CN106883195B

CN106883195B - Compound, coloring composition, color filter and display device

Info

Publication number: CN106883195B
Application number: CN201611149400.4A
Authority: CN
Inventors: 嘉村亮平; 栂井学; 朴昭妍
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2015-12-15
Filing date: 2016-12-13
Publication date: 2022-06-24
Anticipated expiration: 2036-12-13
Also published as: TWI716505B; JP2017110187A; JP6920048B2; CN106883195A; KR20170071435A; TW201731968A; KR102185986B1

Abstract

The invention provides a color filter with excellent solvent resistance, a display device comprising the color filter, a compound capable of providing the color filter and the display device, and a coloring composition. The compounds of the present invention are represented by formula (A-I).

Description

Compound, coloring composition, color filter and display device

Technical Field

The present invention relates to a compound and a coloring composition comprising the same.

Background

The colored composition is used for producing a color filter used in a display device such as a liquid crystal display device, an electroluminescent display device, or a plasma display device. As such a coloring composition, a coloring composition containing a compound represented by the following formula and the like is known.

[ Prior art documents ]

[ patent document ]

Patent document 1: WO2012/053211

Patent document 2: japanese patent laid-open publication No. 2015-38201

Disclosure of Invention

Problems to be solved by the invention

The above-mentioned compounds known in the prior art do not satisfy the requirements for absorbance and voltage holding ratio sufficiently, and a color filter formed from a colored composition containing the compound may not satisfy the solvent resistance sufficiently.

Means for solving the problems

The present invention includes the following inventions.

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

[ in the formula (A-I),

R⁴¹～R⁴⁴each independently represents a hydrogen atom, a 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 aralkyl group having 7 to 30 carbon atoms, and the aromatic hydrocarbon group and the aralkyl group may have a substituent of-SO₃ ^-or-SO₂-N^--SO₂-R^fIn the saturated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or a halogen atom, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, a methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or-CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced by oxygen atoms, and the terminal methylene group is not replaced by an oxygen atom or-CO-. R⁴¹And R⁴²May be combined and form a ring together with the nitrogen atom to which they are combined, R⁴³And R⁴⁴May be bonded to form a ring together with the nitrogen atom to which they are bonded.

R⁴⁷～R⁵⁴Each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or-SO₃ ^-、-SO₂-N^--SO₂-R^fOr an alkyl group having 1 to 8 carbon atoms, wherein a methylene group constituting the alkyl group may be replaced with an oxygen atom or-CO-, R⁴⁸And R⁵²May combine with each other to form-NH-, -S-, or-SO₂-. However, in the alkyl group, adjacent methylene groups are not simultaneously replaced by oxygen atoms, and the terminal methylene group is not replaced by an oxygen atom or-CO-.

Ring T¹Represents a C3-10 aromatic heterocycle which may have a C1-20 saturated hydrocarbon group or substituted or unsubstituted ammoniaOr an aromatic hydrocarbon group having 6 to 20 carbon atoms and having a substituent. The substituent which the aromatic hydrocarbon group may have may be-SO₃ ^-or-SO₂-N^--SO₂-R^f。

M^r+Represents a hydrogen ion, a metal ion having a valence of r, or a substituted or unsubstituted ammonium ion.

k represents-SO that the compound represented by the formula (A-I) has₃ ^-Number of and-SO₂-N^--SO₂-R^fThe sum of the numbers of (a) and (b).

r represents an integer of 1 or more.

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

However, the compound represented by the formula (A-I) has at least 1-SO₂-N^--SO₂-R^f。]

[2][1]The compound of (a), wherein M^r+Is a metal ion.

[3][1]Or [ 2]]The compound of (a), wherein¹The aromatic heterocyclic ring is a ring represented by the following formula (A-t 1).

[ in the formula (A-t1),

ring T²Represents an aromatic heterocycle having 3 to 10 carbon atoms.

R⁴⁵And R⁴⁶Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and when the carbon number of the saturated hydrocarbon group is 2 to 20, a methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or-CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced by oxygen atoms, and the terminal methylene group is not replaced by an oxygen atom or-CO-. R is⁴⁵And R⁴⁶May be bonded to form a ring together with the nitrogen atom to which they are bonded.

R⁵⁵Represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

k1 represents 0 or 1.

Denotes a bonding end to a carbocation. ]

[4] A coloring composition comprising the compound according to any one of [1] to [3 ].

[5] A color filter formed from the colored composition according to [4 ].

[6] A display device comprising the color filter of [5 ].

ADVANTAGEOUS EFFECTS OF INVENTION

The compound of the present invention is excellent in absorbance and voltage holding ratio, and a color filter having excellent solvent resistance can be formed by using a colored composition containing the compound.

Detailed Description

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

[ in the formula (A-I),

R⁴¹～R⁴⁴each independently represents a hydrogen atom, a 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 aralkyl group having 7 to 30 carbon atoms, and the aromatic hydrocarbon group and the aralkyl group may have a substituent of-SO₃ ^-or-SO₂-N^--SO₂-R^fIn the saturated hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or a halogen atom, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, a methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or-CO-. However, in the C2-20 saturated hydrocarbon group, adjacent methylene groups are not simultaneously replaced by oxygen atoms, and the terminal methylene group is not replaced by oxygenAtom or-CO-. R⁴¹And R⁴²May be combined and form a ring together with the nitrogen atom to which they are combined, R⁴³And R⁴⁴May be bonded to form a ring together with the nitrogen atom to which they are bonded.

Ring T¹Represents an aromatic heterocycle having 3 to 10 carbon atoms, which may have a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms and may have a substituent. The substituent which the aromatic hydrocarbon group may have may be-SO₃ ^-or-SO₂-N^--SO₂-R^f。

r represents an integer of 1 or more.

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

By a ring T¹The aromatic heterocyclic ring may be a monocyclic ring or a fused ring. By a ring T¹The aromatic heterocycle has 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms. The aromatic heterocycle is preferably a 5-to 10-membered ring, and more preferably a 5-to 9-membered ring. Examples of the monocyclic aromatic heterocycle include a pyrrole ring, an oxazole ring, a pyrazole ring, a substituted pyrrole ring, a substituted benzene ring, a,A 5-membered ring containing a nitrogen atom such as an imidazole ring or a thiazole ring; a 5-membered ring containing no nitrogen atom such as a furan ring and a thiophene ring; a 6-membered ring containing a nitrogen atom such as a pyridine ring, a pyrimidine ring, a pyridazine ring and a pyrazine ring, and examples of the aromatic heterocycle having a condensed ring include a condensed ring containing a nitrogen atom such as an indole ring, a benzimidazole ring, a benzothiazole ring and a quinoline ring; a fused ring containing no nitrogen atom such as a benzofuran ring, etc.

As a ring T¹The aromatic heterocyclic ring of (2) may have a substituent, such as a halogen atom, a cyano group, a saturated hydrocarbon group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 20 carbon atoms) which may have a substituent, a substituted or unsubstituted amino group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and preferably, a saturated hydrocarbon group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 20 carbon atoms), a substituted or unsubstituted amino group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

Wherein, as ring T¹The aromatic heterocyclic ring of (3) is preferably an aromatic heterocyclic ring containing a nitrogen atom, and more preferably an aromatic heterocyclic ring containing a 5-membered ring containing a nitrogen atom.

In addition, ring T¹More preferably a ring represented by the formula (A-t 1).

[ in the formula (A-t1),

ring T²Represents an aromatic heterocycle having 3 to 10 carbon atoms.

R⁴⁵And R⁴⁶Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and when the number of carbon atoms in the saturated hydrocarbon group is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or-CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced by oxygen atoms, and the terminal methylene group is not replaced by an oxygen atom or-CO-. R⁴⁵And R⁴⁶Nitrogen atoms-to which they may be boundForming a ring.

R⁵⁵Represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms and having a substituent.

k1 represents 0 or 1.

Denotes a bonding end to a carbocation. ]

As a ring T²The aromatic heterocyclic ring of (A) includes a heterocyclic ring with ring T¹The aromatic heterocyclic ring shown in (1) above is the same as the ring shown in (1).

Further, a ring T¹The ring represented by the formula (A-t1-1) is particularly preferred.

[ in the formula (A-t1-1),

R⁵⁶represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

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

R⁵⁷Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R⁴⁵And R⁴⁶Are synonymous with the above.

Denotes a bonding end to a carbocation. ]

In addition, a ring T¹Also preferred is a ring represented by the formula (A-t 2).

[ in the formula (A-t2),

ring T³Represents an aromatic heterocycle having 3 to 10 carbon atoms and having a nitrogen atom.

R⁵⁸Represents a C1-20 saturated hydrocarbon group, an optionally substituted C6-20 aromatic hydrocarbon group, -SO₃ ^-or-SO₂-N^--SO₂-R^f。

R⁵⁹Represents a hydrogen atom and may have a substituentThe carbon number of the saturated hydrocarbon group of 1 to 20, an optionally substituted aromatic hydrocarbon group of 6 to 20 carbon atoms, or an optionally substituted aralkyl group of 7 to 30 carbon atoms.

k2 represents 0 or 1.

Denotes a bonding end to a carbocation. ]

Ring T¹Also more preferred is a ring represented by the formula (A-t 2-1).

[ in the formula (A-t2-1),

R⁶⁰represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

R⁶¹Represents a hydrogen atom, -SO₃ ^-or-SO₂-N^--SO₂-R^f。

R⁵⁹Are synonymous with the above.

Denotes a bonding end to a carbocation. ]

From R⁴¹～R⁴⁶、R⁵⁵、R⁵⁶And R⁵⁸～R⁶⁰The saturated hydrocarbon group having 1 to 20 carbon atoms may be any of straight chain, branched chain and cyclic. Examples of the linear or branched saturated hydrocarbon group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl and eicosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl groups. The number of carbon atoms of the saturated hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, and still more preferably 1 to 6.

From R⁴¹～R⁴⁶、R⁵⁵、R⁵⁶And R⁵⁸～R⁶⁰The cyclic saturated hydrocarbon group may be a single ring or multiple rings. 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 groupPreferably 3 to 10, and more preferably 6 to 10.

As a group consisting of R⁴¹～R⁴⁶、R⁵⁵、R⁵⁶And R⁵⁸～R⁶⁰Specific examples of the saturated hydrocarbon group include those represented by the following formulae. In the following formula, a represents a bonding end.

From R⁴¹～R⁴⁶、R⁵⁵、R⁵⁶And R⁵⁸～R⁶⁰The saturated hydrocarbon group represented may be substituted with a substituted or unsubstituted amino group or a halogen atom. Examples of the substituted amino group include alkylamino groups such as dimethylamino group and diethylamino group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. When the halogen atom is a fluorine atom, the group R⁴¹～R⁴⁶、R⁵⁵、R⁵⁶And R⁵⁸～R⁶⁰The saturated hydrocarbon group represented by the formula (i) which is substituted with a halogen atom (fluorine atom) is preferably a perfluoroalkyl group such as a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, or the like.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms and having a substituent include groups represented by the following formulae. In the following formula, a represents a bonding end with a nitrogen atom or the like.

As a group consisting of R⁴⁷～R⁵⁴The alkyl group having 1 to 8 carbon atoms represented by R⁴¹Examples of the saturated hydrocarbon group include groups having 1 to 8 carbon atoms in a straight or branched saturated hydrocarbon group.

In addition, as represented by R⁵⁷The alkyl group having 1 to 10 carbon atoms represented by R⁴¹Examples of the saturated hydrocarbon group include groups having 1 to 10 carbon atoms in a straight or branched saturated hydrocarbon group.

