutyl (perfluorobutyl), etc. Among them, as the alkyl group (fluoroalkyl group) in which all or part of the hydrogen atoms represented by R ^f are substituted with fluorine atoms, a perfluoroalkyl group is preferable. In addition, the carbon number of the alkyl group (fluoroalkyl group) in which all or part of the hydrogen atoms represented by R ^f are substituted with fluorine atoms is preferably 1-10, more preferably 1-5, and still more preferably 1-3.

The compound (AI) has at least one -SO ₂ -N ^-- SO ₂ -R ^f . The number of -SO ₂ -N ^-- SO ₂ -R ^f is 1 or more, preferably 1 to 7, more preferably 1 to 4, still more preferably 1 or 2, and particularly preferably 2.

Further, the compound (AI) also preferably have -SO ₂ -N ^- -SO ₂ -R ^f does not have -SO ₃ ^-, also preferably having -SO ₂ -N ^- -SO ₂ -R ^f, and -SO ₃ ^-. In the case of having -SO ₂ -N ^-- SO ₂ -R ^f and -SO ₃ ^- , the compound (AI) contains at least one -SO ₂ -N ^-- SO ₂ -R ^f , -SO ₂ -N ^- -SO ₂ -R ^f, and -SO ₃ ^- the total number of preferably 2 to 7, more preferably 2 to 4, more preferably 2.

The -SO ₂ -N ^-- SO ₂ -R ^f or -SO ₃ ^- is preferably contained as any of the above-mentioned R ⁴⁷ to R ⁵⁴ , or is combined with the number of carbon atoms represented by R ⁴¹ to R ⁴⁴ that may have a substituent 6-20 aromatic hydrocarbon groups, optionally substituted aralkyl groups with 7-30 carbons represented by R ⁴¹ to R ⁴⁴ , and 6 to carbon atoms substituted with hydrogen atoms of the aromatic heterocyclic ring represented by T ¹ the aromatic hydrocarbon according to any one of the binding 20, and more preferably, R ⁴¹ ~ by the aromatic hydrocarbon group having 6 to 20 carbon atoms may have a substituent group represented by R ^44, R ⁴¹ ~ R ⁴⁴ may have a substituent represented by the group In combination with an aralkyl group having 7 to 30 carbon atoms, it is more preferable to combine with an aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ⁴¹ to R ⁴⁴ that may have substituents, and those represented by R ⁴¹ to R ⁴⁴ may have The aromatic hydrocarbon ring (benzene ring) in the aralkyl group having 7 to 30 carbon atoms of the substituent is bonded at the para position viewed from the bonding position with the nitrogen atom.

However, when -SO ₂ -N ^-- SO ₂ -R ^f or -SO ₃ ^- is bonded to the aromatic hydrocarbon group or aralkyl group, -SO ₂ -N ^-- SO ₂ -R ^f or -SO ₃ ^-It is preferably directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group or aralkyl group. That is, -SO ₂ -N ^-- SO ₂ -R ^f or -SO ₃ ^- preferably replaces the hydrogen atom bonded to the aromatic hydrocarbon ring.

-SO ₂ -N ^-- SO ₂ -R ^f and -SO ₃ ^- may be bonded to the same aromatic hydrocarbon ring, but are preferably bonded to different aromatic hydrocarbon rings.

Furthermore, the compound (A-I) preferably does not have an ethylenically unsaturated bond.

As the compound (AI), also preferably having -SO ₂ -N ^- -SO ₂ -R ^f does not have -SO ₃ ^- and a compound having -SO ₂ -N ^- -SO ₂ -R ^f, and -SO ₃ ^- The compound used together. In this case, having a -SO ₂ -N ^- -SO ₂ -R ^f does not have -SO ₃ ^- and a compound having -SO ₂ -N ^- mol of compound ^- -SO ₂ -R ^f -SO ₃ and ratio (having a -SO ₂ -N ^- -SO ₂ -R ^f does not have -SO ₃ ^- compound / having -SO ₂ -N ^- -SO ₂ -R ^f, and -SO ₃ ^- compound) is preferably 0.01 or more , More preferably 0.05 or more, still more preferably 0.1 or more, may be 50 or less, more preferably 10 or less, still more preferably 5 or less, particularly preferably, 1 or less.

The compound (A-I) is preferably a compound represented by the following formula (A-I1).

[In formula (A-I1), R ⁸¹ to R ⁹⁰ each independently represent a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbon atoms, a halogen atom, -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f .

k1 represents the sum of the number of -SO ₃ ^-and the number of -SO ₂ -N ^-- SO ₂ -R ^f that the compound represented by the formula (A-I1) has.

R ⁴¹ , R ⁴³ , R ⁴⁷ to R ⁵⁴ , T ¹ , Mr ⁺ , r, R ^f have the same meaning as above.

However, the compound represented by the formula (A-I1) has at least one -SO ₂ -N ^-- SO ₂ -R ^f . ]

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁸¹ to R ⁹⁰ include the same groups as those exemplified as the saturated hydrocarbon group represented by R ⁴¹ . As R ⁸¹ to R ⁹⁰ , a hydrogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms, -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f are preferable, and a hydrogen atom, -SO ₃ ^- or -SO is more preferable ₂ -N ^-- SO ₂ -R ^f , more preferably a hydrogen atom or -SO ₂ -N ^-- SO ₂ -R ^f .

In addition, -SO ₂ -N ^-- SO ₂ -R ^f or -SO ₃ ^- preferably (e) is contained as any of the above-mentioned R ⁴⁷ to R ⁵⁴ , or (f) is contained as any of R ⁸¹ to R ⁹⁰ It is contained in one, or (g) is combined with an aromatic hydrocarbon group having 6 to 20 carbons substituted by a hydrogen atom of an aromatic heterocyclic ring represented by T ¹ , or exists as a combination of these (e) to (g), more preferably It exists as (f), (g), or a combination of these (f)-(g), More preferably, it exists as (f). In addition, among R ⁸¹ to R ⁹⁰ , one or more selected from R ⁸⁶ and R ⁸⁹ is preferred.

The number of -SO ₂ -N ^-- SO ₂ -R ^f contained in the compound (A-I1) is preferably 1-7, more preferably 1-4, and still more preferably 1 or 2. In addition, when the compound (A-I1) has -SO ₂ -N ^-- SO ₂ -R ^f and -SO ₃ ^- , the compound (A-I1) contains at least one -SO ₂ -N ^-- SO ₂ The total number (k1) of -R ^f , -SO ₂ -N ^-- SO ₂ -R ^f and -SO ₃ ^- is preferably 2-7, more preferably 2-4, and still more preferably 2.

As the compound (A-I1), a compound having -SO ₂ -N ^-- SO ₂ -R ^{f but} not -SO ₃ ^-and a compound having -SO ₂ -N ^-- SO ₂ -R ^f and -SO _{Combination of 3} ^- compounds. In this case, having a -SO ₂ -N ^- -SO ₂ -R ^f does not have -SO ₃ ^- and a compound having -SO ₂ -N ^- mol of compound ^- -SO ₂ -R ^f -SO ₃ and ratio (having a -SO ₂ -N ^- -SO ₂ -R ^f does not have -SO ₃ ^- compound / having -SO ₂ -N ^- -SO ₂ -R ^f, and -SO ₃ ^- compound) is preferably 0.01 or more , More preferably 0.05 or more, still more preferably 0.1 or more, may be 50 or less, more preferably 10 or less, still more preferably 5 or less, and particularly preferably, may be 1 or less.

As the compound (A-I), as shown in the following Tables 1 to 12, the compound (A-I-1) to the compound (A-I-632) represented by the formula (A-I-I) and the like can be cited. In the table, * indicates the bonding end.

However, the compound represented by formula (AII) having two -SO ₂ -N ^- -SO ₂ -CF _3, or having an -SO ₂ -N ^- -SO ₂ -CF ₃ and a -SO ₃ ^-, The -SO ₂ -N ^-- SO ₂ -CF ₃ or -SO ₃ ^- is contained as any of R ^h , or is bonded to the aromatic hydrocarbon ring (benzene ring) of the aromatic hydrocarbon group represented by Ph1 to Ph12, Preferably, the para position of the aromatic hydrocarbon ring (benzene ring) bonded to the aromatic hydrocarbon group represented by Ph1 to Ph12 in R ⁴¹ to R ⁴⁴ from the bonding end.

In Tables 1-12, Me means methyl, Et means ethyl, iPr means isopropyl, Bt means n-butyl, EOE means ethoxyethyl, 14Bt means butane-1,4-diyl, Ph1~ Ph12 means a group represented by the following formula. In the formula, * represents the bonding end.

In addition, as the compound (A-I), as shown in Table 13 below, compounds (A-I-634) to (A-I-657) represented by formula (A-I-II) and the like can also be cited. In the table, * indicates the bonding end.

However, the compound represented by the formula (AI-II) has on average one -SO ₂ -N ^-- SO ₂ -CF ₃ and -SO ₂ -NH-SO ₂ -CF ₃ , the -SO ₂ -N ^-- SO ₂ -CF ₃ and -SO ₂ -NH-SO ₂ -CF ₃ are contained as any of R ^h , or an aromatic hydrocarbon ring (benzene ring) with an aromatic hydrocarbon group represented by any of Ph1, Ph13, and Ph14 ) Combine.

In Table 13, Me represents methyl, Et represents ethyl, iPr represents isopropyl, Bt represents n-butyl, EOE represents ethoxyethyl, Hex represents n-hexyl, Ph1, Ph13, Ph14 are represented by the following formula Represents the group.

In the formula, * represents the bonding end.

The compound (A-I) can also be used by mixing a compound represented by the following formula (A-III) (hereinafter also referred to as a compound (A-III)).

[In formula (A-III), R ^21a to R ^24a each independently represent a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbons, or an optionally substituted carbon atoms, an aralkyl group having 7 to 30, the aromatic hydrocarbon group and the aralkyl group may have a substituent group may be ₃ is -SO ^-, in which a saturated hydrocarbon group having 1 to 20 carbon atoms, a saturated hydrocarbon group contained in the The hydrogen atom may be substituted by a substituted or unsubstituted amine group or a halogen atom. When the saturated hydrocarbon group having 1 to 20 carbon atoms is an alkyl group having 2 to 20 carbon atoms, the methylene group contained in the alkyl group may be Replace with oxygen atom or -CO-. However, in this C2-C20 alkyl group, adjacent methylene groups are not simultaneously replaced with oxygen atoms, and terminal methylene groups are not replaced with oxygen atoms or -CO-. R ^21a and R ^22a may be combined with the nitrogen atom to which they are combined to form a ring, and R ^23a and R ^24a may be combined with the nitrogen atom to which they are combined to form a ring.

