CN114265283A

CN114265283A - Colored curable resin composition

Info

Publication number: CN114265283A
Application number: CN202111061583.5A
Authority: CN
Inventors: 森本纯平; 寺川贵清
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2020-09-16
Filing date: 2021-09-10
Publication date: 2022-04-01
Also published as: TW202212485A; KR20220036875A; JP2022049668A

Abstract

The invention aims to provide a colored curable resin composition capable of forming a film-shaped deep-color cured film. The colored curable resin composition of the present invention is characterized in that: the colorant (A) comprises a compound represented by the formula (a), and the polymerizable compound (C) has a hydroxyl value of 100mgKOH/g or more.

Description

Colored curable resin composition

Technical Field

The present invention relates to a colored curable resin composition, and a color filter and a display device using the same.

Background

Color filters used in display devices such as liquid crystal display devices, electroluminescent display devices, and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors are produced from colored curable resin compositions. As a blue coloring material used for such a colored curable resin composition, c.i. pigment blue 24 represented by formula (i) having a triarylmethane skeleton is known (non-patent document 1).

Documents of the prior art

Non-patent document

Non-patent document 1: colour Index International (British dye society, American society for fiber chemistry and dyeing technology)

Disclosure of Invention

However, when a cured film having a dark color is formed from a colored curable resin composition containing the blue coloring material, the film thickness may be increased. Accordingly, an object of the present invention is to provide a colored curable resin composition capable of forming a deep cured film in the form of a thin film, a color filter formed from the colored curable resin composition, and a display device including the color filter.

The gist of the present invention is as follows.

[1] A colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C) and a polymerization initiator (D),

the colorant (A) contains a compound represented by the formula (a),

the hydroxyl value of the polymerizable compound (C) is 100mgKOH/g or more.

[ in the formula (a),

R⁴¹～R⁴⁴each 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 the aromatic hydrocarbon group and the aralkyl group may have a substituent of-SO₃ ^-or-SO₂－N^-－SO₂－R^fWhen the number of carbon atoms of the saturated hydrocarbon group is 2 to 20, -CH contained in the saturated hydrocarbon group₂-may be substituted by-O-or-CO-. However, the-CH adjacent to the saturated hydrocarbon group having 2 to 20 carbon atoms₂-not simultaneously substituted by-O-, terminal-CH₂-is not substituted by-O-or-CO-. R⁴¹And R⁴²May be bonded and form a ring together with the nitrogen atom to which they are bonded, R⁴³And R⁴⁴May be bonded and 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 a saturated hydrocarbon group having 1 to 20 carbon atoms and optionally having a substituent, wherein when the saturated hydrocarbon group has 2 to 20 carbon atoms, it constitutes-CH of the saturated hydrocarbon group₂-may be substituted by-O-or-CO-, R⁴⁸And R⁵²May be bonded to each other to form-NH-, -S-or-SO₂-. However, in the saturated hydrocarbon group, adjacent-CH₂-not simultaneously substituted by-O-, terminal-CH₂-is not substituted by-O-or-CO-.

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

M^r+And (b) a metal ion representing a valence of r.

k represents-SO of the compound represented by the formula (a)₃ ^-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) has a structure represented byLess than 1-SO₃ ^-or-SO₂－N^-－SO₂－R^f。]

[2] The colored curable resin composition according to [1], wherein the hydroxyl value of the polymerizable compound (C) is 200mgKOH/g or more.

[3] The colored curable resin composition according to [1] or [2], wherein the colorant (A) further comprises a xanthene dye.

[4] The colored curable resin composition according to [3], wherein the xanthene dye is a compound represented by the formula (1).

[ in the formula (1), R¹～R⁴Independently of each other, a hydrogen atom, -R⁸Or a C6-10 1-valent aromatic hydrocarbon group, or R¹And R²And R³And R⁴Each together form a ring containing a nitrogen atom. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted by a halogen atom, -OH, -OR⁸、－SO₃ ^-、－SO₃H、－SO₃ ^-M⁺、－CO₂H、－CO₂R⁸、－SO₃R⁸or-SO₂NR⁹R¹⁰And (4) substitution.