From R⁴¹～R⁴⁶When the number of carbon atoms in the saturated hydrocarbon group is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or-CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced by oxygen atoms, and the terminal methylene group is not replaced by an oxygen atom or-CO-. In this case, the saturated hydrocarbon group is preferably a linear or branched saturated hydrocarbon group (i.e., a linear or branched alkyl group), and more preferably a linear saturated hydrocarbon group (i.e., a linear alkyl group). The preferable carbon number of the saturated hydrocarbon group in which the methylene group is replaced with an oxygen atom or-CO-, is 2 to 10, more preferably 2 to 8. When the methylene group is replaced with an oxygen atom or-CO-, the number of carbon atoms between the terminal and the oxygen atom or-CO-, or between the terminal and the oxygen atom or-CO-, is 1 or more, preferably 1 to 5, more preferably 2 to 3, and still 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 is contained; or a polyalkoxyalkyl group such as (alkoxyalkoxy) alkyl, (alkoxyalkoxyalkoxy) alkyl, (alkoxyalkoxyalkoxyalkoxyalkoxy) alkyl, (alkoxyalkoxyalkoxyalkoxyalkoxyalkoxyalkoxy) alkyl, and (alkoxyalkoxyalkoxyalkoxyalkoxyalkoxyalkoxyalkoxy) alkyl, and the number of repeating alkoxy units is, for example, 1 to 6, preferably 1 to 4, and more preferably 1 to 2. More preferred examples include groups represented by the following formulae. In the following formula, a represents a bonding end to a nitrogen atom.

In addition, from R⁴¹～R⁴⁶、R⁵⁵、R⁵⁶And R⁵⁸～R⁶⁰The number of carbon atoms of the aromatic hydrocarbon group which may have a substituent(s) is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 12. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group, and a phenyl group, a naphthyl group, a tolyl group, and a xylyl group are preferable, and a phenyl group is particularly preferable. In addition, the aromatic hydrocarbonThe group may have 1 or 2 or more substituents. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom; a C1-6 haloalkyl group such as chloromethyl group and trifluoromethyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a sulfamoyl group; c1-6 alkylsulfonyl such as methylsulfonyl; alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; -SO₃ ^-；-SO₂-N^--SO₂-R^fEtc. can be-SO₃ ^-or-SO₂-N^--SO₂-R^f. However, -SO₃ ^-or-SO₂-N^--SO₂-R^fIt is preferable that the hydrogen atom bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group is substituted.

Specific examples of the aromatic hydrocarbon group which may have a substituent include groups represented by the following formulae. In the following formula, a represents a bonding end to a nitrogen atom.

As a group consisting of R⁴¹～R⁴⁶、R⁵⁹The aralkyl group which may have a substituent(s) may include a group in which an alkylene group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) such as a methylene group, an ethylene group, a propylene group, etc., is bonded to the group described as the above aromatic hydrocarbon group. The aralkyl group preferably has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, and still more preferably 7 to 17 carbon atoms.

As R⁴¹And R⁴²Combined and forming a ring together with the nitrogen atom to which they are bound, R⁴³And R⁴⁴A ring bound to and formed together with the nitrogen atom to which they are bound, and R⁴⁵And R⁴⁶Examples of the ring to be bonded together with the nitrogen atom bonded to the nitrogen atom include nitrogen-containing nonaromatic 4-7 membered rings such as pyrrolidine ring, morpholine ring, piperidine ring and piperazine ring, and preferably, a ring having only 1 nitrogen atom such as pyrrolidine ring and piperidine ring4-7 membered ring of hetero atom.

As R⁵⁸Preferably, the hydrocarbon group is a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

Wherein, as R⁴¹～R⁴⁴、R⁵⁵、R⁵⁶、R⁵⁸～R⁶⁰The hydrocarbon group is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having a substituent, and each independently, more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group represented by the following formula. R⁵⁵、R⁵⁶、R⁵⁸～R⁶⁰More preferably an aromatic hydrocarbon group represented by the following formula. In the following formula, a represents a bonding end to a nitrogen atom.

R⁴⁵～R⁴⁶Preferably, each independently is a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group in which a methylene group constituting an alkyl group having 2 to 20 carbon atoms is replaced with an oxygen atom or-CO-, or a substituent⁴⁵And R⁴⁶Combine and form a ring together with the nitrogen atom to which they are bound. R⁴⁵～R⁴⁶More preferably, each independently is a C1-8 saturated hydrocarbon group, an alkoxyalkyl group, or an aromatic hydrocarbon group represented by the following formula, or R⁴⁵And R⁴⁶The groups are bonded to form a 4-to 7-membered ring having only 1 nitrogen atom as a heteroatom, and are more preferably each independently 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, a indicates a bonding end to a nitrogen atom.

In addition, as represented by R⁴⁷～R⁵⁴The alkyl group having 1 to 8 carbon atoms represented by R⁴¹Examples of the saturated hydrocarbon group include a linear or branched saturated hydrocarbon group having 1 carbon atomA group of 8. In addition, as represented by R⁴⁷～R⁵⁴Examples of the group in which the methylene group constituting the C2-C8 alkyl group is replaced with an oxygen atom or-CO- (in the alkyl group, adjacent methylene groups are not simultaneously replaced with an oxygen atom, and the terminal methylene group is not replaced with an oxygen atom or-CO-), include the group consisting of R⁴¹～R⁴⁶The methylene group constituting the alkyl group having 2 to 20 carbon atoms is replaced by a group having 8 or less carbon atoms selected from the group consisting of an oxygen atom and a group of-CO-. As a group consisting of R⁴⁷～R⁵⁴The alkyl group having 1 to 8 carbon atoms is more preferably a group represented by the following formula. In the following formula, a represents a bonding end to a carbon atom.

R⁴⁷～R⁵⁴From the viewpoint of ease of synthesis, each is preferably independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, and more preferably independently a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom.

In addition, as R⁵⁷Preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

As R⁶¹Preferably a hydrogen atom.

As by M^r+Examples of the metal ion having a valence of r include alkali metal ions such as lithium ion, sodium ion, and potassium ion; alkaline earth metal ions such as beryllium ions, magnesium ions, calcium ions, strontium ions, and barium ions; transition metal ions such as titanium ions, zirconium ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, and copper ions; typical metal ions such as zinc ions, cadmium ions, aluminum ions, indium ions, tin ions, lead ions, bismuth ions, and the like. r is 1 or more, preferably 2 or more, preferably 5 or less, more preferably 4 or less, and further preferably 3 or less. In addition, as a group consisting of M^r+Examples of the substituted or unsubstituted ammonium ion include quaternary ammonium ions such as tetraalkylammonium ions.

As M^r+From the viewpoint of voltage holding ratioThe metal ion having a valence of r is preferable, an alkaline earth metal ion, a typical metal ion and the like are more preferable, and a magnesium ion, a barium ion and a zinc ion are further preferable. As M^r+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 (A-I), M^r+The number of (a) is in proportion to-SO that the compound represented by the formula (A-I) has₃ ^-Number of and-SO₂-N^--SO₂-R^fThe sum (k) of the numbers of (a) and (b) is less than 1. Therefore, the compound (A-I) has a valence of 0, i.e., is electrically neutral. Having a-SO₃ ^-In the case of (2), -SO₃ ^-The number of (a) is preferably 6 or less, more preferably 3 or less, and may be 1 or more. In addition, -SO₃ ^-The number of (2) is also preferably 0.

As a group R^fExamples of the fluoroalkyl group having 1 to 12 carbon atoms include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group (perfluoromethyl group), a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, a pentafluoroethyl group (perfluoroethyl group), a monofluoropropyl group, a difluoropropyl group, a trifluoropropyl group, a tetrafluoropropyl group, a pentafluoropropyl group, a hexafluoropropyl group, a heptafluoropropyl group (perfluoropropyl group), a fluorobutyl group, a difluorobutyl group, a trifluorobutyl group, a tetrafluorobutyl group, a pentafluorobutyl group, a hexafluorobutyl group, a heptafluorobutyl group, an octafluorobutyl group, and a nonafluorobutyl group (perfluorobutyl group). Wherein as represented by R^fAn alkyl group (fluoroalkyl group) in which all or a part of the hydrogen atoms represented by the formula (i) is substituted with a fluorine atom is preferably a perfluoroalkyl group. In addition, from R^fThe number of carbon atoms of the alkyl (fluoroalkyl) group in which all or a part of the hydrogen atoms are substituted with fluorine atoms is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.

The compound (A-I) has at least 1-SO₂-N^--SO₂-R^f。-SO₂-N^--SO₂-R^fThe number of (A) is 1 or more, preferably 1 to 7, more preferably 1 to 4, still more preferably 1 or 2, and particularly preferably 2.

In addition, the compound (A-I) also preferably has-SO₂-N^--SO₂-R^fAnd does not have-SO₃ ^-Preferably also having-SO₂-N^--SO₂-R^fand-SO₃ ^-. Having a-SO₂-N^--SO₂-R^fand-SO₃ ^-In the case where at least 1-SO is contained in the compound (A-I)₂-N^--SO₂-R^f，-SO₂-N^--SO₂-R^fand-SO₃ ^-The total number of (a) is preferably 2 to 7, more preferably 2 to 4, and still more preferably 2.

the-SO₂-N^--SO₂-R^for-SO₃ ^-Is preferably used as the above-mentioned R⁴⁷～R⁵⁴Or with R⁴¹～R⁴⁴An optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R⁴¹～R⁴⁴An aralkyl group having 7 to 30 carbon atoms which may have a substituent, and a compound represented by formula (T)¹Any one of the aromatic hydrocarbon groups having 6 to 20 carbon atoms substituted with a hydrogen atom of the aromatic heterocycle represented by (A) is bonded, more preferably with R⁴¹～R⁴⁴An optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R⁴¹～R⁴⁴The aralkyl group having 7 to 30 carbon atoms which may have a substituent(s) is bonded to R⁴¹～R⁴⁴An optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R⁴¹～R⁴⁴The aromatic hydrocarbon ring (benzene ring) in the aralkyl group having 7 to 30 carbon atoms which may have a substituent is bonded at the para-position in terms of the bonding position with the nitrogen atom.

However, in which-SO is bound to an aromatic hydrocarbon group or an aralkyl group₂-N^--SO₂-R^for-SO₃ ^-In the case of (2), -SO₂-N^--SO₂-R^for-SO₃ ^-Preferably directly bonded to the aromatic hydrocarbon ring of the aromatic hydrocarbon group or aralkyl group. namely-SO₂-N^--SO₂-R^for-SO₃ ^-It is preferable to substitute a hydrogen atom bonded to the aromatic hydrocarbon ring.

-SO₂-N^--SO₂-R^fand-SO₃ ^-Can be bound to the same aromatic hydrocarbon ring, but is preferably bound to different aromatic hydrocarbon rings.

Further, the compound (A-I) preferably has no ethylenically unsaturated bond.

As compound (A-I), it will also be preferred to have-SO₂-N^--SO₂-R^fAnd has no-SO₃ ^-And a compound having-SO₂-N^--SO₂-R^fand-SO₃ ^-The compound (4) is used in combination. In this case, having-SO₂-N^--SO₂-R^fAnd does not have-SO₃ ^-With a compound having-SO₂-N^--SO₂-R^fand-SO₃ ^-Molar ratio of the compound (having-SO)₂-N^--SO₂-R^fAnd does not have-SO₃ ^-has-SO₂-N^--SO₂-R^fand-SO₃ ^-The compound of (1) is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, and may be 50 or less, more preferably 10 or less, further preferably 5 or less, and particularly preferably 1 or less.

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

[ in the formula (A-I1),

R⁸¹～R⁹⁰each independently represents a hydrogen atom, a C1-20 saturated hydrocarbon group, a halogen atom or-SO₃ ^-or-SO₂-N^--SO₂-R^f。

k1 represents-SO that the compound represented by the formula (A-I1) has₃ ^-Number of and-SO₂-N^--SO₂-R^fThe sum of the numbers of (a) and (b).