R ^27a to R ^34a each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, -SO ₃ ^- or an alkyl group having 1 to 8 carbons, and the methylene group constituting the alkyl group may be replaced with an oxygen atom or- CO-. R ^28a and R ^32a may combine with each other to form -NH-, -S-, or -SO ₂ -.

The ring T ¹⁰ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms. The aromatic hydrocarbon group may have a substituent group may be -SO ₃ ^-.

M ^r+ and r have the same meaning as above.

k2 represents the number of -SO ₃ ^- possessed by the compound represented by formula (A-III).

However, the compound represented by the formula (A-III) having at least one -SO ₃ ^-. ]

The saturated hydrocarbon groups, aromatic hydrocarbon groups, and aralkyl groups represented by R ^21a to R ^24a each include the same groups as the saturated hydrocarbon groups, aromatic hydrocarbon groups, and aralkyl groups represented by R ⁴¹ to R ⁴⁴ .

In addition, as the alkyl group represented by R ^27a to R ^34a , the same groups as the alkyl group represented by R ⁴⁷ to R ^{54 can be} cited.

Further, (A-III) is preferably a compound having one or more -SO ₃ ^-, in particular, -SO ₃ ^- and more preferably (a ') according to any R ^27a ~ R ^34a is a contained, or is used as (b') Combine with the above-mentioned R ^21a to R ^24a and optionally substituted aromatic hydrocarbon groups having 6 to 20 carbon atoms, or (c') and R ^21a to R ^24a and optionally substituted carbon numbers 7 to 30 Or (d') and any one of the aromatic hydrocarbon groups having 6 to 20 carbon atoms substituted by the hydrogen atom of the aromatic heterocyclic ring represented by T ³ , or these (a') ~(d The combination of') is more preferably (b'), (c'), (d') or a combination of these (b') to (d'). The number of -SO ₃ ^- is preferably 0-6, more preferably 1-6, and still more preferably 1-3.

-SO ₃ ^- may be bonded to the same aromatic hydrocarbon ring, but is preferably bonded to different aromatic hydrocarbon rings.

In the case of mixing compound (AI) and compound (A-III), the content of compound (A-III) relative to 100 mol of compound (AI) is preferably 1 mol or more, more preferably 20 mol or more, and still more preferably 40 mol or more, preferably 90 mol or less, more preferably 80 mol or less, and even more preferably 70 mol or less.

Compound (AI), for example, can be made into compound (A-III) by sulfonating a compound represented by formula (A-IV) (hereinafter sometimes referred to as compound (A-IV)), and can be made into compound (A-III) by the following formula (A-IV) II) The compound shown is produced by reacting. The compound (AI) can react with halide (preferably chloride), acetate, phosphate, sulfate, silicate, cyanide, etc., containing the r-valent metal ion Mr ⁺ as required. Compound (A-IV) is preferably hydrochloride, phosphate, perchlorate, BF ₄ salt, PF ₆ salt, or the like.

[In formula (A-IV), R ^1a to R ^4a each independently represent a saturated hydrocarbon group with 1 to 20 carbons, an alkyl group with 2 to 20 carbons, which may be substituted by a substituted or unsubstituted amine group or a halogen atom, and The methylene group constituting the alkyl group is substituted with an oxygen atom or -CO-, an aromatic hydrocarbon group having 6 to 20 carbons which may have a substituent, and an aralkyl group having 7 to 30 carbons which may have a substituent Or a hydrogen atom. R ^1a and R ^2a may be combined with the nitrogen atom to which they are combined to form a ring, and R ^3a and R ^4a may be combined with the nitrogen atom to which they are combined to form a ring.

R ^7a to R ^14a each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and the methylene group constituting the alkyl group may be replaced with an oxygen atom or -CO-. R ^8a and R ^12a may be combined with each other to form -NH-, -S-, or -SO ₂ -.

The ring T ¹¹ represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms.

M ¹ represents Cl ^-, phosphate ion, perchlorate _{^{ion, BF 4 -, PF 6 -}} . ]

[In formula (A-III), R ^21a to R ^24a , R ^27a to R ^34a , ring T ¹⁰ , Mr ⁺ , r, and k2 have the same meaning as above.

However, the compound represented by the formula (A-III) having at least one -SO ₃ ^-. ]

[In formula (A-II), R ^f has the same meaning as above. ]

[In formula (AI), R ⁴¹ to R ⁴⁴ , R ⁴⁷ to R ⁵⁴ , ring T ¹ , k, Mr ⁺ and r have the same meaning as above. ]

As the method of sulfonation, various known methods can be cited, for example, the method described in Journal of Organic Chemistry, (1994), Vol. 59, #11, pp. 3232-3236.

The compound (A-I) of the present invention can be applied to fiber products, for example, the fiber material can be colored by kneading, impregnating, adhering, etc. in the fiber material.

The coloring composition of the present invention contains a colorant (A), and the colorant (A) contains a compound (A-I). The coloring composition of the present invention preferably further contains a solvent (E), and more preferably further contains a resin (B), a polymerizable compound (C), and a polymerization initiator (D). The polymerization initiator (D1) and the leveling agent (F) may be further included.

Hereinafter, the colored composition containing the resin (B), the polymerizable compound (C), and the polymerization initiator (D) may be referred to as a colored curable resin composition.

In this specification, the compound exemplified as each component can be used singly or in combination of multiple types unless otherwise specified.

Solvent (E)

The solvent (E) is not particularly limited, and solvents generally used in this field can be used. For example, ester solvents (solvents containing -COO- and no -O- in the molecule), ether solvents (solvents that contain -O- and no -COO- in the molecule), ether ester solvents (Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- and no -COO- in the molecule), alcohol-soluble Agents (solvents containing OH in the molecule and not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfide, etc.

As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isoamyl acetate, Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetyl acetate, ethyl acetyl acetate, cyclohexane Alcohol acetate, γ-butyrolactone, etc.

As the ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methyl Oxyoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, Diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether and methyl anisole, etc.

Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. Ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Ester, 2-methoxypropyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate, 2-methoxy-2-methyl propionate, 2-ethyl Ethyl oxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol mono B Base ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate Alcohol monobutyl ether acetate and dipropylene glycol methyl ether acetate, etc.

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

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

As an aromatic hydrocarbon solvent, benzene, toluene, xylene, 1,3,5-trimethylbenzene, etc. are mentioned.

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 kinds.

Among them, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, Dipropylene glycol methyl ether acetate, 3-methoxy-1-butanol, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl lactate, N-methylpyrrolidone , 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, etc., more preferably ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetic acid Ester, dipropylene glycol methyl ether acetate, 3-methoxy-1-butanol, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl lactate, N-methyl Pyrrolidone.

When the solvent (E) is included, the content of the solvent (E) is preferably 70 to 95% by mass relative to the total amount of the coloring composition, and more Preferably it is 75-92 mass %. In other words, the total solid content of the coloring composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. If the content of the solvent (E) is in the above-mentioned range, the flatness during application becomes good, and the color density is not insufficient when the color filter is formed, so there is a tendency for the display characteristics to become good.

In this specification, the "total amount of solid content" refers to the total amount of the components from the coloring composition from which the solvent (E) has been removed. The total amount of solid content and the content of each component relative to it can be measured by a known analysis means such as liquid chromatography or gas chromatography.

Colorant (A)

The colorant (A) may be a dye containing the compound (AI) of the present invention as an active ingredient alone, but for the purpose of toning, that is, to adjust the spectral characteristics, it may further contain other dyes (A1), pigments (P), Or a mixture of them.

Examples of the dye (A1) include dyes such as oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. Examples include A compound classified as a dye in Society of Dyers and Colourists, and a known dye described in the dyeing note (Sei Dyesha). In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, azomethine dyes, square Acid dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes. Among these, organic solvent-soluble dyes are preferably used.

Specific examples of the dye (A1) include CI Solvent Yellow 4 (hereinafter the description of CI Solvent Yellow is omitted, and only the serial number is given.), 14, 15, 23, 24, 25, 38, 62, 63, 68, 79 , 81, 82, 83, 89, 94, 98, 99, 162; CI Solvent Red 24, 45, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 145, 160, 218; CI solvent orange 2, 7, 11, 15, 26, 41, 54, 56, 99; CI solvent blue 4, 5, 37, 67, 70, 90; CI solvent green 1, 4, 5, 7, 34 , 35 and other CI solvent dyes, CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 91, 92, 97, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 151, 155, 157, 160, 161, 163,168,169,172,177,178,179,184,190,193,196,197,199,202,203,204,205,207,211,212,214,220,221,228,230, 232, 235, 238, 240, 242, 243, 251, 274, 289; CI 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; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64 , 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet 6B, 7, 9, 17, 19, 30, 102, 120; CI 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; CI acid green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109 and other CI acid dyes, CI 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; CI 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; 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 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 Direct Orange 26 , 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI direct purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI 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; CI direct green 25, 27, 31, 32, 34, CI direct dyes such as 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, CI disperse dyes such as CI Disperse Yellow 51, 54, 76, CI Basic Red 1, 10; CI Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68; CI basic dyes such as CI Basic Green 1, CI Reactive Yellow 2, 76, 116; CI Reactive Orange 16; CI Reactive Dyes such as CI Reactive Red 36, CI Mordant Yellow 5, 8, 10, 16, 20, 26, 30 , 31, 33, 42, 43, 45, 56, 61, 62, 65; CI Mordant Red 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; CI mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI Mordant Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; CI Mordant 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; CI mordant green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53 and other CI mordant dyes, CI vat green 1 and other CI vat dyes, etc. Among them, purple dyes are preferred.

The pigment (P) is not particularly limited, and known pigments can be used. For example, pigments classified as pigments in the Excellent Index (published by The Society of Dyers and Colourists) can be cited.

Examples of pigments include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; 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 , 216, 224, 242, 254, 255, 264, 265 and other red pigments; CI pigment blue 15, 15: 3, 15: 4, 15: 6, 60 and other cyan pigments; CI pigment violet 1, 19, 23, 29 , 32, 36, 38 and other purple pigments; CI Pigment Green 7, 36, 58 and other green pigments; CI Pigment Brown 23, 25 and other brown pigments; CI Pigment Black 1, 7 and other black pigments.