R⁴¹、R⁴³、R⁴⁷～R⁵⁴、T¹、M^r+、r、R^fSynonymous with the above.

However, the compound represented by the formula (A-I1) has at least 1-SO₂-N^--SO₂-R^f。]

As a group consisting of R⁸¹～R⁹⁰The saturated hydrocarbon group having 1 to 20 carbon atoms includes R⁴¹Examples of the saturated hydrocarbon group shown are the same groups as those shown above. As R⁸¹～R⁹⁰Preferably hydrogen atom, C1-8 saturated hydrocarbon group, -SO₃ ^-or-SO₂-N^--SO₂-R^fMore preferably a hydrogen atom, -SO₃ ^-or-SO₂-N^--SO₂-R^fFurther, hydrogen atom or-SO is preferable₂-N^--SO₂-R^f。

In addition, -SO₂-N^--SO₂-R^for-SO₃ ^-Preferably (e) is as the above R⁴⁷～R⁵⁴Either (f) as R⁸¹～R⁹⁰Either of (a) and (b) contains, or is related to¹The aromatic heterocyclic ring represented by (a) is bonded to an aromatic hydrocarbon group having 6 to 20 carbon atoms substituted with a hydrogen atom, or is present as a combination of (e) to (g) thereof, more preferably (f) and (g) or a combination of (f) to (g) thereof, and still more preferably (f). In addition, R⁸¹～R⁹⁰In (1), preferably selected from R⁸⁶And R⁸⁹1 or more of (1).

-SO contained in Compound (A-I1)₂-N^--SO₂-R^fThe number of (A) is preferably 1 to 7, more preferably 1 to 4, and further preferably 1 or 2. Further, the compound (A-I1) has-SO₂-N^--SO₂-R^fand-SO₃ ^-In the case of (A-I1), at least 1-SO is contained in the compound (A-I1)₂-N^--SO₂-R^f，-SO₂-N^--SO₂-R^fand-SO₃ ^-The total number of(k1) Preferably 2 to 7, more preferably 2 to 4, and still more preferably 2.

As compound (A-I1), it will also be preferred to have-SO₂-N^--SO₂-R^fAnd does not have-SO₃ ^-And a compound having-SO₂-N^--SO₂-R^fand-SO₃ ^-The compound (4) is used in combination. In this case, having-SO₂-N^--SO₂-R^fAnd does not have-SO₃ ^-With a compound having-SO₂-N^--SO₂-R^fand-SO₃ ^-Molar ratio of the compound (having-SO)₂-N^--SO₂-R^fAnd does not have-SO₃ ^-has-SO₂-N^--SO₂-R^fand-SO₃ ^-The compound of (1) is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, and may be 50 or less, more preferably 10 or less, further preferably 5 or less, and particularly preferably 1 or less.

Examples of the compound (A-I) include compounds (A-I-1) to (A-I-632) represented by the formula (A-I-I), as shown in tables 1 to 12 below. In the table, a indicates a bonding end.

However, the compound represented by the formula (A-I-I) has 2-SO₂-N^--SO₂-CF₃Or having 1-SO₂-N^--SO₂-CF₃And 1-SO₃ ^-the-SO₂-N^--SO₂-CF₃or-SO₃ ^-Is taken as R^hIs bonded to an aromatic hydrocarbon ring (benzene ring) having an aromatic hydrocarbon group represented by Ph1 to Ph12, preferably bonded to R⁴¹～R⁴⁴The aromatic hydrocarbon ring (benzene ring) having an aromatic hydrocarbon group represented by Ph1 to Ph12 in (b) is para as viewed from the bonding end.

[ TABLE 1]

[ TABLE 2]

[ TABLE 3]

[ TABLE 4]

[ TABLE 5]

[ TABLE 6]

[ TABLE 7 ]

[ TABLE 8 ]

[ TABLE 9 ]

[ TABLE 10 ]

[ TABLE 11 ]

[ TABLE 12 ]

In tables 1 to 12, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, Bt represents a n-butyl group, EOE represents an ethoxyethyl group, 14Bt represents a butane-1, 4-diyl group, and Ph1 to Ph12 represent groups represented by the following formulae. In the formula, a indicates a bonding end.

Further, as shown in Table 13 below, examples of the compound (A-I) include compounds (A-I-634) to (A-I-657) represented by the formula (A-I-II). In the table, a indicates a bonding end.

However, the compound represented by the formula (A-I-II) has 1-SO on average₂-N^--SO₂-CF₃and-SO₂-NH-SO₂-CF₃the-SO₂-N^--SO₂-CF₃and-SO₂-NH-SO₂-CF₃Is taken as R^hAnd an aromatic hydrocarbon ring (benzene ring) containing an aromatic hydrocarbon group represented by any one of Ph1, Ph13 and Ph 14.

[ TABLE 13 ]

R⁴¹

R⁴²

R⁴³

R⁴⁴

R⁵⁹

R⁶⁰

R^h

k-1

r

M^r+

(A-I-634)

Et

Me

Ph1

H

1

H⁺

(A-I-635)

Et

Hex

Ph13

H

1

H⁺

(A-I-636)

iBu

Me

Ph1

H

1

H⁺

(A-I-637)

Me

Ph1

Me

Ph1

Hex

Ph14

H

1

H⁺

(A-I-638)

Et

Ph1

Et

Ph1

Hex

Ph14

H

1

H⁺

(A-I-639)

Pr

Ph1

Pr

Ph1

Hex

Ph14

H

1

H⁺

(A-I-640)

Et

Me

Ph1

H

1

2

Mg²⁺

(A-I-641)

Et

Hex

Ph13

H

1

2

Mg²⁺

(A-I-642)

iBu

Me

Ph1

H

1

2

Mg²⁺

(A-I-643)

Me

Ph1

Me

Ph1

Hex

Ph14

H

1

2

Mg²⁺

(A-I-644)

Et

Ph1

Et

Ph1

Hex

Ph14

H

1

2

Mg²⁺

(A-I-645)

Pr

Ph1

Pr

Ph1

Hex

Ph14

H

1

2

Mg²⁺

(A-I-646)

Et

Me

Ph1

H

1

2

Zn²⁺

(A-I-647)

Et

Hex

Ph13

H

1

2

Zn²⁺

(A-I-648)

iBu

Me

Ph1

H

1

2

Zn²⁺

(A-I-649)

Me

Ph1

Me

Ph1

Hex

Ph14

H

1

2

Zn²⁺

(A-I-650)

Et

Ph1

Et

Ph1

Hex

Ph14

H

1

2

Zn²⁺

(A-I-651)

Pr

Ph1

Pr

Ph1

Hex

Ph14

H

1

2

Zn²⁺

(A-I-652)

Et

Me

Ph1

H

1

2

Ba²⁺

(A-I-653)

Et

Hex

Ph13

H

1

2

Ba²⁺

(A-I-654)

iBu

Me

Ph1

H

1

2

Ba²⁺

(A-I-655)

Me

Ph1

Me

Ph1

Hex

Ph14

H

1

2

Ba²⁺

(A-I-656)

Et

Ph1

Et

Ph1

Hex

Ph14

H

1

2

Ba²⁺

(A-I-657)

Pr

Ph1

Pr

Ph1

Hex

Ph14

H

1

2

Ba²⁺

In table 13, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, Bt represents a n-butyl group, EOE represents an ethoxyethyl group, Hex represents a n-hexyl group, and Ph1, Ph13, and Ph14 represent groups represented by the following formulae.

In the formula, a represents a 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 compound (a-III)).

[ in the formula (A-III),

R^21a～R^24aeach independently represents a hydrogen atom, a 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 aralkyl group having 7 to 30 carbon atoms, and the aromatic hydrocarbon group and the aralkyl group may have a substituent of-SO₃ ^-In the C1-20 saturated hydrocarbon group, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by a substituted or unsubstituted amino group or a halogen atom, and when the C1-20 saturated hydrocarbon group is a C2-20 alkyl group, the methylene group contained in the alkyl group may be replaced by an oxygen atom or-CO-. However, in the alkyl group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced by oxygen atoms, and the terminal methylene group is not replaced by an oxygen atom or-CO-. R^21aAnd R^22aMay be combined and form a ring together with the nitrogen atom to which they are combined, R^23aAnd R^24aMay be bonded to form a ring together with the nitrogen atom to which they are bonded.

R^27a～R^34aEach independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or-SO₃ ^-Or an alkyl group having 1 to 8 carbon atoms, wherein a methylene group constituting the alkyl group may be replaced with an oxygen atom or-CO-. R^28aAnd R^32aMay combine with each other to form-NH-, -S-, or-SO₂-。

Ring T¹⁰Represents a C3-10 aromatic heterocycle, which may have a C1-20 saturated hydrocarbon group or a C6-20 aromatic hydrocarbon group which may have a substituent. The substituent which the aromatic hydrocarbon group may have may be-SO₃ ^-。

M^r+And r are synonymous with the above.

k2 represents-SO that the compound represented by the formula (A-III) has₃ ^-The number of the cells.

However, the compound represented by the formula (A-III) has at least 1-SO₃ ^-。]

From R^21a～R^24aThe saturated hydrocarbon group, aromatic hydrocarbon group and aralkyl group represented by the formula are respectively represented by R⁴¹～R⁴⁴A saturated hydrocarbon group represented by,Aromatic hydrocarbon groups and aralkyl groups.

In addition, as represented by R^27a～R^34aExamples of the alkyl group represented by the formula (I) include⁴⁷～R⁵⁴The alkyl groups represented are the same groups.

Further, the compound (A-III) preferably has 1 or more-SO₃ ^-In particular, -SO₃ ^-More preferably (a') is taken as R^27a～R^34aOr (b') with the above-mentioned R^21a～R^24aA C6-20 aromatic hydrocarbon group which may have a substituent, or (c') and R^21a～R^24aA C7-30 aralkyl group which may have a substituent, or (d') with an aralkyl group to be represented by T³Any one of the aromatic heterocyclic groups represented by (a) to (d ') is bonded to an aromatic hydrocarbon group having 6 to 20 carbon atoms substituted with a hydrogen atom, and more preferably (b'), (c '), (d') or a combination of (b ') to (d'). -SO₃ ^-The number of (b) is preferably 0 to 6, more preferably 1 to 6, and further preferably 1 to 3.

-SO₃ ^-Can be bound to the same aromatic hydrocarbon ring, but is preferably bound to different aromatic hydrocarbon rings.

When the compound (a-I) and the compound (a-III) are mixed, the content of the compound (a-III) is preferably 1 mol or more, more preferably 20 mol or more, further preferably 40 mol or more, preferably 90 mol or less, more preferably 80 mol or less, and further preferably 70 mol or less based on 100 mol of the compound (a-I).

The compound (a-I) can be produced, for example, by sulfonating a compound represented by the formula (a-IV) (hereinafter, sometimes referred to as a compound (a-IV)) to produce a compound (a-III), and reacting the compound with a compound represented by the following formula (a-II). The compound (A-I) may be optionally combined with a metal ion M having a valence of r^r+Preferably chloride, acetate, phosphate, sulfate, silicate, cyanide, and the like. The compound (A-IV) is preferably hydrochloride, phosphate, perchlorate, BF₄Salt, PF₆Salts and the like.

[ in the formula (A-IV),

R^1a～R^4aeach independently represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a substituted or unsubstituted amino group or a halogen atom, an alkyl group having 2 to 20 carbon atoms in which a methylene group constituting the alkyl group is replaced with an oxygen atom or-CO-, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, an aralkyl group having 7 to 30 carbon atoms which may have a substituent, or a hydrogen atom. R^1aAnd R^2aMay be combined and form a ring together with the nitrogen atom to which they are combined, R^3aAnd R^4aMay be bonded to form a ring together with the nitrogen atom to which they are bonded.