The pigment (P) is preferably a phthalocyanine pigment and a dioxazine pigment, and more preferably at least one selected from the group consisting of C.I. Pigment Blue 15:6 and Pigment Violet 23. By including the above-mentioned pigment, the transmission spectrum is easily optimized, and the light resistance and chemical resistance of the color filter become good.

For pigments, if necessary, rosin treatment, surface treatment using pigment derivatives introduced with acidic or basic groups, etc., grafting treatment to the surface of the pigment using polymer compounds, etc., and micronization with sulfuric acid Method, etc., or use to remove impurities Cleaning treatment of organic solvents, water, etc., removal treatment of ionic impurities by ion exchange methods, etc. The pigment preferably has a uniform particle size.

The pigment contains a pigment dispersant and is subjected to a dispersion treatment to obtain a pigment dispersion in a state where the pigment is uniformly dispersed in the solution. The pigments may be separately subjected to dispersion treatment, or plural kinds may be mixed and subjected to dispersion treatment.

(共榮社化學(株)製造)、

(註冊商標)(

(株)製造)、EFKA(註冊商標)(BASF公司製造)、

(註冊商標)(味之素

(株)製造)、Disperbyk(註冊商標)(

一株式會社製造)等。 As said pigment dispersing agent, surfactant is mentioned, for example, It may be any surfactant of a cationic type, an anionic type, a nonionic type, and amphoteric. Specifically, a polyester-based, polyamine-based, acrylic-based pigment dispersant, etc. can be cited. These pigment dispersants can be used individually or in combination of 2 or more types. As a pigment dispersant, it is represented by a trade name, and includes KP (manufactured by Shin-Etsu Chemical Co., Ltd.),

(Manufactured by Kyoeisha Chemical Co., Ltd.),

(Trademark)(

(Manufactured by Co., Ltd.), EFKA (registered trademark) (manufactured by BASF Corporation),

(Registered trademark) (Ajinomoto

(Manufactured by Co., Ltd.), Disperbyk (registered trademark) (

One Co., Ltd.) and so on.

In the case of using a pigment dispersant, the amount used is preferably 100 parts by mass or less, and more preferably 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the pigment. If the amount of the pigment dispersant used is within the above range, there is a tendency to obtain a pigment dispersion in a uniformly dispersed state.

The content of the compound (AI) relative to the total solid content is preferably 5% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and still more preferably 5% by mass or more and 50% by mass. Less than mass%.

In addition, the content of the compound (A-I) relative to the total amount of the colorant (A) is preferably 1% by mass or more and 100% by mass or less, and more preferably 10% by mass or more and 100% by mass or less.

In addition, when compound (AI) and compound (A-III) are used in combination, the total content of compound (AI) and compound (A-III) is preferably 10% by mass relative to the total solid content. Above and 70% by mass or less, and more preferably 15% by mass or more and 60% by mass or less.

When the dye (A1) is contained, its content relative to the total amount of the colorant (A) is preferably 0.5% by mass or more and 90% by mass or less, and more preferably 0.5% by mass or more and 70% by mass or less. When the pigment (P) is contained, its content relative to the total amount of the colorant (A) 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 or less.

The content of the coloring agent (A) relative to the total solid content is preferably 5 mass% or more and 70 mass% or less, more preferably 5 mass% or more and 60 mass% or less, and still more preferably 5 mass% or more and 50% by mass or less.

Resin (B)

The resin (B) is preferably an alkali-soluble resin (B). The alkali-soluble resin (B) (hereinafter sometimes referred to as "resin (B)") is a copolymer containing structural units derived from at least one monomer (Ba) selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides.

As such resin (B), the following resin [K1]-[K6] etc. are mentioned.

Resin [K1] has a resin derived from unsaturated carboxylic acid and unsaturated carboxylic anhydride The structural unit of at least one of the monomers (a) (hereinafter sometimes referred to as "(a)") and the monomer (b) derived from a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (Hereinafter sometimes referred to as "(b)") copolymer of structural units; resin [K2] has structural units derived from (a), structural units derived from (b), and monomers copolymerizable with (a) Body (c) (However, it is different from (a) and (b).) (hereinafter sometimes referred to as "(c)") copolymer of structural units; resin [K3] has structural units derived from (a) and Copolymer of the structural unit derived from (c); resin [K4] has a structural unit added to the structural unit from (a) and a resin (copolymer) derived from the structural unit of (c); resin [ K5] A resin (copolymer) having a structural unit added to (a) and a structural unit derived from (b) and a structural unit derived from (c); resin [K6] has a resin (a) added to the structural unit derived from (b) A resin (copolymer) derived from the structural unit of (c) and the structural unit to which carboxylic anhydride is added further.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ortho-, meta-, and p-vinyl benzoic acid; maleic acid, fumaric acid, citraconic acid , Mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6- Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, dimethyltetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid; Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[ 2.2.1]Hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, itaconic anhydride , 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride Unsaturated dicarboxylic acid anhydrides such as formic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; succinic acid mono[2-(methyl) Unsaturated mono[(meth)acryloxy group of polycarboxylic acid with two or more valences, such as acryloxyethyl] ester and phthalic acid mono[2-(meth)acryloxyethyl] ester Alkyl]esters; α-(hydroxymeth)acrylic acid, such as unsaturated acrylates containing hydroxyl and carboxyl groups in the same molecule.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an aqueous alkali solution.

(b) refers to, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond Polymeric compound.

(b) A monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group is preferred.

It should be noted that in this specification, "(meth)acrylic acid" means selected from At least one of acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

Examples of (b) include monomers (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), and an oxetanyl group and an ethylenically unsaturated bond. The monomer (b2) (hereinafter sometimes referred to as "(b2)"), the monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), etc.

Examples of (b1) include monomers (b1-1) having a structure in which linear or branched aliphatic unsaturated hydrocarbons are epoxidized (hereinafter sometimes referred to as "(b1-1)"), A monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter may be referred to as "(b1-2)").

Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidyl vinyl ether , O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-Methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2, 4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3, 4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidoxymethyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, etc.

(註冊商標)2000；(株)大賽璐製造)、(甲基)丙烯酸3,4-環氧環己基甲酯(例如，

(註冊商標)A400；(株)大賽璐製造)、(甲基)丙烯酸3,4-環氧環己基甲酯(例如，

M100；(株)大賽璐製造)、由式(BI)表示的化合物和由式(BII)表示的化合物等。 As (b1-2), vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example,

(Registered trademark) 2000; (manufactured by Daicel), 3,4-epoxycyclohexyl methyl (meth)acrylate (for example,

(Registered trademark) A400; (manufactured by Daicel), 3,4-epoxycyclohexyl methyl (meth)acrylate (for example,

M100; (manufactured by Daicel Co., Ltd.), a compound represented by formula (BI), a compound represented by formula (BII), and the like.

[In formula (BI) and formula (BII), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group.

X ^a and X ^b represents a single ^{bond, * - R c -, *} - R c -O -, * - R c -S- or * -R ^c -NH-.

R ^c represents an alkylene group having 1 to 6 carbon atoms.

* Indicates the bonding end with O. ]

As R ^a, R ^b is an alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl and the like.

Examples of the alkyl groups in which the hydrogen atoms of R ^a and R ^b are substituted with hydroxy groups include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, and 3-hydroxypropyl. Group, 1-hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.

As R ^a and R ^b , a hydrogen atom, an alkyl group having 1 to 4 carbons, or a hydroxyalkyl group having 1 to 4 carbons is preferable, and a hydrogen atom or an alkyl group having 1 to 4 carbons is more preferable. Specifically, Preferably, a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group are mentioned, and more preferably, a hydrogen atom and a methyl group are mentioned.

Examples of the alkylene group of R ^c include linear or branched alkylene groups, and specific examples include methylene, ethylene, propane-1,3-diyl, and butane-1 ,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl and other linear alkylene groups; propane-1,2-diyl and other branched chain alkylene groups.

X ^a and X ^{b are} preferably a single bond, *-R ^c -, or *-R ^c -O-, more preferably a single bond, or *-R ^c -O-, and particularly preferably a single bond and methylene , Ethylene, *-CH ₂ -O- and *-CH ₂ CH ₂ -O-, more preferably single bond, *-CH ₂ CH2-O- (* represents the bonding end with O) .

As the compound represented by formula (BI), a compound represented by any one of formula (BI-1) to formula (BI-15), and the like can be cited. Among them, the formula (BI-1), the formula (BI-3), the formula (BI-5), the formula (BI-7), the formula (BI-9) or the formula (BI-11) ~ the formula (BI- The compound represented by 15) is more preferably a compound represented by formula (BI-1), formula (BI-7), formula (BI-9), or formula (BI-15).

As a compound represented by formula (BII), the compound etc. which are represented by any one of formula (BII-1)-formula (BII-15) are mentioned. Among them, the formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) or formula (BII-11) ~ formula (BII- The compound represented by 15) is more preferably a compound represented by formula (BII-1), formula (BII-7), formula (BII-9), or formula (BII-15).

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

As (b2), a monomer having an oxetanyl group and a (meth)acryloxy group is more preferable. As (b2), 3-methyl-3- Methacryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane Cyclobutane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methylpropenyloxyethyloxetane, 3-methyl-3 -Acrylic oxyethyl oxetane, 3-ethyl-3-methacrylic oxyethyl oxetane, 3-ethyl-3-propenoxy ethyl oxetane Butane etc.

V # 150、大阪有機化學工業(株)製造)、甲基丙烯酸四氢糠酯等。 As (b3), a monomer having a tetrahydrofuran group and a (meth)acryloxy group is more preferable. As (b3), specifically, tetrahydrofurfuryl acrylate (for example,

V # 150, Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, etc.