R^7a～R^14aEach independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or an alkyl group having 1 to 8 carbon atoms, and a methylene group constituting the alkyl group may be replaced with an oxygen atom or-CO-. R is^8aAnd R^12aMay combine with each other to form-NH-, -S-, or-SO₂-。

Ring T¹¹Represents a C3-10 aromatic heterocycle, which may have a C1-20 saturated hydrocarbon group or a C6-20 aromatic hydrocarbon group which may have a substituent.

M¹Represents Cl^-Phosphate ion, perchlorate ion, BF₄ ^-、PF₆ ^-。]

[ in the formula (A-III), R^21a～R^24a、R^27a～R^34aRing T¹⁰、M^r+R and k2 are the same as above.

[ in the formula (A-II), R^fAre synonymous with the above.]

[ in the formula (A-I), R⁴¹～R⁴⁴、R⁴⁷～R⁵⁴Ring T¹、k、M^r+And r are synonymous with the above.]

Examples of the sulfonation include known methods, for example, the methods described in Journal of Organic Chemistry (1994), volume 59, #11, pages 3232 and 3236.

The compound (a-I) of the present invention can be applied to a fiber product, and for example, a fiber material can be colored by kneading, dipping, adhering, or the like in the fiber material.

The coloring composition of the present invention comprises a colorant (a) comprising the 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 composition may further contain a polymerization initiation aid (D1) and a leveling agent (F).

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 the present specification, the compounds exemplified as the respective components may be used alone or in combination of a plurality of compounds unless otherwise specified.

Solvent (E)

The solvent (E) is not particularly limited, and a solvent generally used in this field can be used. Examples thereof include ester solvents (solvents containing-COO-or not-O-in the molecule), ether solvents (solvents containing-O-or not-COO-in the molecule), ether ester solvents (solvents containing-COO-or not-O-in the molecule), ketone solvents (solvents containing-CO-or not-COO-in the molecule), alcohol solvents (solvents containing OH, not-O-, -CO-or-COO-in the molecule), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

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

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1, 4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methylanisole.

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

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

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

As the aromatic hydrocarbon solvent, benzene, toluene, xylene, 1,3, 5-trimethylbenzene, and the like can be mentioned.

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

These solvents may be used alone, or 2 or more of them may be used in combination.

Of these, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene 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-dimethylformamide and the like are preferable, more preferred are ethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol methyl ether acetate, 3-methoxy-1-butanol, 3-methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl lactate, and N-methylpyrrolidone.

When the solvent (E) is contained, the content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass, based on the total amount of the coloring composition. In other words, the total amount of solid components in the coloring composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is in the above range, the flatness at the time of coating becomes good, and the color density does not become insufficient at the time of forming a color filter, so that the display characteristics tend to become good.

The "total amount of solid components" in the present specification means the total amount of components obtained by removing the solvent (E) from the coloring composition. The total amount of the solid components and the contents of the components relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.

Colorant (A)

The colorant (a) may be a dye containing the compound (a-I) of the present invention as an active ingredient, but may further contain another dye (a1), a pigment (P), or a mixture thereof for toning, that is, for adjusting spectral characteristics.

Examples of The dye (a1) include oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, sulfonamide derivatives of acid dyes, and The like, and examples thereof include compounds classified as dyes in The color index (published by The Society of Dyers and Colourists) and known dyes described in dyeing notes (chromo). Further, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and the like can be cited. Among these, organic solvent-soluble dyes are preferably used.

Specific examples of the dye (a1) include c.i. solvent yellow 4 (c.i. solvent yellow is not described below, and only the serial numbers are described), 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;

c.i. solvent red 24, 45, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 145, 160, 218;

c.i. solvent orange 2, 7, 11, 15, 26, 41, 54, 56, 99;

c.i. solvent blue 4,5, 37, 67, 70, 90;

C.I. solvent green 1,4, 5, 7, 34, 35, etc,

C.i. 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, 251, 274, 243;

c.i. acid red 1,4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 289, 412, 417, 418, 422, 426;

c.i. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

c.i. acid violet 6B, 7, 9, 17, 19, 30, 102, 120;

c.i. acid blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 62, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;

C.I. acid dyes such as C.I. acid green 1,3,5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106 and 109,

C.i. direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;

c.i. direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

c.i. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;

c.i. direct yellow 2,4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;

c.i. direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

c.i. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

c.i. direct blue 1,2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;

c.i. direct dyes such as c.i. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc,

C.I. disperse dyes such as C.I. disperse yellows 51, 54 and 76,

C.i. basic red 1, 10;

c.i. basic blue 1,3,5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;

C.I. basic dyes such as C.I. basic green 1,

C.i. reactive yellow 2, 76, 116;

c.i. reactive orange 16;

C.I. reactive dyes such as C.I. reactive red 36,

C.i. mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

c.i. 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;

c.i. mordant oranges 3,4,5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

c.i. mordant violet 1,2, 4,5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

c.i. 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;

C.I. mordant dyes such as C.I. mordant green 1,3, 4,5, 10, 15, 26, 29, 33, 34, 35, 41, 43 and 53,

C.i. vat dyes such as c.i. vat green 1, and the like. Among them, violet dyes are preferred.

The pigment (P) is not particularly limited, and known pigments can be used, and examples thereof include pigments classified as pigments in The Society of Dyers and Colourists.

Examples of the pigment include

C.i. pigment yellow 1,3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and the like;

orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

red pigments such as c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;

c.i. pigment blue 15, 15: 3. 15: 4. 15: 6. 60, and the like cyan pigments;

c.i. pigment violet 1, 19, 23, 29, 32, 36, 38 and the like violet pigment;

green pigments such as c.i. pigment green 7, 36, 58;

c.i. brown pigments such as pigment brown 23, 25;

and black pigments such as c.i. pigment black 1 and 7.

The pigment (P) is preferably a phthalocyanine pigment and a dioxazine pigment, more preferably selected from c.i. pigment blue 15: 6 and pigment violet 23. By containing the above pigment, optimization of the transmission spectrum is facilitated, and the light resistance and chemical resistance of the color filter are improved.

The pigment may be subjected to, if necessary, rosin treatment, surface treatment using a pigment derivative or the like into which an acidic group or a basic group has been introduced, grafting treatment on the pigment surface using a polymer compound or the like, micronization treatment using a sulfuric acid micronization method or the like, washing treatment using an organic solvent, water or the like for removing impurities, removal treatment using an ion exchange method or the like for removing ionic impurities, or the like. The pigment is preferably uniform in particle size.

The pigment is dispersed by containing a pigment dispersant, whereby a pigment dispersion liquid in which the pigment is uniformly dispersed in a solution can be obtained. The pigments may be dispersed individually or in combination.

Examples of the pigment dispersant include surfactants, which may be any of cationic, anionic, nonionic and amphoteric surfactants. Specifically, polyester, polyamine, acrylic, and other pigment dispersants can be mentioned. These pigment dispersants may be used alone or in combination of 2 or more. Examples of the pigment dispersant include, as a trade name, KP (manufactured by shin-Etsu chemical Co., Ltd.), フローレン (manufactured by Kyoho chemical Co., Ltd.), ソルスパース (registered trademark) (manufactured by ゼネカ (Co.), EFKA (registered trademark) (manufactured by BASF corporation), アジスパー (registered trademark) (manufactured by Weisuo ファインテクノ (Co., Ltd.), Disperbyk (registered trademark) (manufactured by ビックケミー corporation).

When a pigment dispersant is used, the amount thereof is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, per 100 parts by mass of the pigment. When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

The content of the compound (a-I) 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 further preferably 5% by mass or more and 50% by mass or less, based on the total amount of the solid content.

The content of the compound (a-I) is preferably 1 mass% to 100 mass%, more preferably 10 mass% to 100 mass%, based on the total amount of the colorant (a).

When the compound (a-I) and the compound (a-III) are used in combination, the total content of the compound (a-I) and the compound (a-III) is preferably 10% by mass or more and 70% by mass or less, and more preferably 15% by mass or more and 60% by mass or less, based on the total amount of solid components.

When the dye (a1) is contained, the content thereof is preferably 0.5% by mass or more and 90% by mass or less, more preferably 0.5% by mass or more and 70% by mass or less, with respect to the total amount of the colorant (a). When the pigment (P) is contained, the content thereof 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, with respect to the total amount of the colorant (a).

The content of the colorant (a) 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 further preferably 5% by mass or more and 50% by mass or less, based on the total amount of solid components.

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 a structural unit derived from a monomer (Ba) selected from at least one of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride.

Examples of such resins (B) include the following resins [ K1] to [ K6 ].

A resin [ K1] which is a copolymer having a structural unit derived from a monomer (a) (hereinafter sometimes referred to as "(a)") which is at least one selected from unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a structural unit derived from a monomer (b) (hereinafter sometimes referred to as "(b)") which has a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;

a resin [ K2] having a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from a monomer (c) (which is different from (a) and (b)) (hereinafter, may be referred to as "(c)");

the resin [ K3] has a copolymer of a structural unit derived from (a) and a structural unit derived from (c);

a resin [ K4] having a structural unit obtained by adding a structural unit derived from (b) to a structural unit derived from (a) and a structural unit derived from (c) (copolymer);

a resin [ K5] having a structural unit obtained by adding a structural unit derived from (b) to (a) and a structural unit derived from (c) (a copolymer);

the resin [ K6] is a resin (copolymer) having a structural unit derived from (c) and a structural unit derived from (b) to which (a) is added and further a structural unit derived from carboxylic anhydride is added.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, p-vinylbenzoic acid;

unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5, 6-tetrahydrophthalic acid, 1,2,3, 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1, 4-cyclohexene dicarboxylic acid;

carboxyl group-containing bicyclic unsaturated compounds such as 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 and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

unsaturated dicarboxylic anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;

unsaturated mono [ (meth) acryloyloxyalkyl ] esters of 2-or more-membered polycarboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl ] ester and phthalic acid mono [2- (meth) acryloyloxyethyl ] ester;

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as α - (hydroxymethyl) acrylic acid.

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

(b) For example, the polymerizable compound has a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond.

(b) Preferred are monomers having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

In the present specification, "(meth) acrylic acid" means at least 1 selected from acrylic acid and methacrylic acid. The expressions "(meth) acryloyl group" and "(meth) acrylate" and the like have the same meaning.

Examples of (b) include a monomer (b1) (hereinafter sometimes referred to as "(b 1)") having an oxiranyl group and an ethylenically unsaturated bond, a monomer (b2) (hereinafter sometimes referred to as "(b 2)") having an oxetanyl group and an ethylenically unsaturated bond, and a monomer (b3) (hereinafter sometimes referred to as "(b 3)") having a tetrahydrofuranyl group and an ethylenically unsaturated bond.

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

Examples of (b1-1) include glycidyl (meth) acrylate, β -methylglycidyl (meth) acrylate, β -ethylglycidyl (meth) acrylate, 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 (glycidoxymethyl) styrene, 2, 4-bis (glycidoxymethyl) styrene, 2, 5-bis (glycidoxymethyl) styrene, 2-bis (glycidoxymethyl) styrene, p-vinylbenzyl glycidyl ether, p-vinylbenzyl ether, vinylbenzyl (vinylbenzyl), vinylbenzyl (vinylbenzyl) acrylate, vinylbenzyl (B-1) acrylate, vinylbenzyl (vinylbenzyl) acrylate, vinylbenzyl (b-1) acrylate, vinylbenzyl (vinylbenzyl) acrylate, vinylbenzyl (b-1) acrylate, vinylbenzyl (b) acrylate, vinylbenzyl (meth) acrylate, and (meth) acrylate, wherein (meth) acrylate, and (b) acrylate, wherein (b) acrylate, and (wherein (b) acrylate (wherein (1) acrylate) and (wherein (b) and (wherein (b) and (wherein (1) and (b) and (wherein (b) are optionally) and (wherein (b) and (wherein (b) and (wherein) and (wherein) are indicated) and (wherein) and (b) and (wherein) are indicated) and, 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 and the like.