As (b), (b1) is preferable from the point which can further improve the reliability of the heat resistance, chemical resistance, etc. of the color filter obtained. Furthermore, (b1-2) is more preferable in terms of excellent storage stability of the coloring composition.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, and tert-butyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, Cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (in this technical field As a common name, it is called "dicyclopentyl (meth)acrylate." In addition, it is sometimes called "tricyclodecyl (meth)acrylate".), tricyclo (meth)acrylate [5.2.1.0 ^{2 ,6} ] decene-8-yl ester (in this technical field, as a common name, called "(meth)acrylate dicyclopentenyl ester".), (meth)acrylate dicyclopentyloxyethyl, (meth) Base) isobornyl acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (Meth)acrylates such as benzyl (meth)acrylate; (meth)acrylates containing hydroxyl groups such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; horses Diethyl ester, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters; 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 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-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5, 6-Bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxy Bicyclo[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-cyclohexyloxy Carbonyl carbonyl bicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonyl bicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1 ]Hept-2-ene, 5,6-bis(cyclohexoxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide, N-ring Hexylmaleimide, N-benzylmaleimide, N-succinimidyl- 3-maleimidin benzoate, N-succinimidyl-4-maleimidin butyrate, N-succinimidyl-6-maleimidin caproate, Dicarbonylimine derivatives such as N-succinimidyl-3-maleimine propionate, N-(9-acridinyl)maleimine; styrene, α-methylbenzene Aromatic compounds containing vinyl groups such as ethylene, m-methylstyrene, p-methylstyrene, vinyl toluene, and p-methoxystyrene; nitriles containing vinyl groups such as acrylonitrile and methacrylonitrile; Halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; vinyl-containing amides such as acrylamide and methacrylamide; esters such as vinyl acetate; 1,3-butadiene, isoprene, 2,3 -Diene such as dimethyl-1,3-butadiene, etc.

Among these, as (c), from the viewpoints of copolymerization reactivity and heat resistance, aromatic compounds containing vinyl groups, dicarbonylimine derivatives, and bicyclic unsaturated compounds are preferred. Specifically, styrene, vinyl toluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]heptane-2 -Ene, etc.

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

If the ratio of the structural units of the resin [K1] is within the above-mentioned range, the storage stability of the coloring composition, the developability when forming a colored pattern, and And the color filter obtained tends to be excellent in solvent resistance.

The resin [K1] can, for example, refer to the method described in the document "Experimental Method of Polymer Synthesis" (Otsu Takayuki Publishing Co., Ltd., Chemical Doujin 1st Edition, First Printing Issued on March 1, 1972) and the document Manufactured by the cited literature.

Specifically, it can be exemplified by filling the predetermined amounts of (a) and (b), polymerization initiator, solvent, etc. in a reaction vessel, for example, replacing oxygen with nitrogen to form a deoxygenating atmosphere, heating and keeping warm while stirring method. In addition, the polymerization initiator, solvent, etc. used here are not particularly limited, and those generally used in this field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), organic peroxides (Benzyl peroxide etc.) As a solvent, what is necessary is just to dissolve each monomer, and the solvent etc. mentioned as the solvent (E) of the coloring composition of this invention are mentioned.

In addition, for the obtained copolymer, the reaction solution may be used as it is, a concentrated or diluted solution may be used, or a product taken out as a solid (powder) by a method such as reprecipitation may be used. In particular, during the polymerization, by using the solvent contained in the coloring composition of the present invention as a solvent, the reacted solution can be used as it is in the preparation of the coloring composition of the present invention, so that the The manufacturing process of the coloring composition is simplified.

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

If the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the colored composition, the developability when forming a colored pattern, and the resulting color filter have excellent solvent resistance, heat resistance, and mechanical strength Propensity.

The resin [K2] can be manufactured in the same manner as the method described as the manufacturing method of the resin [K1], for example.

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

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

Resin [K4] can be produced by obtaining a copolymer of (a) and (c) and adding the cyclic ether with 2 to 4 carbon atoms in (b) to the carboxylic acid and/or carboxylic anhydride of (a) .

First, the copolymer of (a) and (c) can be produced in the same manner as the method described as the production method of resin [K1]. In this case, the ratio of the structural unit derived from each monomer is preferably the same as the ratio listed in the resin [K3].

Next, the cyclic ether having 2 to 4 carbon atoms in (b) is reacted with a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the above-mentioned copolymer.

Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced by nitrogen to air, and the reaction catalyst of (b), carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris(dimethylamino) (Methyl)phenol, etc.) and a polymerization inhibitor (for example, hydroquinone, etc.) are put in a flask, and reacted at 60 to 130°C for 1 to 10 hours, for example, to produce resin [K4].

The amount of (b) used is preferably 5 to 80 moles, and more preferably 10 to 75 moles relative to 100 moles of (a). By adjusting the use amount of (b) to this range, the storage stability of the coloring composition, the developability during pattern formation, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern become good. Propensity. Since the reactivity of the cyclic ether is high, and the unreacted (b) is unlikely to remain, the (b) used for the resin [K4] is preferably (b1), and more preferably (b1-1).

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

For the feeding method, reaction temperature and reaction time of each reagent The reaction conditions for the intermittence can be appropriately adjusted in consideration of manufacturing equipment, heat generation from polymerization, and the like. In addition, in the same manner as the polymerization conditions, it is possible to appropriately adjust the feeding method and the reaction temperature in consideration of the production equipment, the amount of heat generated by polymerization, and the like.

In the production of resin [K5], as the first stage, the copolymer of (b) and (c) is obtained in the same manner as the method for producing resin [K1] described above. In the same manner as described above, the resulting copolymer may be used as it is, a concentrated or diluted solution, or a product taken out as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c), relative to the total number of moles of all the structural units constituting the copolymer of (b) and (c), is preferably a structural unit derived from (b): 5~ 95 mol% of structural units derived from (c): 5 to 95 mol%, more preferably structural units derived from (b): 10 to 90 mol% structural units derived from (c): 10 to 90 mol%.

Furthermore, as the second stage, under the same conditions as the production method of resin [K4], the copolymer of (a) having carboxylic acid or carboxylic anhydride and (b) and (c) derived from (b) The cyclic ether reacts to obtain resin [K5].

In the second stage, the amount of (a) used to react with the copolymer of (b) and (c) above is preferably 5 to 80 moles relative to 100 moles of (b). Due to the high reactivity of the cyclic ether, the unreacted (b) is not easy to remain, so it is used as For (b) of resin [K5], (b1) is preferable, and (b1-1) is more preferable.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride and resin [K5]. The carboxylic acid anhydride is reacted with the hydroxyl group produced by the reaction of the cyclic ether with the carboxylic acid or the carboxylic anhydride.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5]. Specifically, it can be obtained by reacting carboxylic anhydride with the cyclic ether derived from (b) and the carboxylic acid or carboxylic anhydride of (a) The generated hydroxyl groups are produced by reaction.

Examples of carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. . The amount of carboxylic anhydride used is preferably 0.5 to 1 mole with respect to 1 mole of the use amount of (a).

As the resin (B), specifically, 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, and 3,4-epoxy tricyclo (meth)acrylate [5.2 .1.0 ^2.6 ] Resins such as decyl ester/(meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (meth)acrylic acid Glycidyl ester/styrene/(meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2.6 ] decyl ester/(meth)acrylic acid/N-cyclohexyl maleate Imine copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2.6 ]decyl ester/(meth)acrylic acid/vinyl toluene copolymer, 3-methyl-3-(methyl) Resins such as acryloxymethyl oxetane/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(methyl) )Acrylic acid copolymer, benzyl (meth)acrylate/tricyclodecyl (meth)acrylate/(meth)acrylic acid copolymer and other resins [K3]; make glycidyl (meth)acrylate and (meth)acrylate Resin made by addition of benzyl acrylate/(meth)acrylic acid copolymer, adding glycidyl (meth)acrylate and tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer Resins such as resins made by the addition of glycidyl (meth)acrylate and tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer [K4 ]; Make (meth)acrylic acid and (meth)acrylic acid tricyclodecyl ester/(meth)acrylic acid glycidyl ester copolymer reaction resin, make (meth)acrylic acid and (meth)acrylic acid tricyclodecyl ester /Styrene/glycidyl (meth)acrylate copolymer resin and other resins [K5]; make (meth)acrylic acid and tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate Resin [K6] etc., such as the resin obtained by reacting the copolymer of ester, and tetrahydrophthalic anhydride.

The resin (B) is preferably one selected from the group consisting of resin [K1], resin [K2] and resin [K3], and more preferably one selected from resin [K2] and resin [K3]. If it is these resins, the developability of a coloring composition will be excellent. From the viewpoint of the adhesion between the colored pattern and the substrate, resin [K2] is more preferable.

The weight average molecular weight in terms of polystyrene of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. If the molecular weight is within the above range, there is coating The film hardness is improved, the residual film rate is also high, the solubility of the unexposed area in the developer is good, and the resolution of the colored pattern tends to be improved.

The degree of dispersion [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 in terms of solid content of the resin (B) is preferably 30 to 170 mg-KOH/g, more preferably 40 to 150 mg-KOH/g, and still 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 it can be determined, for example, by titration using an aqueous potassium hydroxide solution.

When the resin (B) is included, the content of the resin (B) relative to the total solid content is preferably 7 to 70% by mass, more preferably 13 to 65% by mass, and still more preferably 17 to 60% by mass . If the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film rate tend to increase.

Polymeric compound (C)

The polymerizable compound (C) is a compound that can be polymerized by living radicals and/or acid generated by the polymerization initiator (D), and examples thereof include compounds having polymerizable ethylenic unsaturated bonds, etc., preferably (former Base) Acrylate compound.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexyl carbitol acrylate. Ester, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc. and the above-mentioned (Ba), (Bb) and (Bc).

As the polymerizable compound having two ethylenically unsaturated bonds, for example, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate Base) acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. , Dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol nine (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, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) Among them, 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 2900 or less, and more preferably 250 to 1500.

When the polymerizable compound (C) is contained, the content of the polymerizable compound (C) relative to the total solid content is preferably 7 Mass% or more and 65% by mass or less, more preferably 10% by mass or more and 60% by mass or less, and still more preferably 12% by mass or more and 55% by mass or less.

In addition, when the resin (B) and the polymerizable compound (C) are contained, the content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] is calculated on a mass basis, It is preferably 20:80 to 80:20, more preferably 30:70 to 80:20.

If the content of the polymerizable compound (C) is within the above-mentioned range, the residual film rate during the formation of the colored pattern and the chemical resistance of the color filter tend to increase.

Polymerization initiator (D)

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids, etc., to initiate polymerization by the action of light and heat, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include O-acyl oxime compounds, alkyl phenyl ketone compounds, biimidazole compounds, triazine compounds, and acyl phosphine oxide compounds.

The above-mentioned O-acetoxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents the bonding end.

As the above-mentioned O- oxime compound, for example, N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzyl oxime Oxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-ylidene Amine, N-benzyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[ 9-Ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl- 6-{2-Methyl-4-(3,3-dimethyl-2,4-dioxolylmethoxy)benzyl}-9H-carbazol-3-yl]ethane -1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane -1-imine, N-benzyloxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-3-cyclopentyl Propan-1-one-2-imine, etc. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (the above are made by BASF), and N-1919 (made by ADEKA) can be used. Among them, the O- oxime compound is preferably selected from N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzyloxy 1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-benzyloxy-1-(4-phenylsulfanylphenyl)-3 -At least one of cyclopentylpropane-1-one-2-imine, more preferably N-benzyloxy-1-(4-phenylsulfanylphenyl)octane-1-one- 2-imine.

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

As a compound having a partial structure represented by formula (d2), for example, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl) Propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, 2-(dimethylamino)-2-[ (4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (the above are made by BASF Corporation) can be used.

As a compound having a partial structure represented by the formula (Dd3), for example, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4- (2-Hydroxyethoxy)phenyl)propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1- Oligomers of ketones, α,α-diethoxyacetophenone, benzyl dimethyl ketal, etc.

In terms of sensitivity, the alkyl phenyl ketone compound is preferably a compound having a partial structure represented by formula (d2).

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

[In formula (d4), R ^d1 to R ^d6 represent optionally substituted aryl groups having 6 to 10 carbon atoms. ]

Examples of the aryl group having 6 to 10 carbon atoms of ^Rd1 to ^Rd6 include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, and the like, and phenyl is preferred.

As a substituent which can substitute the aryl group of said R ^d1 -R ^d6 , a halogen atom, a C1-C4 alkoxy group, etc. are mentioned, for example. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example, Preferably it is a chlorine atom. As a C1-C4 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc. are mentioned, for example, Preferably it is a methoxy group.

As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-di (Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'- Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra (Alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2' -Bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Application Publication No. 62- 174204, etc.), imidazole compounds in which the phenyl group at the 4, 4', 5, 5'-position is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Application Laid-Open No. 7-10913 etc.). Among them, the compounds represented by the following formulas and their mixtures are preferred.

As the above-mentioned triazine compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(5-Methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl) Vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine Wait.

As the above-mentioned acylphosphine oxide compound, 2,4,6-trimethylbenzyldiphenylphosphine oxide, etc. are mentioned.

Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether can be cited ; Benzophenone, o-benzyl methyl benzoate, 4-phenyl benzophenone, 4-benzyl-4'-methyl diphenyl sulfide, 3,3',4 ,4'-Tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethyl Quinone compounds such as anthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, etc.

These are preferably used in combination with the polymerization initiator (D1) (particularly amines) described later.

As a polymerization initiator that generates acid, for example, 4-hydroxyphenyl dimethyl sulfonium-p-toluenesulfonate, 4-hydroxyphenyl dimethyl sulfonium hexafluoroantimonate, 4-acetoxy Phenyl dimethyl sulfonium-p-toluene sulfonate, 4-acetoxy phenyl methyl benzyl hexafluoroantimonate, triphenyl sulfonium-p-toluene sulfonic acid Onium salts such as triphenyl iodonium hexafluoroantimonate, diphenyl iodonium p-toluenesulfonate, diphenyl iodonium hexafluoroantimonate, etc., nitrobenzyl tosylate, benzene Azoin tosylate and so on.

As the polymerization initiator (D), a polymerization initiator that generates living radicals is preferred, specifically, a polymerization initiator selected from the group consisting of alkyl phenyl ketone compounds, triazine compounds, acyl phosphine oxide compounds, O- acyl oxime compounds, and The polymerization initiator of at least one of the imidazole compounds, more preferably, is a polymerization initiator containing an O-acetoxime compound.

When the polymerization initiator (D) is included, the content of the polymerization initiator (D) is preferably 0.1 parts by mass or more and 40 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) Hereinafter, it is more preferably 1 part by mass or more and 30 parts by mass or less.

Polymerization initiator (D1)

The polymerization initiation adjuvant (D1) is a compound or a sensitizer for accelerating the polymerization of a polymerizable compound whose polymerization has been initiated by a polymerization initiator. When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D).

As the polymerization initiation assistant (D1), amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like can be cited.

Examples of the above-mentioned amine compounds include alkanolamines such as triethanolamine, methyldiethanolamine, and triisopropanolamine; methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl ester, benzoic acid 2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl ester and other amino benzoic acid esters; N, N-Dimethyl p-toluidine; 4,4'- Bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino) ) Alkylamino benzophenones such as benzophenone and the like, among them, alkylamino benzophenones are preferred, and 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) can be used.

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

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Chloro-4-propoxythioxanthone and so on.

Examples of the above-mentioned carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, and dimethylphenylsulfide. Alkyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, Phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, etc.

When using these polymerization initiation aids (D1), the content is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and polymerizable compound (C) Copies. If the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to increase.

Leveling agent (F)

As the leveling agent (F), organosilicon surfactants, fluorine surfactants, organosilicon surfactants having fluorine atoms, and the like can be cited. These may have a polymerizable group in the side chain.

DC3PA、SH7PA、DC11PA、SH21PA、SH28PA、SH29PA、SH30PA、SH8400(東麗-道康寧(株)製造)、KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越化學工業(株)製造)、TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF4446、TSF4452和TSF4460(

‧

‧

‧

合同會社製造)等。 Examples of the organosilicon-based surfactant include surfactants having siloxane bonds in the molecule, and the like. Specifically, one can cite

DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (manufactured by Toray-Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400 , TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460(

‧

‧

‧

Contract company manufacturing) etc.

(註冊商標)FC430、FC431(住友3M(株)製造)、

(註冊商標)F142D、F171、F172、F173、F177、F183、F554、R30、RS-718-K(DIC(株)製造)、

(註冊商標)EF301、EF303、EF351、EF352(三菱

電子化成(株)製造)、

(註冊商標)S381、S382、SC101、SC105(旭硝子(株)製造)和E5844((株)

研究所製造)等。 Examples of the above-mentioned fluorine-based surfactants include surfactants having a fluorocarbon chain in the molecule, and the like. Specifically, one can cite

(Registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.),

(Registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC Corporation),

(Registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi

Electronic Chemicals Co., Ltd.),

(Registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (co., Ltd.)

Research Institute) etc.

(註冊商標)R08、BL20、F475、F477和F443(DIC(株)製造)等。 Examples of the aforementioned organosilicon surfactants having fluorine atoms include surfactants having siloxane bonds and fluorocarbon chains in the molecule. Specifically, one can cite

(Registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Co., Ltd.), etc.

When the leveling agent (F) is contained, its content relative to the total amount of the coloring composition is preferably 0.001% by mass to 0.5% by mass, more preferably 0.002% by mass to 0.4% by mass, and still more preferably 0.005 mass% or more and 0.3 mass% or less. If the content of the leveling agent (F) is within the above-mentioned range, the flatness of the color filter can be improved.

Other ingredients

The coloring composition may contain additives known in the technical field such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and the like as necessary.

Manufacturing method of coloring composition

Furthermore, the coloring composition in the case of containing resin (B), polymerizable compound (C), polymerization initiator (D), and solvent (E), for example, can be obtained by combining compound (AI), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), coloring agent (A) other than compound (AI), leveling agent (F), polymerization initiator (D1) and others if necessary The ingredients are mixed and prepared.

When the pigment (P) is included, the pigment is preferably mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle size of the pigment becomes about 0.2 μm or less. At this time, a part or all of the above-mentioned pigment dispersant and resin (B) can be blended as needed. By mixing the remaining components in the pigment dispersion liquid obtained in this way to a predetermined concentration, The target coloring composition can be prepared.

In the present invention, the above-mentioned compound (A-I) can be mixed with a solvent to prepare a colored dispersion. After the colored dispersion liquid is prepared, it is further mixed with the resin (B), the polymerizable compound (C), the polymerization initiator (D), etc. to form a coloring composition, and the heat resistance when used as a color filter can be further improved.

As the solvent, any solvent can be used as long as it can be used as the solvent (E) of the coloring composition. In order to disperse the compound (AI), a particularly preferred solvent (E1) is, for example, an ether ester solvent. More preferably, it may be exemplified by etherification of one hydroxyl group of an alkylene glycol or polyalkylene glycol, and etherification of the remaining hydroxyl group. Esterification solvents, such as 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, dipropylene glycol methyl ether acetate, etc. These may be used alone or in plural.

The amount of the solvent (E1) is, for example, 4 to 1000 parts by mass, preferably 6 to 200 parts by mass, and more preferably 9 to 100 parts by mass relative to 1 part by mass of the compound (A-I).

(共榮社化學(株)製造)、

(

(株)製造)、EFKA(BASF公司製造)、

(味之素

(株)製造)、Disperbyk、BYK(

公司製造)等。 When preparing a colored dispersion, it is preferable to use a dispersant. As the dispersant, for example, known pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, etc. can be used. These pigment dispersants may be used alone or in combination of two or more kinds. As a pigment dispersant, it is represented by a trade name, and includes KP (manufactured by Shin-Etsu Chemical Co., Ltd.),

(Manufactured by Kyoeisha Chemical Co., Ltd.),

(

(Manufactured by Co., Ltd.), EFKA (manufactured by BASF Corporation),

(Ajinomoto

(Manufactured by Co., Ltd.), Disperbyk, BYK (

Company manufacturing) etc.

The amount of the dispersant is, for example, 1 to 1000 parts by mass, preferably 3 to 100 parts by mass, more preferably 5 to 90 parts by mass, and particularly preferably 10 to 80 parts by mass relative to 100 parts by mass of compound (A-I).

In addition, when the dye (A1) is contained in the coloring composition, a part or all, preferably all of the dye (A1) may be contained in advance as necessary. The amount of the dye (A1) in the coloring dispersion liquid is, for example, 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass relative to 100 parts by mass of the compound (A-I).

The above-mentioned colored dispersion liquid may contain a part or all of the resin (B) used in the colored composition in advance, preferably a part, if necessary. By including the resin (B) in advance, it is possible to further improve the dispersibility when it is made into a colored composition. The solid content conversion amount of the resin (B) in the colored dispersion liquid is, for example, 1 to 300 parts by mass, preferably 10 to 100 parts by mass, and more preferably 20 to 70 parts by mass relative to 100 parts by mass of the compound (AI) .