Examples of (b1-2) include vinylcyclohexene monoxide, 1, 2-epoxy-4-vinylcyclohexane (for example, セロキサイド (registered trademark) 2000, (manufactured by laugaku), (manufactured by 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, サイクロマー (registered trademark) a400, (manufactured by laugaku), (manufactured by 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, サイクロマー M100, (manufactured by laugaku)), a compound represented by the formula (BI), a compound represented by the formula (BII), and the like.

[ formula (BI) and formula (BII) wherein R^aAnd R^bEach independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X^aAnd X^bRepresents a single bond, — R^c-、*-R^c-O-、*-R^c-S-or R^c-NH-。

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

Denotes a bond end to O. ]

As R^a、R^bExamples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, and the like.

As R^a、R^bExamples of the alkyl group in which the hydrogen atom is substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.

As R^aAnd R^bThe alkyl group is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and specific examples thereof include a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl groupMore preferably, a hydrogen atom or a methyl group is mentioned.

As R^cExamples of the alkylene group of (a) include linear or branched alkylene groups, and specifically include linear alkylene groups such as methylene, ethylene, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl and hexane-1, 6-diyl; propane-1, 2-diyl and branched alkylene groups.

As X^aAnd X^bPreferably a single bond,. about. -R^c-, or-R^c-O-, more preferably a single bond, or-R^c-O-, particularly preferably a single bond, methylene, ethylene or-CH₂-O-and-CH₂CH₂-O-more preferably a single bond,. or-CH₂CH₂-O- (. indicates a bonding end to O).

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

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

The compound represented by the formula (BI) and the compound represented by the formula (BII) may each be used alone, or the compound represented by the formula (BI) may be used in combination with the compound represented by the formula (BII). When they are used in combination, the content ratio of the compound represented by the formula (BI) and the compound represented by the formula (BII) is preferably 5: 95-95: 5, more preferably 10: 90-90: 10, more preferably 20: 80-80: 20.

as (b2), monomers having an oxetanyl group and a (meth) acryloyloxy group are more preferable. Examples of (b2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxyethyloxetane, 3-methyl-3-acryloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxetane and 3-ethyl-3-acryloxyethyloxetane.

As (b3), monomers having a tetrahydrofuranyl group and a (meth) acryloyloxy group are more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., ビスコート V #150, manufactured by Osaka organic chemical industries, Ltd.), and tetrahydrofurfuryl methacrylate.

As (b), it is preferable to use (b1) in order to further improve the reliability of the obtained color filter, such as heat resistance and chemical resistance. Further, (b1-2) is more preferable in that the coloring composition has excellent storage stability.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 ] meth) acrylate^2,6]Decan-8-yl ester (in the technical field, known by the customary name bicyclopentyl (meth) acrylate)". Also, it is sometimes referred to as "tricyclodecyl (meth) acrylate". ) And (meth) acrylic acid tricyclo [5.2.1.0^2,6]Decen-8-yl ester (commonly known in the art as "dicyclopentenyl (meth) acrylate"), (meth) acrylates such as dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate;

hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2 '-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5, 6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, Bicyclo-2-enes such as 5, 6-dimethoxybicyclo [2.2.1] hept-2-ene, 5, 6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonybicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5, 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene A species;

dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

vinyl group-containing aromatic compounds such as styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene; vinyl group-containing nitriles such as acrylonitrile and methacrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; vinyl group-containing amides such as acrylamide and methacrylamide; esters such as vinyl acetate; dienes such as 1, 3-butadiene, isoprene, and 2, 3-dimethyl-1, 3-butadiene.

Among these, the (c) is preferably an aromatic compound containing a vinyl group, a dicarbonylimine derivative, or a bicyclic unsaturated compound, from the viewpoints of copolymerization reactivity and heat resistance. Specifically, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable.

In the resin [ K1], the ratio of the structural units derived from the respective monomers is preferably such that all the structural units constituting the resin [ K1]

Structural unit from (a): 2 to 60 mol%

Structural units from (b): 40 to 98 mol percent of the total amount of the catalyst,

more preferably

Structural unit from (a): 10 to 50 mol%

Structural units from (b): 50 to 90 mol%.

When the ratio of the constituent units of the resin [ K1] is within the above range, the colored composition tends to have excellent storage stability, developability in forming a colored pattern, and solvent resistance of the resulting color filter.

The resin [ K1] can be produced, for example, by a method described in "Experimental methods for Polymer Synthesis" (published by Otsuka-shogaku Kogyo, 1 st edition, 1972, 3/1) and a cited document described in the above document.

Specifically, a method in which the predetermined amounts of (a) and (b), a polymerization initiator, a solvent and the like are charged into a reaction vessel, oxygen is replaced with nitrogen, for example, to form a deoxygenated atmosphere, and heating and heat-maintaining are carried out while stirring. The polymerization initiator, solvent, and the like used herein are not particularly limited, and those generally used in the art can be used. Examples of the polymerization initiator include azo compounds (e.g., 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile)), organic peroxides (e.g., benzoyl peroxide), solvents that dissolve the respective monomers, and solvents that are exemplified as the solvent (E) of the coloring composition of the present invention.

The obtained copolymer may be used as it is as a solution after the reaction, may be used as a concentrated or diluted solution, or may be used as a product taken out as a solid (powder) by a method such as reprecipitation. In particular, in the polymerization, the solvent contained in the colored composition of the present invention is used as a solvent, and thus the solution after the reaction can be used as it is for the preparation of the colored composition of the present invention, and therefore the production process of the colored composition of the present invention can be simplified.

In the resin [ K2], the ratio of the structural units derived from the respective monomers is preferably such that all the structural units constituting the resin [ K2]

Structural unit from (a): 2 to 45 mol%

Structural units from (b): 2 to 95 mol%

Structural units from (c): 1 to 65 mol% of a surfactant,

more preferably

Structural unit from (a): 5 to 40 mol%

Structural units from (b): 5 to 80 mol%

Structural units from (c): 5 to 60 mol%.

When the ratio of the constituent units of the resin [ K2] is within the above range, the colored composition tends to have excellent storage stability, developability in forming a colored pattern, and solvent resistance, heat resistance, and mechanical strength of the resulting color filter.

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

In the resin [ K3], the ratio of the structural units derived from the respective monomers is preferably such that the structural units constituting the resin [ K3] are all

Structural unit from (a): 2 to 60 mol%

Structural units from (c): 40 to 98 mol percent of the total amount of the catalyst,

more preferably

Structural unit from (a): 10 to 50 mol%

Structural units from (c): 50 to 90 mol%.

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

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

First, the copolymer of (a) and (c) can be produced in the same manner as the method described as the method for producing the resin [ K1 ]. In this case, the ratio of the structural units derived from the respective monomers is preferably the same ratio as that listed in the resin [ K3 ].

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

Then, the copolymer of (a) and (c) is produced by replacing the atmosphere in the flask with nitrogen to air, charging (b), a reaction catalyst for a carboxylic acid or a carboxylic anhydride and a cyclic ether (for example, tris (dimethylaminomethyl) phenol) and a polymerization inhibitor (for example, hydroquinone) into the flask, and reacting at 60 to 130 ℃ for 1 to 10 hours, for example, to produce a resin [ K4 ].

(b) The amount of (b) to be used is preferably 5 to 80 moles, more preferably 10 to 75 moles, based on 100 moles of (a). By adjusting the amount of (b) to be used within this range, the storage stability of the coloring composition, the developability during pattern formation, and the balance among solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern tend to be good. Since the cyclic ether has high reactivity and unreacted (b) hardly remains, the (b) used for the resin [ K4] is preferably (b1), and more preferably (b 1-1).

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

The reaction conditions such as the method of feeding each reagent, the reaction temperature and the reaction time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. Further, similarly to the polymerization conditions, the feeding method and the reaction temperature can be appropriately adjusted in consideration of the production facilities, the amount of heat generated by polymerization, and the like.

In the first step of producing the resin [ K5], a copolymer of (b) and (c) was obtained in the same manner as in the production method of the resin [ K1 ]. The copolymer obtained may be used as it is as a solution after the reaction, as a concentrated or diluted solution, or as a solid (powder) obtained by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c) to the total molar number of all the structural units constituting the copolymer of (b) and (c) is preferably each

Structural units from (b): 5 to 95 mol%

Structural units from (c): 5 to 95 mol% of a surfactant,

more preferably

Structural units from (b): 10 to 90 mol%

Structural units from (c): 10 to 90 mol%.

Further, as a second stage, the resin [ K5] can be obtained by reacting the carboxylic acid or carboxylic anhydride having (a) with the cyclic ether derived from (b) which is contained in the copolymer of (b) and (c) under the same conditions as the production method of the resin [ K4 ].

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

The resin [ K6] is a resin obtained by further reacting a carboxylic acid anhydride with the resin [ K5 ]. Reacting a carboxylic anhydride with a hydroxyl group resulting from the reaction of a cyclic ether with a carboxylic acid or carboxylic anhydride.

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

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5, 6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride. The amount of the carboxylic anhydride to be used is preferably 0.5 to 1 mol based on 1 mol of the amount of (a).

Specific examples of the resin (B) include a 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid copolymer, and a 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2.6]Resins [ K1] such as decyl ester/(meth) acrylic acid copolymers](ii) a Glycidyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, 3, 4-epoxy tricyclo (meth) acrylate [5.2.1.0 ]^2.6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3, 4-epoxy tricyclo [5.2.1.0 ] acrylic acid^2.6]Resins such as decyl ester/(meth) acrylic acid/vinyltoluene copolymer and 3-methyl-3- (meth) acryloyloxymethyl oxetane/(meth) acrylic acid/styrene copolymer [ K2](ii) a Resins [ K3] such as benzyl (meth) acrylate/(meth) acrylic acid copolymer, styrene/(meth) acrylic acid copolymer, benzyl (meth) acrylate/(meth) acrylic acid tricyclodecanyl ester/(meth) acrylic acid copolymer](ii) a A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate/(meth) acrylic acid copolymer, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, and a resin obtained by adding glycidyl (meth) acrylate to tricyclodecyl (meth) acrylate/(meth) acrylic acid benzylResins obtained by addition of ester/(meth) acrylic acid copolymers [ K4](ii) a Resins obtained by reacting (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate/(glycidyl (meth) acrylate), and resins obtained by reacting (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate/styrene/(glycidyl (meth) acrylate) [ K5]](ii) a Resins obtained by reacting a copolymer of (meth) acrylic acid and tricyclodecanyl (meth) acrylate/(glycidyl (meth) acrylate), and resins obtained by further reacting tetrahydrophthalic anhydride [ K6]]And the like.

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 the group consisting of resin [ K2] and resin [ K3 ]. These resins provide a colored composition having excellent developability. From the viewpoint of adhesion between the colored pattern and the substrate, resin [ K2] is more preferable.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3000 to 100000, more preferably 5000 to 50000, and still more preferably 5000 to 30000. When the molecular weight is within the above range, the coating film hardness tends to be high, the residual film ratio tends to be high, the unexposed portion tends to have good solubility in a developer, and the resolution of the colored pattern tends to be improved.

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

The acid value of the resin (B) in terms of solid content is preferably 30 to 170mg-KOH/g, more preferably 40 to 150mg-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 1g of the resin (B), and can be determined by titration using an aqueous solution of potassium hydroxide, for example.