When preparing a dispersion, it is preferable to finely disperse it using a dispersing device after adding necessary components as appropriate. As the dispersion device, a bead mill device can be used. The beads used are generally hard beads such as zirconia beads, and the particle size is selected from the range of 0.05 mm or more and 20 mm or less, for example, preferably 0.1 to 10 mm, and more preferably 0.1 to 0.5 mm.

In addition, it is preferable to dissolve the compound (A-I) in the solvent (E) in advance Part or all of the solution is prepared. It is more preferable to filter the solution with a filter having a pore diameter of about 0.01 to 1 μm.

It is preferable to filter the mixed coloring composition with a filter having a pore diameter of about 0.01 to 10 μm.

Manufacturing method of color filter

As a method of producing a colored pattern from the coloring composition of the present invention, a photolithography method, an inkjet method, a printing method, etc. may be mentioned. Among them, photolithography is preferred. The photolithography method is a method of applying the coloring composition described above to a substrate, drying to form a coloring composition layer, and exposing the coloring composition layer through a photomask to develop it. In the photolithography method, by not using a photomask and/or not developing during exposure, it is possible to form a colored coating film that is a cured product of the colored composition layer. The colored pattern and colored coating film formed in this way can be used as a color filter.

The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted according to the purpose, use, etc., and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass coated with silica, polycarbonate, polymethyl methacrylate, and poly-p-phenylene can be used. Resin plates such as ethylene dicarboxylate, silicon, aluminum, silver, silver/copper/palladium alloy thin films, etc. are formed on the above-mentioned substrates. Additional color filter layers, resin layers, transistors, circuits, etc. can be formed on these substrates.

The formation of pixels of each color by photolithography can be performed under known or customary equipment and conditions. For example, it can be produced as follows.

First, the coloring composition is coated on the substrate and dried by heating (pre- Bake) and/or drying under reduced pressure to remove volatile components such as the solvent and dry to obtain a smooth coloring composition layer.

As the coating method, a spin coating method, a slit coating method, a slit and spin coating method, etc. can be cited.

The temperature at the time of heat drying is preferably 30 to 120°C, and more preferably 50 to 110°C. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

In the case of drying under reduced pressure, it is preferably performed under a pressure of 50 to 150 Pa and a temperature range of 20 to 25°C.

The film thickness of the coloring composition layer is not particularly limited, and can be appropriately selected according to the film thickness of the target color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern suitable for the intended use can be used.

As a light source used for exposure, a light source that generates light with a wavelength of 250 to 450 nm is preferable. For example, it is possible to use a filter that cuts light below 350 nm with a wavelength range that cuts off, or use a band pass filter that cuts light in the vicinity of 436 nm, 408 nm, and 365 nm to extract these wavelength ranges. Specifically, as the light source, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. can be cited.

Since parallel light rays can be uniformly irradiated to the entire exposure surface and the photomask and the substrate on which the coloring composition layer is formed can be accurately aligned, it is preferable to use exposure devices such as a mask aligner and a stepper.

By contacting the exposed coloring composition layer with the developer Touch and develop to form a colored pattern on the substrate. By development, the unexposed part of the coloring composition layer is dissolved and removed in the developer. As the developer, for example, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and tetramethylammonium hydroxide are preferred. The concentration in the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Furthermore, the developer may contain a surfactant.

The development method may be any of the rotary immersion method, dipping method, and spray method. Furthermore, the substrate can be inclined at an arbitrary angle during development.

It is preferable to wash with water after development.

Furthermore, it is preferable to post-bak the obtained colored pattern. The post-baking temperature is preferably 150 to 250°C, more preferably 160 to 235°C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

The compound of the present invention has a high absorbance, and a coloring composition using the compound can be used to produce a color filter having excellent solvent resistance. This color filter 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 elements.

Example

Hereinafter, the present invention will be described in more detail through examples, but the present invention is not limited by these examples. In the examples, it means the content and the used amount in% and parts. Unless otherwise specified, it is a quality standard.

In addition, unless otherwise specified, the reaction proceeds under a nitrogen atmosphere. In the following, the structure of the compound was confirmed by mass analysis (LC; Agilent 1200 type, MASS; Agilent LC/MSD type).

Example 1

After putting 10.0 parts of potassium thiocyanate and 55.0 parts of acetonitrile in a flask equipped with a cooling tube and a stirring device, the mixture was stirred at room temperature for 30 minutes. 13.6 parts of 2-fluorobenzyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dripped over 10 minutes, and it stirred at room temperature for 2 hours. 11.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped, and the mixture was stirred at room temperature for 30 minutes. 30.0 parts of sodium chloroacetate was dissolved in 40.8 parts of ion-exchange water, and after this solution was dropped, 22.9 parts of a 30% sodium hydroxide aqueous solution was dropped. After the dripping, it was stirred at room temperature for 20 hours. After adding 204.0 parts of ion exchange water, the mixture was stirred at room temperature for 1 hour, and the precipitated solid was collected by filtration. The obtained solid was washed with 41.0 parts of acetonitrile and then washed with 200.0 parts of ion-exchange water to obtain a wet cake of the compound represented by formula (B-I-1). 68.0 parts of ion-exchanged water, 68.0 parts of toluene, and 15.8 parts of acetic acid were put into a flask equipped with a cooling tube and a stirring device, and stirred at room temperature for 30 minutes. The entire amount of the obtained wet cake of the compound represented by formula (B-I-1) was added, and stirred at room temperature for 2 hours. 35.4 parts of 30% sodium hydroxide aqueous solution was added, and the organic layer was obtained by liquid separation and purification. After liquid separation and purification of the obtained organic layer using 68.0 parts of ion-exchange water, 35% hydrochloric acid aqueous solution was used for liquid separation and purification. Magnesium sulfate was added to the obtained organic layer, and after stirring for 1 hour, the solid was separated by filtration. The solvent was distilled to obtain 18.5 parts of the compound represented by formula (B-I-2). The yield was 69%.

After putting 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N,N-dimethylformamide into a flask equipped with a cooling tube and a stirring device, the mixed solution was ice-cooled. After 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes under ice cooling, the mixture was stirred for 1 hour while raising the temperature to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little, and stirred at room temperature for 24 hours. The reaction liquid was added little by little to 200 parts of ice water, and the mixture was allowed to stand at room temperature for 15 hours, and the water was removed by decantation to obtain a viscous solid as a residue. After adding 60 parts of methanol to this viscous solid, it was stirred at room temperature for 15 hours. After the precipitated solid was separated by filtration, it was purified by column chromatography. The purified pale yellow solid was dried at 60°C under reduced pressure to obtain 9.8 parts of the compound represented by the formula (BP-1). The yield was 53%.

After putting 8.2 parts of the compound represented by the formula (BI-2), 10.0 parts of the compound represented by the formula (BP-1), and 20.0 parts of toluene into a flask with a cooling tube and a stirring device, then, oxychlorination was added Phosphorus 12.2 It was stirred at 95-100°C for 3 hours. Next, after cooling the reaction mixture to room temperature, it was diluted with 170.0 parts of isopropanol. Next, after pouring the diluted reaction solution into 300.0 parts of saturated brine, 100 parts of toluene was added, and the mixture was stirred for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes. As a result, it was separated into an organic layer and an aqueous layer. After the water layer was discarded by the liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of Glauber's salt was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dry organic layer. The solvent of the obtained organic layer was distilled off with an evaporator to obtain a purple solid. Furthermore, the blue-violet solid was dried at 60°C under reduced pressure to obtain 18.4 parts of the compound represented by the formula (A-IV-1). The yield was 100%.

Identification (mass analysis) of the compound represented by formula (A-IV-1) Ionization mode=ESI+: m/z=687.3[M-Cl] ⁺ exact mass: 722.3

12.4 parts of the compound represented by formula (A-IV-1) and 45.5 parts of chloroform were put into a flask equipped with a cooling tube and a stirring device, and stirred. Next, 10 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 25 to 30°C for 18 hours. After cooling to room temperature, add 210 parts of N,N-dimethylformamide, and drop 2610 parts of toluene into the reaction solution. in. After stirring for 1 hour, the solid obtained by filtration was washed with 870 parts of toluene, and then dried at 60° C. under reduced pressure to obtain 12.9 parts of the compound represented by the formula (A-III-1). The yield was 89%.

Identification (mass analysis) of the compound represented by formula (A-III-1) Ionization mode=ESI+: m/z=845.3[M] ⁺ exact mass: 846.2

69.8 parts of the compound represented by formula (A-III-1) and 418 parts of chloroform were added to a flask equipped with a cooling tube and a stirring device, and stirred. 369.7 parts of phosphorus oxychloride were dropped, and the mixture was stirred at 60°C for 4 hours. After allowing to cool to room temperature, the reaction solution was poured into 5000 parts of cold water and stirred for 30 minutes. The stirring was stopped, and the mixture was allowed to stand for 30 minutes. As a result, it was separated into an organic layer and an aqueous layer. The obtained organic layer was separated and washed twice with 4000 parts of cold water. After dissolving 14.7 parts of trifluoromethanesulfonamide and 10 parts of triethylamine in 100 parts of chloroform, they were added to the organic layer and reacted at room temperature for 12 hours. After pouring the reaction solution into 5000 parts of ion-exchange water, it was stirred for 30 minutes. The stirring was stopped, and the mixture was allowed to stand for 30 minutes. As a result, it separated into an organic layer and an aqueous layer. The obtained organic layer was separated and washed twice with 4000 parts of ion exchange water. 200 parts of magnesium sulfate was added to the organic layer, and after stirring for 1 hour, the organic layer The solvent was distilled off to obtain a blue-purple solid. Furthermore, the blue-purple solid was dried at 60°C under reduced pressure to obtain 44.2 parts of compounds represented by formula (A-III-1), formula (A-II-1), and formula (A-II-2) 32:41:16 mixture (on a molar basis). This mixture is called a colorant (A-II-3).