When the resin (B) is contained, the content of the resin (B) is preferably 7 to 70% by mass, more preferably 13 to 65% by mass, and still more preferably 17 to 60% by mass, based on the total amount of solid components. If the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and the residual film ratio of the colored pattern tend to be improved.

Polymerizable Compound (C)

The polymerizable compound (C) is a compound which can be polymerized by an active radical and/or an acid generated by the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and preferably (meth) acrylate compounds.

Examples of the polymerizable compound having 1 ethylenically unsaturated bond include nonylphenylcarbinol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the above-mentioned (Ba), (Bb), and (Bc).

Examples of the polymerizable compound having 2 ethylenically unsaturated bonds include 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol a, 3-methylpentanediol di (meth) acrylate, and the like.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and mixtures thereof, Caprolactone-modified dipentaerythritol hexa (meth) acrylate, etc., and 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 to 2900, more preferably 250 to 1500.

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

In addition, in the case of including the resin (B) and the polymerizable compound (C), the content ratio of the resin (B) to the polymerizable compound (C) [ resin (B): the polymerizable compound (C) ] is preferably 20: 80-80: 20, more preferably 30: 70-80: 20.

when the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a colored pattern and the chemical resistance of a color filter tend to be improved.

Polymerization initiator (D)

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

Examples of the polymerization initiator (D) include an O-acyloxime compound, an alkylphenone compound, a bisimidazole compound, a triazine compound, and an acylphosphine oxide compound.

The O-acyloxime compound is a compound having a partial structure represented by the formula (d 1). Hereinafter, denotes a bonding end.

Examples of the O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine, and N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4-yl ] ethane-1-imine - (3, 3-dimethyl-2, 4-dioxocyclopentylmethoxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine, and the like. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF Co., Ltd.), N-1919 (manufactured by ADEKA Co., Ltd.) and the like can be used. Among them, the O-acyloxime compound is preferably at least 1 selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, and more preferably N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine.

The alkylphenyl ketone compound is, for example, a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d 3). In these partial structures, the benzene ring may have a substituent.

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

Examples of the compound having a partial structure represented by the formula (Dd3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, benzildimethylketal, and the like.

In terms of sensitivity, as the alkylphenyl ketone compound, a compound having a partial structure represented by the formula (d2) is preferable.

Examples of the bisimidazole compound include compounds represented by the formula (d 4).

[ formula (d4), R^d1～R^d6Represents an aryl group having 6 to 10 carbon atoms which may have a substituent.]

As R^d1～R^d6Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl and naphthyl, and phenyl is preferable.

As a substituent for the above R^d1～R^d6Examples of the substituent for the aryl group in (1) include a halogen atom, an alkoxy group having 1 to 4 carbon atoms and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom is preferable. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy and butoxy groups, and a methoxy group is preferable.

Examples of the biimidazole compound include 2,2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenylbiimidazole, 2 ' -bis (2, 3-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenylbiimidazole (see, for example, japanese unexamined patent publication No. 6-75372, japanese unexamined patent publication No. 6-75373, etc.), 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenylbiimidazole, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetrakis (alkoxyphenyl) biimidazole, 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetrakis (dialkoxyphenyl) biimidazole, 2,2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetrakis (trialkoxyphenyl) biimidazole (see, for example, Japanese patent publication No. 48-38403, Japanese patent publication No. 62-174204, etc.), and imidazole compounds in which the phenyl group at the 4,4 ', 5,5 ' -position is substituted with an alkoxycarbonyl group (see, for example, Japanese patent publication No. 7-10913, etc.). Among them, compounds represented by the following formula and mixtures thereof are preferable.

Examples of the triazine compound include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl ] -1,3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl ] -1,3, 5-triazine A group ] -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, and the like.

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

Further, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3 ', 4,4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2,4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone, etc.; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, and the like.

These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) described later.

Examples of the polymerization initiator generating an acid include onium salts such as 4-hydroxyphenyl dimethylsulfonium-p-toluenesulfonate, 4-hydroxyphenyl dimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyl dimethylsulfonium-p-toluenesulfonate, 4-acetoxyphenyl methylbenzyl sulfonium hexafluoroantimonate, triphenyl sulfonium-p-toluenesulfonate, triphenyl sulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylates and benzoin tosylates.

As the polymerization initiator (D), a polymerization initiator that generates an active radical is preferable, specifically, a polymerization initiator containing at least one selected from the group consisting of an alkylphenyl ketone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a bisimidazole compound, and more preferably, a polymerization initiator containing an O-acyloxime compound.

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

Polymerization initiation assistant (D1)

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

Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the amine compound include alkanolamines such as triethanolamine, methyldiethanolamine, triisopropanolamine and the like; aminobenzoate such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate and 2-ethylhexyl 4-dimethylaminobenzoate; n, N-dimethyl-p-toluidine; and alkylaminobenzophenones such as 4,4 ' -bis (dimethylamino) benzophenone (known as michler's ketone), 4 ' -bis (diethylamino) benzophenone, and 4,4 ' -bis (ethylmethylamino) benzophenone, and among them, alkylaminobenzophenones are preferable, and 4,4 ' -bis (diethylamino) benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Baotu chemical Co., Ltd.) can be used.

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

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

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

When the polymerization initiator aid (D1) is used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). If the amount of the polymerization initiating assistant (D1) is within this range, a colored pattern can be further formed with high sensitivity, and the productivity of the color filter tends to be improved.

Flatting agent (F)

Examples of the leveling agent (F) include a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, トーレシリコーン DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (manufactured by toray-dow corning corporation), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by shin-Etsu chemical industry corporation), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by モメンティブ, パフォーマンス, マテリアルズ, ジャパン contract).

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, フロラード (registered trademark) FC430, FC431 (manufactured by sumitomo 3M), メガファック (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (manufactured by DIC), エフトップ (registered trademark) EF301, EF303, EF351, EF352 (manufactured by mitsubishi マテリアル), サーフロン (registered trademark) S381, S382, SC101, SC105 (manufactured by asahi nitre), E5844 (manufactured by strain ダイキンファインケミカル), and the like can be mentioned.

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, メガファック (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC corporation) and the like are exemplified.

When the leveling agent (F) is contained, the content thereof is preferably 0.001 mass% or more and 0.5 mass% or less, more preferably 0.002 mass% or more and 0.4 mass% or less, and further preferably 0.005 mass% or more and 0.3 mass% or less, based on the total amount of the coloring composition. If the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

Other ingredients

The coloring composition may contain, if necessary, additives known in the art, such as a filler, another polymer compound, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent.

Method for producing coloring composition

Further, the coloring composition containing the resin (B), the polymerizable compound (C), the polymerization initiator (D) and the solvent (E) can be prepared, for example, by mixing the compound (a-I), the resin (B), the polymerizable compound (C), the polymerization initiator (D), the solvent (E), the coloring agent (a) other than the compound (a-I) used as needed, the leveling agent (F), the polymerization initiation assistant (D1) and other components.

When the pigment (P) is contained, the pigment is preferably mixed with a part or the whole of the solvent (E) in advance, and dispersed by using a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. In this case, a part or all of the pigment dispersant and the resin (B) may be blended as necessary. By mixing the remaining components into the pigment dispersion liquid thus obtained so as to have a predetermined concentration, a desired coloring composition can be prepared.

In the present invention, the compound (a-I) may be mixed with a solvent to prepare a colored dispersion. When the colored dispersion liquid is prepared and then mixed with the resin (B), the polymerizable compound (C), the polymerization initiator (D), and the like to form a colored composition, the heat resistance in the production of 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. For dispersing the compound (a-I), a particularly preferable solvent (E1) is, for example, an ether ester solvent, and more preferably, a solvent in which one hydroxyl group of an alkylene glycol or a polyalkylene glycol is etherified and the remaining hydroxyl group is esterified, and examples thereof include 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 monobutyl ether acetate, dipropylene glycol methyl ether acetate, and the like. These may be used alone or in combination of two or more.

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, based on 1 part by mass of the compound (A-I).

When preparing the coloring dispersion, a dispersant is preferably used. Examples of the dispersant include known pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic dispersants. These pigment dispersants may be used alone, or 2 or more kinds may be used in combination. Examples of the pigment dispersant include KP (manufactured by shin-Etsu chemical Co., Ltd.), フローレン (manufactured by Kyoho chemical Co., Ltd.), ソルスパース (manufactured by ゼネカ (Co., Ltd.), EFKA (manufactured by BASF Co., Ltd.), アジスパー (manufactured by monosodium glutamate ファインテクノ (Co., Ltd.), Disperbyk and BYK (manufactured by ビックケミー Co., Ltd.), which are trade names.

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, based on 100 parts by mass of the compound (A-I).

In addition, in the case where 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 needed. 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, based on 100 parts by mass of the compound (A-I).

The coloring dispersion liquid may contain a part or all, preferably a part, of the resin (B) used in the coloring composition in advance, as necessary. By including the resin (B) in advance, the dispersibility when the coloring composition is prepared can be further improved. The amount of the resin (B) in the colored dispersion 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 per 100 parts by mass of the compound (A-I) in terms of solid content.

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

Further, it is preferable to prepare a solution by dissolving the compound (a-I) in a part or all of the solvent (E) in advance. More preferably, the solution is filtered through a filter having a pore size of about 0.01 to 1 μm.

The mixed colored composition is preferably filtered by a filter having a pore diameter of about 0.01 to 10 μm.

Method for manufacturing color filter

Examples of the method for producing a colored pattern from the colored composition of the present invention include photolithography, ink jet printing, and printing. Among them, photolithography is preferable. The photolithography method is a method in which the colored composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed to light through a photomask and developed. In the photolithography method, a colored coating film, which is a cured product of the colored composition layer, can be formed without using a photomask and/or without developing during exposure. The colored pattern and the colored coating film thus formed can be used as a color filter.

The film thickness of the color filter to be produced is not particularly limited, and can be suitably adjusted according to the purpose, application, and the like, 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, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass having a silica-coated surface, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, or silicon, a product obtained by forming a thin film of aluminum, silver/copper/palladium alloy, or the like on the above substrate, or the like can be used. Additional color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of each color pixel by photolithography can be performed under known or conventional apparatus and conditions. For example, it can be produced as follows.

First, the coloring composition is applied onto a substrate, and is dried by heating (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent and dry the resultant, thereby obtaining a smooth coloring composition layer.

Examples of the coating method include spin coating, slit and spin coating.

The temperature for heating and drying is preferably 30 to 120 ℃, more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

When the drying is carried out under reduced pressure, it is preferably carried out under a pressure of 50 to 150Pa and at a temperature of 20 to 25 ℃.

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

Next, the coloring composition layer is exposed to light through a photomask for forming a coloring pattern of an object. The pattern on the photomask is not particularly limited, and a pattern suitable for the intended use may be used.

As the light source for exposure, a light source generating light having a wavelength of 250 to 450nm is preferable. For example, light of less than 350nm may be selectively extracted by a filter for cutting the wavelength range, or light of about 436nm, 408nm, or 365nm may be selectively extracted by a band-pass filter for extracting the wavelength ranges. Specifically, the light source may be a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, or the like.

Since the entire exposure surface can be uniformly irradiated with parallel light rays to perform accurate alignment of the photomask and the substrate on which the colored composition layer is formed, an exposure apparatus such as a mask aligner or a stepper is preferably used.

The exposed colored composition layer is developed by contacting it with a developing solution, thereby forming a colored pattern on the substrate. By the development, the unexposed portions of the colored composition layer are dissolved in the developer and removed. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.

The developing method may be any of spin coating immersion, dipping, spraying, and the like. Further, the substrate can be tilted at an arbitrary angle during development.

After development, washing with water is preferred.

Further, the obtained colored pattern is preferably subjected to post-baking. The post-baking temperature is preferably 150 to 250 ℃, and more preferably 160 to 235 ℃. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

The compound of the present invention has high absorbance, and a color filter having excellent solvent resistance can be produced by using a colored composition using the compound. The color filter can be used as a color filter for display devices (e.g., liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, the% and parts of the content or amount used are by mass unless otherwise specified.

Unless otherwise specified, the reaction was carried out under a nitrogen atmosphere. Hereinafter, the structure of the compound was confirmed by MASS analysis (LC, model 1200 by Agilent, MASS, and LC/MSD by Agilent).

Example 1

10.0 parts of potassium thiocyanate and 55.0 parts of acetonitrile were put into a flask equipped with a cooling tube and a stirrer, and then stirred at room temperature for 30 minutes. 13.6 parts of 2-fluorobenzoyl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise over 10 minutes, and the mixture was stirred at room temperature for 2 hours. 11.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo chemical industry Co., Ltd.) was added dropwise thereto, 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-exchanged water, and after dropping the solution, 22.9 parts of 30% aqueous sodium hydroxide solution was dropped. After completion of the dropwise addition, the mixture was stirred at room temperature for 20 hours. 204.0 parts of ion-exchanged water was added thereto, and 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 with 200.0 parts of ion-exchanged water to obtain a wet cake of the compound represented by the 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 stirrer, and stirred at room temperature for 30 minutes. The whole amount of the obtained wet cake of the compound represented by the formula (B-I-1) was added and stirred at room temperature for 2 hours. 35.4 parts of a 30% aqueous sodium hydroxide solution was added thereto, and the mixture was purified by liquid separation to obtain an organic layer. The obtained organic layer was subjected to liquid separation purification using 68.0 parts of ion-exchanged water, and then subjected to liquid separation purification using a 35% aqueous hydrochloric acid solution. 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 off to obtain 18.5 parts of a compound represented by the formula (B-I-2). The yield thereof was found to be 69%.

15.3 parts of N-methylaniline (manufactured by Tokyo chemical industry Co., Ltd.) and 60 parts of N, N-dimethylformamide were placed in a flask equipped with a cooling tube and a stirring device, and then the mixed solution was cooled in ice. 5.7 parts of 60% sodium hydride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added little by little over 30 minutes under ice-cooling, and the mixture was stirred for 1 hour while being warmed to room temperature. 10.4 parts of 4, 4' -difluorobenzophenone (manufactured by Tokyo chemical industries, Ltd.) was added little by little to the reaction mixture, and stirred at room temperature for 24 hours. The reaction solution was gradually added to 200 parts of ice water, and then, the mixture was allowed to stand at room temperature for 15 hours, and water was removed by decantation, whereby a viscous solid was obtained as a residue. After 60 parts of methanol was added to the viscous solid, the mixture was stirred at room temperature for 15 hours. The precipitated solid was separated by filtration and purified by column chromatography. The purified pale yellow solid was dried under reduced pressure at 60 ℃ to obtain 9.8 parts of a compound represented by the formula (BP-1). The yield thereof was found to be 53%.

After 8.2 parts of the compound represented by the formula (B-I-2), 10.0 parts of the compound represented by the formula (BP-1) and 20.0 parts of toluene were charged into a flask equipped with a cooling tube and a stirrer, 12.2 parts of phosphorus oxychloride was added thereto and the mixture was stirred at 95 to 100 ℃ for 3 hours. Next, the reaction mixture was cooled to room temperature, and then diluted with 170.0 parts of isopropyl alcohol. Then, the diluted reaction solution was poured into 300.0 parts of saturated brine, 100 parts of toluene was added thereto, and the mixture was stirred for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes, whereby an organic layer and an aqueous layer were separated. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of a saturated saline solution. An appropriate amount of mirabilite was added to the organic layer, stirred for 30 minutes, and then filtered to obtain a dried organic layer. The solvent of the obtained organic layer was distilled off by an evaporator to obtain a bluish purple solid. Further, the bluish-purple solid was dried at 60 ℃ under reduced pressure to obtain 18.4 parts of a compound represented by the formula (A-IV-1). The yield thereof was found to be 100%.

Identification of Compound represented by formula (A-IV-1)

(Mass analysis) ionization mode ═ ESI +: m/z 687.3[ M-Cl ═]⁺

Accurate quality: 722.3

12.4 parts of the compound represented by the formula (A-IV-1) and 45.5 parts of chloroform were placed in a flask equipped with a cooling tube and a stirrer, and stirred. Next, 10 parts of chlorosulfonic acid (manufactured by Tokyo chemical industry Co., Ltd.) was added thereto, and the mixture was stirred at 25 to 30 ℃ for 18 hours. After cooling to room temperature, 210 parts of N, N-dimethylformamide was added thereto, and the reaction mixture was dropped little by little into 2610 parts of toluene. After stirring for 1 hour, the solid obtained by filtration was washed with 870 parts of toluene and then dried at 60 ℃ under reduced pressure to obtain 12.9 parts of a compound represented by the formula (A-III-1). The yield thereof was found to be 89%.

Identification of Compound represented by formula (A-III-1)

(mass analysis) ionization mode ═ ESI +: 845.3[ M/z ═ M]⁺

Accurate quality: 846.2

69.8 parts of the compound represented by the formula (A-III-1) and 418 parts of chloroform were placed in a flask equipped with a cooling tube and a stirrer and stirred. Phosphorus oxychloride 369.7 parts was added dropwise thereto, and the mixture was stirred at 60 ℃ for 4 hours. After cooling 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, resulting in separation into an organic layer and an aqueous layer. The obtained organic layer was subjected to 2-time liquid separation washing using 4000 parts of cold water. After 14.7 parts of trifluoromethanesulfonamide and 10 parts of triethylamine were dissolved in 100 parts of chloroform, the resulting solution was added to the organic layer, and the mixture was reacted at room temperature for 12 hours. The reaction solution was poured into 5000 parts of ion-exchanged water, and then stirred for 30 minutes. The stirring was stopped, and the mixture was allowed to stand for 30 minutes, resulting in separation into an organic layer and an aqueous layer. The obtained organic layer was subjected to 2 times of liquid separation washing using 4000 parts of ion-exchanged water. To the organic layer was added 200 parts of magnesium sulfate, and after stirring for 1 hour, the solvent of the resulting organic layer was distilled off by an evaporator to obtain a bluish-purple solid. Further, the bluish-purple solid was dried at 60 ℃ under reduced pressure to obtain 44.2 parts of 32 of compounds represented by the formulae (A-III-1), (A-II-1) and (A-II-2): 41: 16 mixture (molar basis). This mixture was called colorant (A-II-3).

Identification of Compound represented by formula (A-II-1)

(mass analysis) ionization mode ═ ESI +: 978.5[ M/z ═ M]⁺

Accurate quality: 977.2

Identification of Compound represented by formula (A-II-2)

(mass analysis) ionization mode ═ ESI +: 1109.5[ M/z ═ M]⁺

Accurate quality: 1108.1

Example 2

2.0 parts of the compound represented by (A-IV-1) and 5.7 parts of methylene chloride were put into a flask equipped with a cooling tube and a stirrer, and 1.6 parts of chlorosulfonic acid was dropped into the flask at 25 to 30 ℃ and stirred at the same temperature for 3 hours. Next, a mixture of 3.3 parts of DMF and 0.3 part of ion-exchanged water was added dropwise so as not to exceed 25 ℃ to prepare a solution. The solution was poured into 32.7 parts of toluene, the liquid portion was separated, and the residue was washed with 16.3 parts of toluene again. The remaining residue was concentrated under reduced pressure by an evaporator, and the concentrate was poured into 31.2 parts of ion-exchanged water to precipitate crystals, followed by filtration. The crude filtrate was suspended in 13.0 parts of a 20% aqueous sodium chloride solution, filtered, and the solid obtained by filtration was washed with 13.0 parts of a 20% aqueous sodium chloride solution and dried under reduced pressure at 35 ℃. Then, this dried product was dissolved in 6.2 parts of methanol, and the insoluble matter was filtered, concentrated under reduced pressure using an evaporator, and dried under reduced pressure at 35 ℃ to obtain 1.9 parts of a compound represented by the formula (a-III-1) as a cyan solid. The yield thereof was found to be 97.9%.

Identification of Compound represented by formula (A-III-1)

(mass analysis) ionization mode ═ ESI +: 845.3[ M/z ═ M]⁺

Accurate quality: 846.2

The following reaction was carried out under nitrogen atmosphere. 2.0 parts of the compound represented by the formula (A-III-1) obtained above and 10.0 parts of acetonitrile were put into a flask equipped with a cooling tube and a stirrer, and 1.0 part of phosphorus oxychloride was dropped at 70 to 80 ℃. Stirred at the same temperature for 2 hours. Then, the reaction mixture was cooled to 5 ℃ and 1.0 part of trifluoromethanesulfonamide was added thereto. Then, 2.3 parts of triethylamine was added dropwise at 5 to 15 ℃ and stirred at 15 to 30 ℃ for 2 hours. To the reaction solution, 10.0 parts of methyl ethyl ketone and 10.0 parts of a 20% aqueous solution of sodium chloride were injected, and the mixture was concentrated under reduced pressure using an evaporator. To the concentrated residue were poured 15.0 parts of methylene chloride and 10.0 parts of ion-exchanged water to separate an organic layer from a water layer, and the organic layer was concentrated under reduced pressure using an evaporator and dried under reduced pressure at 35 ℃ to obtain 3.1 parts of a compound represented by the formula (a-II-2) as a cyan solid. The yield thereof was found to be 107.7%.

Identification of Compound represented by formula (A-II-2)

(mass analysis) ionization mode ═ ESI +: 1109.5[ M/z ═ M]⁺

Accurate quality: 1108.1

Example 3

Into a flask equipped with a cooling tube and a stirrer, 2.0 parts of the compound represented by formula (A-II-2), 3.4 parts of magnesium chloride hexahydrate, 40.0 parts of dimethyl sulfoxide, and 16.0 parts of ion-exchanged water were charged, and the mixture was stirred at 80 ℃ 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 added dropwise thereto, and the mixture was stirred at 40 ℃ for 30 minutes. The obtained suspension was filtered, and the filtered solid was washed with 20.0 parts and 50.0 parts of ion-exchanged water 2 times. The obtained solid was dried at 60 ℃ under reduced pressure to obtain 1.9 parts of a compound represented by the formula (A-II-4).

Example 4

A compound represented by the formula (a-II-5) was synthesized by the same reaction as in example 3, except that magnesium chloride hexahydrate was changed to zinc chloride.

Example 5

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

Example 6

30 of the compounds represented by the formulae (A-III-2), (A-II-7) and (A-II-8) were obtained in the same manner as in example 1, except that the compound represented by the formula (BP-1) was changed to the compound represented by the formula (BP-2): 52: 9 mixture (molar basis). This mixture is called colorant (A-II-9). In the formula, — SO₃ ^-and-SO₂-N^--SO₂-CF₃This means that any of the hydrogen atoms contained in the partial structure in parentheses is substituted.

Identification of Compound represented by formula (A-III-2)

(mass analysis) ionization mode ═ ESI +: m/z 931.5[ M]⁺

Accurate quality: 930.3

Identification of Compound represented by formula (A-II-7)

(mass analysis) ionization mode ═ ESI +: m/z 1063.5[ M [ ]]⁺

Accurate quality: 1061.3

Identification of Compound represented by formula (A-II-8)

(mass analysis) ionization mode ═ ESI +: 1193.5[ M/z ═ M]⁺

Accurate quality: 1192.2

Example 7

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

Identification of Compound represented by formula (A-II-8)

(mass analysis) ionization mode ═ ESI +: 1193.5[ M/z ═ M]⁺

Accurate quality: 1192.2

Example 8

The same reaction as in example 3 was carried out except that the compound represented by the formula (A-II-2) was changed to the compound represented by the formula (A-II-8), so as to synthesize a compound represented by the formula (A-II-10).