Identification (mass analysis) of the compound represented by formula (A-II-1) Ionization mode=ESI+: m/z=978.5[M] ⁺ exact mass: 977.2

Identification (mass analysis) of the compound represented by formula (A-II-2) Ionization mode=ESI+: m/z=1109.5[M] ⁺ exact mass: 1108.1

Example 2

Put into the flask with cooling pipe and stirring device (A-IV-1) 2.0 parts of the indicated compound, 5.7 parts of dichloromethane, 1.6 parts of chlorosulfonic acid were dropped at 25-30°C, and the mixture was stirred at the same temperature for 3 hours. Next, a mixture of 3.3 parts of DMF and 0.3 parts of ion-exchange water was dropped so as not to exceed 25°C to prepare a solution. This solution was poured into 32.7 parts of toluene, the liquid part was separated, and the residue was washed again with 16.3 parts of toluene. The remaining residue was concentrated under reduced pressure with an evaporator, and the concentrate was poured into 31.2 parts of ion-exchanged water to precipitate crystals and filtered. This crude filter was suspended with 13.0 parts of 20% sodium chloride aqueous solution, filtered, and the filtered solid was washed with 13.0 parts of 20% sodium chloride aqueous solution, and dried under reduced pressure at 35°C. Next, the dried product was dissolved in 6.2 parts of methanol, the insoluble matter was filtered, concentrated under reduced pressure with an evaporator, and dried under reduced pressure at 35°C to obtain the formula (A-III-1) as a cyan solid 1.9 parts of the indicated compound. The yield was 97.9%.

Identification (mass analysis) of the compound represented by formula (A-III-1) Ionization mode=ESI+: m/z=845.3[M] ⁺ exact mass: 846.2

The following reactions were carried out in a nitrogen atmosphere. Put 2.0 parts of the compound represented by the formula (A-III-1) and 10.0 parts of acetonitrile obtained above into a flask equipped with a cooling tube and a stirring device, and drop phosphorus oxychloride at 70~80℃ 1.0 copies. Stir at the same temperature for 2 hours. Next, it cooled to 5 degreeC, and 1.0 part of trifluoromethanesulfonamide was put into this reaction liquid. Next, 2.3 parts of triethylamine was dripped at 5-15 degreeC, and it stirred at 15-30 degreeC for 2 hours. 10.0 parts of methyl ethyl ketone and 10.0 parts of 20% sodium chloride aqueous solution were poured into this reaction liquid, and it concentrated under reduced pressure with an evaporator. 15.0 parts of dichloromethane and 10.0 parts of ion-exchanged water were poured into the concentrated residue to separate the organic layer from the water layer. The organic layer was concentrated under reduced pressure with an evaporator and dried under reduced pressure at 35°C to obtain a blue solid 3.1 parts of the compound represented by formula (A-II-2) were obtained. The yield was 107.7%.

Identification (mass analysis) of the compound represented by formula (A-II-2) Ionization mode=ESI+: m/z=1109.5[M] ⁺ exact mass: 1108.1

Example 3

Put 2.0 parts of the compound represented by the formula (A-II-2), 3.4 parts of magnesium chloride hexahydrate, 40.0 parts of dimethyl sulfide, and 16.0 parts of ion exchange water into a flask with a cooling tube and a stirring device, at 80°C Stirred for 2 hours. After the reaction mixture was cooled to room temperature, a solution of 161.3 parts of ion-exchanged water and 53.8 parts of magnesium chloride hexahydrate was dropped, and the mixture was stirred at 40°C for 30 minutes. The obtained suspension was filtered, and the filtered solid was washed twice with 20.0 parts and 50.0 parts of ion exchange water. The obtained solid was dried under reduced pressure at 60°C to obtain 1.9 parts of a compound represented by formula (A-II-4).

Example 4

Except that magnesium chloride hexahydrate was changed to zinc chloride, the same reaction as in Example 3 was performed to synthesize a compound represented by formula (A-II-5).

Example 5

Except that magnesium chloride hexahydrate was changed to barium chloride dihydrate, the same reaction as in Example 3 was performed to synthesize a compound represented by formula (A-II-6).

[Chemical formula 47]

Example 6

Except that the compound represented by the formula (BP-1) was changed to the compound represented by the formula (BP-2), in the same manner as in Example 1, the formula (A-III-2) and the formula (A-II-7 ) 30:52:9 mixture of the compound represented by the formula (A-II-8) (on a molar basis). This mixture is called a colorant (A-II-9). In addition, in the formula, -SO ₃ ^- and -SO ₂ -N ^-- SO ₂ -CF ₃ mean that any one of the hydrogen atoms contained in the partial structure in parentheses is substituted.

Identification (mass analysis) of the compound represented by formula (A-III-2) Ionization mode=ESI+: m/z=931.5[M] ⁺ exact mass: 930.3

Identification (mass analysis) of the compound represented by formula (A-II-7) Ionization mode=ESI+: m/z=1063.5[M] ⁺ exact mass: 1061.3

Identification (mass analysis) of the compound represented by formula (A-II-8) Ionization mode=ESI+: m/z=1193.5[M] ⁺ exact mass: 1192.2

Example 7

Except that the compound represented by the formula (BP-1) was changed to the compound represented by the formula (BP-2), the formula (A-II-8) was obtained in the same manner as in Example 2. Represents the compound.

Identification (mass analysis) of the compound represented by formula (A-II-8) Ionization mode=ESI+: m/z=1193.5[M] ⁺ exact mass: 1192.2

Example 8

Except that the compound represented by formula (A-II-2) was changed to the compound represented by formula (A-II-8), the same reaction as in Example 3 was performed to synthesize the compound represented by formula (A-II-10) compound of.

Example 9

Except that the compound represented by formula (A-II-2) was changed to the compound represented by formula (A-II-8), the same reaction as in Example 4 was performed to synthesize the compound represented by formula (A-II-11) compound of.

Example 10

Except that the compound represented by formula (A-II-2) was changed to the compound represented by formula (A-II-8), the same reaction as in Example 5 was performed to synthesize the compound represented by formula (A-II-12) compound of.

Comparative examples 1, 2

The compound represented by formula (AX-1) (hereinafter also referred to as compound (AX-1)) and the compound represented by formula (AX-2) (hereinafter referred to as compound (AX-1)) were synthesized according to the method described in Japanese Patent Application Laid-Open No. 2015-38201 Also called compound (AX-2)).

[Synthesis Example 1]

An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to make a nitrogen atmosphere, 100 parts of propylene glycol monomethyl ether acetate was charged, and the mixture was heated to 85°C while stirring. Next, 19 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl ester and methacrylic acid were dropped into the flask for about 5 hours using a drip pump. Acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2,6 ]decane-9-yl ester mixture (the content ratio is 50:50 in molar ratio) (trade name "E-DCPA", Co., Ltd. Made by Lu) 171 parts of solution dissolved in 40 parts of propylene glycol monomethyl ether acetate. On the other hand, 26 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in propylene glycol monomethyl by dripping into the flask for about 5 hours using another drip pump. A solution in 120 parts of base ether acetate. After the dripping of the polymerization initiator was completed, 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 (B-1)) with a solid content of 43.5%. The weight average molecular weight of the obtained resin (B-1) was 8000, the degree of dispersion was 1.98, and the acid value in terms of solid content was 53 mg-KOH/g.

[Synthesis Example 2]

An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to make a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was charged, and the mixture was heated to 80°C while stirring. Next, 38 parts of acrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8 and 9-yl ester of acrylic acid were dropped into the flask for about 5 hours using a dropping pump. A solution in which 289 parts of the mixture (the content ratio is 50:50 in molar ratio) (trade name "E-DCPA", manufactured by Daicel Co., Ltd.) was dissolved in 125 parts of propylene glycol monomethyl ether acetate. On the other hand, a separate drip pump was used to drop 33 parts of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) into the flask over about 6 hours. A solution in 235 parts of ether acetate. After the dripping of the polymerization initiator was completed, it was kept at the same temperature for about 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-2)) with a solid content of 35.1%. The weight average molecular weight of the obtained resin (B-2) was 9,200, the degree of dispersion was 2.08, and the acid value in terms of solid content was 77 mg-KOH/g.

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

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

Column: TSK-GELG2000HXL

Column temperature: 40℃

Solvent: THF

Flow rate: 1.0mL/min

The concentration of solid content of the tested liquid: 0.001~0.01% 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 Co., Ltd.)

Divide the weight average molecular weight and number average of the polystyrene obtained above The ratio of particles (Mw/Mn) is taken as the degree of dispersion.

[Preparation of colored curable resin composition]

Examples 11~20 and Comparative Examples 3~4

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

In Table 14, each component represents the following compound.

(A-II-2): Compound represented by formula (A-II-2)

(A-II-3): Pigment (A-II-3)

(A-II-4): Compound represented by formula (A-II-4)

(A-II-5): Compound represented by formula (A-II-5)

(A-II-6): Compound represented by formula (A-II-6)

(A-II-8): Compound represented by formula (A-II-8)

(A-II-9): Pigment (A-II-9)

(A-II-10): Compound represented by formula (A-II-10)

(A-II-11): Compound represented by formula (A-II-11)

(A-II-12): Compound represented by formula (A-II-12)

(A-X-1): Compound represented by formula (A-X-1)

(A-X-2): Compound represented by formula (A-X-2)

(B-1): Resin (B-1) (calculated as solid content)

(C-1): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D-1): N-Benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF Corporation Manufacturing; O-acetoxime compound)

(E-1): Propylene glycol monomethyl ether acetate

(E-2): N-methylpyrrolidone

(E-3): Ethyl lactate

SH8400；東麗道康寧(株)製造) (F-1): Polyether modified silicone oil (conversion of solid content) (

SH8400; manufactured by Toray Dow Corning Co., Ltd.)

[Making of Color Filter]

(株)製造)，在大氣氣氛下、以150mJ/cm²的曝光量(365nm基準)曝光。應予說明，没有使用光掩模。通過將曝光後的著色組合物層在烘箱中、180℃下進行20分鐘後烘焙，從而製作濾色器(膜厚2.0μm)。 The colored curable resin composition was applied on a 2-inch square glass substrate (# 1737; manufactured by Corning Incorporated) by spin coating, and then pre-baked at 100°C for 3 minutes to form a colored composition layer. After cooling, use the exposure machine (TME-150RSK;

(Manufactured by Co., Ltd.), exposed to an exposure amount of 150 mJ/cm ² (based on 365 nm) in an atmospheric atmosphere. It should be noted that no photomask was used. The coloring composition layer after exposure was post-baked in an oven at 180°C for 20 minutes to produce a color filter (film thickness 2.0 μm).

[Measurement of absorbance]

Dissolve 0.35 g of the compound or colorant in chloroform to make the volume 250cm ³ , dilute 2cm ^{3 of it} with chloroform to make the volume 100cm ³ (concentration: 0.028g/L), use a spectrophotometer (quartz cell , Optical path length; 1cm) The absorption spectrum was measured. The absorbance at the maximum absorption wavelength converted to 0.028 g/L was evaluated according to the following criteria.