Example 9

The same reaction as in example 4 was carried out except that the compound represented by the formula (A-II-2) was changed to the compound represented by the formula (A-II-8), so as to synthesize a compound represented by the formula (A-II-11).

Example 10

The same reaction as in example 5 was carried out except that the compound represented by the formula (A-II-2) was changed to the compound represented by the formula (A-II-8), so as to synthesize a compound represented by the formula (A-II-12).

Comparative examples 1 and 2

A compound represented by the formula (A-X-1) (hereinafter also referred to as compound (A-X-1)) and a compound represented by the formula (A-X-2) (hereinafter also referred to as compound (A-X-2)) were synthesized according to the method described in Japanese patent laid-open publication No. 2015-38201.

[ Synthesis example 1]

An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, 100 parts of propylene glycol monomethyl ether acetate was charged, and the mixture was heated to 85 ℃ with stirring. Then, 19 parts of methacrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid were added dropwise to the flask over about 5 hours using a dropping pump^2,6]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0^2,6]Mixture of decan-9-yl esters (containing ratios in terms of mole ratios)Is 50: 50) 171 parts of a solution (trade name: E-DCPA, manufactured by Daiiluo Co., Ltd.) of propylene glycol monomethyl ether acetate (40 parts) was dissolved in the aqueous solution. On the other hand, a solution in which 26 parts of 2, 2' -azobis (2, 4-dimethylvaleronitrile), which is a polymerization initiator, was dissolved in 120 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over about 5 hours using a separate dropping pump. After completion of dropping of the polymerization initiator, the mixture was kept at the same temperature for about 3 hours and then cooled to room temperature to obtain a copolymer (resin (B-1)) solution having 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 introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was charged and heated to 80 ℃ with stirring. Then, 38 parts of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid were dropped into the flask using a dropping pump for about 5 hours^2,6]A mixture of decane-8 and 9-yl ester (containing a molar ratio of 50: 50) (trade name: E-DCPA, manufactured by Dacellosolve, Ltd.) was dissolved in 125 parts of propylene glycol monomethyl ether acetate 289. On the other hand, a solution in which 33 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile), a polymerization initiator, was dissolved in 235 parts of propylene glycol monomethyl ether acetate, was added dropwise to the flask over about 6 hours using a separate dropping pump. After completion of dropping of the polymerization initiator, the mixture was kept at the same temperature for about 4 hours and then cooled to room temperature, whereby a copolymer (resin (B-2)) having a solid content of 35.1% was obtained. The weight average molecular weight of the obtained resin (B-2) was 9200, the degree of dispersion was 2.08, and the acid value in terms of solid content was 77 mg-KOH/g.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin in terms of polystyrene were measured by GPC under the following conditions.

The device comprises the following steps: HLC-8120GPC (manufactured by Toso Cao Co., Ltd.)

Column: TSK-GELG2000HXL

Column temperature: 40 deg.C

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0mL/min

Concentration of solid component in test liquid: 0.001 to 0.01% by mass

Injection amount: 50 μ L

A detector: RI (Ri)

Calibration standard substance: TSK STANDARD POLYSTYRENE

F-40、F-4、F-288、A-2500、A-500

(manufactured by Tosoh corporation)

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

[ preparation of colored curable resin composition ]

Examples 11 to 20 and comparative examples 3 to 4

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

[ TABLE 14 ]

In table 14, each component represents the following compound.

(A-II-2): a compound represented by the formula (A-II-2)

(A-II-3): colorant (A-II-3)

(A-II-4): a compound represented by the formula (A-II-4)

(A-II-5): a compound represented by the formula (A-II-5)

(A-II-6): a compound represented by the formula (A-II-6)

(A-II-8): a compound represented by the formula (A-II-8)

(A-II-9): colorant (A-II-9)

(A-II-10): a compound represented by the formula (A-II-10)

(A-II-11): a compound represented by the formula (A-II-11)

(A-II-12): a compound represented by the formula (A-II-12)

(A-X-1): a compound represented by the formula (A-X-1)

(A-X-2): a compound represented by the formula (A-X-2)

(B-1): resin (B-1) (conversion of solid content)

(C-1): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemicals, Inc.)

(D-1): n-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Co., Ltd.; O-acyloxime compound)

(E-1): propylene glycol monomethyl ether acetate

(E-2): n-methyl pyrrolidone

(E-3): lactic acid ethyl ester

(F-1): polyether-modified silicone oil (in terms of solid content) (トーレシリコーン SH 8400; manufactured by Tolydakangning Co., Ltd.)

[ production of color Filter ]

The colored curable resin composition was applied to a 2-inch square glass substrate (# 1737; manufactured by corning) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a colored composition layer. After cooling, the resultant was exposed to 150mJ/cm at an atmospheric pressure using an exposure apparatus (TME-150 RSK; manufactured by トプコン Co., Ltd.)²Exposure with an exposure amount of (365nm basis). Note that a photomask is not used. The color filter (film thickness 2.0 μm) was produced by post-baking the exposed colored composition layer in an oven at 180 ℃ for 20 minutes.

[ measurement of Absorbance ]

Dissolving the obtained compound or coloring material 0.35g in chloroform to make the volume 250cm³2cm of it³Diluting with chloroform to make the volume 100cm³(concentration: 0.028g/L) was measured using a spectrophotometer (quartz cell, optical path length; 1cm)The absorption spectrum is defined. The absorbance at the maximum absorption wavelength converted to 0.028g/L was evaluated in accordance with 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 ]

A coating film of the colored photosensitive resin composition was immersed in N-methylpyrrolidone at room temperature for 40 minutes, and the color difference (. DELTA.Eab.) before and after the impregnation of the coating film was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS corporation), and evaluated according to the following criteria. The Δ Eab value is a value obtained from the following color difference formula in CIE1976(L, a, b) space color system (page 266 of japan color society, new color science manual (sho 60)).

ΔEab*＝{(ΔL*)2+(Δa*)2+(Δb*)2}1/2

A: less than 5.0

B: 5.0 or more and less than 10.0

C: 10.0 or more

[ TABLE 15 ]

[ measurement of Voltage holding ratio ]

0.025g of the obtained compound and 1g of liquid crystal (MCL-6608, メルク, Co., Ltd.) were mixed, and the mixture was heated at 120 ℃ for 50 minutes in a sample bottle. The mixture was transferred to a tube for centrifugal separation, and centrifugal separation was performed for 2 times for 30 minutes using MICRO SIX (manufactured by アズワン Co., Ltd.). The supernatant of the mixture was sealed in a cell for liquid crystal evaluation (KSRT-05/BIIIMINTS05X, e.h.c.co., ltd.), and the voltage holding ratio was measured under the following measurement conditions using a liquid crystal property evaluation device (manufactured by 6254, tokyo テクニカ co., ltd.) and evaluated according to the following criteria.

Measurement conditions

Applied voltage pulse amplitude: 5V

Voltage holding ratio: potential difference of liquid crystal cell after 1000 msec/value of voltage applied at 0 msec

Evaluation criteria

A: more than 95 percent

B: more than 85 percent and less than 95 percent

C: less than 85 percent

[ TABLE 16 ]

Examples 21 to 24 and comparative examples 5 and 6

[ method for producing Dispersion ]

The components shown in Table 17 were weighed, and 600 parts of 0.4 μm zirconia beads were put in the mixture, and shaken for 1 hour by using a paint conditioner (manufactured by LAU Co.) to prepare dispersions 1 to 6.

[ TABLE 17 ]

In table 17, each component represents the following compound.

(A-II-5): a compound represented by the formula (A-II-5)

(A-II-10): a compound represented by the formula (A-II-10)

(A-II-11): a compound represented by the formula (A-II-11)

(A-II-12): a compound represented by the formula (A-II-12)

(A-X-1): a compound represented by the formula (A-X-1)

(A-X-2): a compound represented by the formula (A-X-2)

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

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

(E-1): propylene glycol monomethyl ether acetate

[ method for producing colored curable resin composition ]

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

[ TABLE 18 ]

In table 18, each component represents the following compound.

(B-1): resin (B-1) (conversion of solid content)

(E-1): propylene glycol monomethyl ether acetate

[ measurement of Voltage holding ratio ]

The colored curable resin composition was applied to a 3-inch square glass substrate (# 1737; manufactured by corning corporation) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a colored composition layer. After cooling, the resultant was exposed to 150mJ/cm in an air atmosphere using an exposure apparatus (TME-150 RSK; manufactured by トプコン Co., Ltd.)²Exposure with an exposure amount of (365nm basis). Note that a photomask is not used. The color composition layer after exposure was post-baked in an oven at 230 ℃ for 20 minutes to produce a coating film (film thickness: 2.0 μm). The coating film was scraped off from the glass substrate, thereby obtaining a powder. 0.025g of the obtained powder was mixed with 1g of liquid crystal (MCL-6608, manufactured by メルク Co., Ltd.), and the mixture was heated at 120 ℃ for 50 minutes in a sample bottle. The mixture was transferred to a tube for centrifugal separation, and centrifugal separation was performed 2 times for 30 minutes using MICRO SIX (manufactured by アズワン Co.). The supernatant part of the mixture was sealed in a cell for liquid crystal evaluation (KSRT-05/BIIIMINTS05X, E.H.C.Co., Ltd.).Manufactured by tokyo テクニカ co., ltd., 6254) under the following measurement conditions, the voltage holding ratio was measured, and the evaluation was performed according to the following criteria.

Measurement conditions

Applied voltage pulse amplitude: 5V

Voltage holding ratio: evaluation criteria for liquid crystal cell potential difference after 1000 milliseconds/value of voltage applied at 0 millisecond

A: more than 95 percent

B: more than 85 percent and less than 95 percent

C: less than 85 percent

[ TABLE 19 ]

Industrial applicability

The compound of the present invention is excellent in absorbance and voltage holding ratio, and a color filter excellent in solvent resistance can be produced by using a colored composition using the compound.

Claims

1. A compound represented by the formula (A-I1):

in the formula (A-I1),

R⁴¹and R⁴³Each independently represents a C1-20 saturated hydrocarbon group,

R⁴⁷～R⁵⁴each independently represents a hydrogen atom, -SO₃ ^-、-SO₂-N^--SO₂-R^fOr an alkyl group having 1 to 8 carbon atoms,

R⁸¹～R⁹⁰each independently represents a hydrogen atom, a C1-20 saturated hydrocarbon group, a halogen atom or-SO₃ ^-or-SO₂-N^--SO₂-R^f，

Ring T¹Represents a ring represented by the formula (A-t1-1),

M^r+represents a hydrogen ion, a metal ion having a valence of r, or a substituted or unsubstituted ammonium ion,

k1 represents-SO that the compound represented by the formula (A-I1) has₃ ^-Number of and-SO₂-N^--SO₂-R^fThe sum of the number of the (c) is,

r represents an integer of 1 or more,

R^frepresents a C1-12 fluoroalkyl group,

however, the compound represented by the formula (A-I1) has at least 1-SO₂-N^--SO₂-R^f，

In the formula (A-t1-1),

R⁵⁶represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,

x2 represents a sulfur atom, and X2 represents,

R⁵⁷represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms,

R⁴⁵and R⁴⁶Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, and when the carbon number of the saturated hydrocarbon group is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or-CO-, but in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not replaced by oxygen atoms at the same time, and the terminal methylene group is not replaced by an oxygen atom or-CO-,

denotes a bonding end to a carbocation.

2. The compound of claim 1, wherein M^r+Is a metal ion with a valence of r.

3. A coloring composition comprising the compound according to any one of claims 1 to 2.

4. A color filter formed from the colored composition according to claim 3.

5. A display device comprising the color filter according to claim 4.