A: 2.0 or more

B: 1.5 or more and less than 2.0

C: less than 1.5

[Evaluation of Solvent Resistance]

The coating film of the colored photosensitive resin composition was immersed in N-methylpyrrolidone at room temperature for 40 minutes, and the color difference (△) before and after the immersion of the coating film was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS) Eab*), evaluated according to the following criteria. It should be stated that △Eab* The value is calculated from the following color difference formula based on the CIE1976 (L*, a*, b*) space table color system (The Color Science Handbook (Showa 60), page 266, edited by the Color Society of Japan).

△Eab*={(△L*)2+(△a*)2+(△b*)2}1/2

A: Less than 5.0

B: 5.0 or more and less than 10.0

C: 10.0 or more

[Measurement of voltage holding rate]

株式會社製造)1g混合，在樣品瓶中在120℃下加熱了50分鐘。將混合物轉移到離心分離用管中，使用MICRO SIX(

株式會社製造)進行了2次30分鐘的離心分離。將混合物的上清部分封入液晶評價用單元(KSRT-05/BIIIMINTS05X、E.H.C.Co.，Ltd.製造)，使用液晶物性評價裝置(6254型東陽

株式會社製造)在下述的測定條件下測定電壓保持率，按照下述的標準進行了評價。 The obtained compound 0.025g and liquid crystal (MCL-6608,

Co., Ltd.) 1 g was mixed and heated in a sample bottle at 120°C for 50 minutes. Transfer the mixture to a centrifuge tube and use MICRO SIX (

Co., Ltd.) centrifuged twice for 30 minutes. The supernatant portion of the mixture was enclosed in a liquid crystal evaluation unit (KSRT-05/BIIIMINTS05X, manufactured by EHC Co., Ltd.), and a liquid crystal property evaluation device (type 6254 Toyo

Co., Ltd.) The voltage holding ratio was measured under the following measurement conditions, and the evaluation was performed according to the following criteria.

Measurement conditions

‧Applied voltage pulse amplitude: 5V

*Voltage retention rate: the potential difference of the liquid crystal cell after 1000 milliseconds/the value of the applied voltage at 0 milliseconds

evaluation standard

A: More than 95%

B: More than 85% and less than 95%

C: Less than 85%

Examples 21-24, Comparative Examples 5 and 6

[Method of Making Dispersion]

After each component shown in Table 17 was weighed, 600 parts of 0.4 μm zirconia beads were put in, and they were shaken for 1 hour using a paint conditioner (manufactured by LAU) to prepare dispersions 1 to 6.

In Table 17, each component represents the following compound.

(A-II-5): Compound represented by formula (A-II-5)

(A-II-10): Compound represented by formula (A-II-10)

(A-II-11): Compound represented by formula (A-II-11)

(A-II-12): Compound represented by formula (A-II-12)

(A-X-1): Compound represented by formula (A-X-1)

(A-X-2): Compound represented by formula (A-X-2)

Dispersant 1: DISPERBYK-162 (Propylene glycol monomethyl ether acetate solution with 38% solid content)

Dispersing resin 1: Resin (B-2) propylene glycol monomethyl ether acetate solution (solid content 35.1%)

(E-1): Propylene glycol monomethyl ether acetate

[Production method of colored curable resin composition]

The components shown in Table 18 were mixed to obtain a colored curable resin composition.

In Table 18, each component represents the following compound.

(B-1): Resin (B-1) (calculated as solid content)

(C-1): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D-1): N-Benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF Corporation Manufacturing; O-acetoxime compound)

(E-1): Propylene glycol monomethyl ether acetate

SH8400；東麗道康寧(株)製造) (F-1): Polyether modified silicone oil (conversion of solid content) (

SH8400; manufactured by Toray Dow Corning Co., Ltd.)

[Measurement of voltage holding rate]

(株)製造)在大氣氣氛下以150mJ/cm²的曝光量(365nm基準)曝光。應予說明，没有使用光掩模。通過將曝光後的著色組合物層在烘箱中、230℃下進行20分鐘後烘焙，從而制作了塗膜(膜厚2.0μm)。通過將該塗膜從玻璃基板刮掉，從而得到了粉體。將得到的粉體0.025g和液晶(MCL-6608、

株式會社製造)1g混合，在樣品瓶中在120℃下加熱了50分鐘。將混合物轉移到離心分離用管中，採用MICRO SIX(

株式會社製造)進行了2次30分鐘的離心分離。將混合物的上清部分封入液晶評價用單元(KSRT-05/BIIIMINTS05X、E.H.C.Co.，Ltd.製造)，使用液晶物性評價裝置(6254型東陽

株式會社製造)在下述的測定條件下測定電壓保持率，按照下述的標準進行了評價。 After coating the colored curable resin composition on a 3-inch square glass substrate (# 1737; manufactured by Corning Corporation) by spin coating, it was pre-baked at 100° C. for 3 minutes to form a colored composition layer. After cooling, use the exposure machine (TME-150RSK;

(Product made by Co., Ltd.) Exposure was performed in an atmospheric atmosphere at an exposure amount of 150 mJ/cm ² (365 nm standard). It should be noted that no photomask was used. The coloring composition layer after exposure was post-baked in an oven at 230°C for 20 minutes to produce a coating film (film thickness 2.0 μm). By scraping off the coating film from the glass substrate, a powder was obtained. The obtained powder 0.025g and liquid crystal (MCL-6608,

Co., Ltd.) 1 g was mixed and heated in a sample bottle at 120°C for 50 minutes. Transfer the mixture to a centrifuge tube and use MICRO SIX (

Co., Ltd.) centrifuged twice for 30 minutes. The supernatant portion of the mixture was enclosed in a liquid crystal evaluation unit (KSRT-05/BIIIMINTS05X, manufactured by EHC Co., Ltd.), and a liquid crystal property evaluation device (type 6254 Toyo

Co., Ltd.) The voltage holding ratio was measured under the following measurement conditions, and the evaluation was performed according to the following criteria.

Measurement conditions

‧Applied voltage pulse amplitude: 5V

*Voltage retention rate: the potential difference of the liquid crystal cell after 1000 milliseconds/the value of the applied voltage at 0 milliseconds

evaluation standard

A: More than 95%

B: More than 85% and less than 95%

C: Less than 85%

Industrial availability

The compound of the present invention has excellent absorbance and voltage retention, and a coloring composition using the compound can be used to produce a color filter having excellent solvent resistance.

Claims (6)

A compound represented by formula (AI):

In the formula (AI), R ⁴¹ to R ⁴⁴ each independently represent a hydrogen atom, a saturated hydrocarbon group with 1 to 20 carbons, an optionally substituted aromatic hydrocarbon group with 6 to 20 carbons, or a substituted carbon number 7 ~30 aralkyl group, the aromatic hydrocarbon group and the substituent that the aralkyl group may have may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , the saturated hydrocarbon group having 1 to 20 carbon atoms In the saturated hydrocarbon group, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a substituted or unsubstituted amine group or halogen atom. When the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group may be It is replaced by an oxygen atom or -CO-. However, in this saturated hydrocarbon group with 2-20 carbon atoms, adjacent methylene groups will not be replaced by oxygen atoms at the same time, and the terminal methylene groups will not be replaced by oxygen atoms or -CO-, R ⁴¹ and R ⁴² can be combined with their combined nitrogen atom to form a ring, R ⁴³ and R ⁴⁴ can be combined with their combined nitrogen atom to form a ring, R ⁴⁷ ~ R ⁵⁴ each independently represents hydrogen atom, a halogen atom, a nitro group, a hydroxyl _{^{group, -SO 3 -, -SO 2 -N}} - methylene -SO ₂ -R ^f, or an alkyl group having 1 to 8 carbon atoms constituting the alkyl group may be replaced Oxygen atom or -CO-, R ⁴⁸ and R ⁵² can combine with each other to form -NH-, -S-, or -SO ₂ -, but in this alkyl group, adjacent methylene groups will not be replaced with oxygen at the same time Atom, the methylene group at the end will not be replaced with an oxygen atom or -CO-. Ring T ¹ represents an aromatic heterocyclic ring with 3 to 10 carbon atoms. The aromatic heterocyclic ring with 3 to 10 carbon atoms may have the following substitutions Group: a saturated hydrocarbon group with 1 to 20 carbons, a substituted or unsubstituted amine group, or an optionally substituted aromatic hydrocarbon group with 6 to 20 carbons. The substituent that the aromatic hydrocarbon group may have may be -SO ₃ ^- or -SO ₂ -N ^-- SO ₂ -R ^f , M ^r+ represents hydrogen ion, r-valent metal ion or substituted or unsubstituted ammonium ion, and k represents -SO ₃ ^- of the compound represented by formula (AI) The sum of the number and the number of -SO ₂ -N ^-- SO ₂ -R ^f , and k represents an integer of 2-7, r represents an integer of 1 or more, and R ^f represents a fluoroalkyl group with carbon number 1-12, However, the compound represented by the formula (AI) has at least one -SO ₂ -N ^-- SO ₂ -R ^f . Such as the compound of claim 1, wherein Mr ⁺ is an r-valent metal ion. The compound of claim 1, wherein the aromatic heterocyclic ring represented by the above T ¹ is a ring represented by the following formula (A-t1):

In the formula (A-t1), ring T ² represents an aromatic heterocyclic ring having 3 to 10 carbons, R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons that may have a substituent, and A substituted aromatic hydrocarbon group with 6 to 20 carbons or an optionally substituted aralkyl group with 7 to 30 carbons. When the saturated hydrocarbon group has 2 to 20 carbon atoms, the saturated hydrocarbon group contains The methylene group can be replaced with an oxygen atom or -CO-. However, in this saturated hydrocarbon group with 2 to 20 carbon atoms, the adjacent methylene group will not be replaced with an oxygen atom at the same time, and the terminal methylene group will not be replaced It is an oxygen atom or -CO-, R ⁴⁵ and R ⁴⁶ can be combined and form a ring together with the nitrogen atom to which they are combined, R ⁵⁵ represents a saturated hydrocarbon group with 1 to 20 carbons, or a substituted group with 6 to 20 carbons In the aromatic hydrocarbon group, k1 represents 0 or 1, and * represents the bonding terminal to the carbocation. A coloring composition comprising the compound of any one of claims 1 to 3. A color filter formed from the coloring composition of claim 4. A display device including the color filter of claim 5.