R⁵represents-OH or-SO₃ ^-、－SO₃H、－SO₃ ^-M⁺、－CO₂H、－CO₂ ^-M⁺、－CO₂R⁸、－SO₃R⁸or-SO₂NR⁹R¹⁰。

m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of R⁵May be the same or different from each other.

R⁶And R⁷Independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

M⁺To represent⁺N(R¹¹)₄、Na⁺Or K⁺And X represents a halogen atom.

a represents 0 or 1.

R⁸Represents a C1-20 saturated hydrocarbon group, the hydrogen atom in the saturated hydrocarbon group may be substituted by a C6-10 aromatic hydrocarbon group, a carboxyl group or a halogen atom, and the-CH group in the saturated hydrocarbon group₂May be represented by-S-, -O-, -CO-or-NR¹¹-substitution. However, in the saturated hydrocarbon group, adjacent-CH₂-is not simultaneously substituted with-O-. R¹¹Represents a hydrogen atom, a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, R¹¹When a plurality of them exist, all or a part of them may be the same.

R⁹And R¹⁰Independently represent a hydrogen atom or a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by-OH or a halogen atom, and the-CH contained in the saturated hydrocarbon group₂May be substituted by-S-, -O-, -CO-, -NH-or-NR⁸-substitution. However, in the saturated hydrocarbon group, adjacent-CH₂-is not simultaneously substituted with-O-.

R⁹And R¹⁰May be bonded to each other to form a heterocyclic ring of three to ten membered rings containing a nitrogen atom.]

[5] A color filter comprising the colored curable resin composition according to any one of [1] to [4 ].

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

According to the present invention, a colored curable resin composition capable of forming a deep-colored cured film in the form of a film, a color filter formed from the colored curable resin composition, and a display device including the color filter can be provided.

Detailed Description

The colored curable resin composition of the present invention comprises a colorant (a), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

The colorant (a) contains a compound represented by formula (a) (hereinafter, sometimes referred to as compound (a)).

The colored curable resin composition of the present invention preferably further contains a solvent (hereinafter, may be referred to as solvent (E)).

The colored curable resin composition of the present invention may contain a leveling agent (hereinafter, sometimes referred to as a leveling agent (F)).

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

< colorant (A) >)

< Compound (a) >)

The colorant (A) contains a compound (a). The present invention will be described in detail below with reference to the formula (a), but the compound (a) also includes tautomers and salts thereof.

[ in the formula (a),

R⁴¹～R⁴⁴each 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 the aromatic hydrocarbon group and the aralkyl group may have a substituent of-SO₃ ^-or-SO₂－N^-－SO₂－R^fWhen the number of carbon atoms of the saturated hydrocarbon group is 2 to 20, -CH contained in the saturated hydrocarbon group₂-may be substituted by-O-or-CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent-CH₂-not simultaneously substituted by-O-, terminal-CH₂-is not substituted by-O-or-CO-. R⁴¹And R⁴²May be bonded and form a ring together with the nitrogen atom to which they are bonded, R⁴³And R⁴⁴May be bonded and 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,－SO₃ ^-、－SO₂－N^-－SO₂－R^fOr a saturated hydrocarbon group having 1 to 20 carbon atoms and optionally having a substituent, wherein when the saturated hydrocarbon group has 2 to 20 carbon atoms, it constitutes-CH of the saturated hydrocarbon group₂-may be substituted by-O-or-CO-, R⁴⁸And R⁵²May be bonded to each other to form-NH-, -S-or-SO₂-. However, in the saturated hydrocarbon group, adjacent-CH₂-not simultaneously substituted by-O-, terminal-CH₂-is not substituted by-O-or-CO-.

M^r+And (b) a metal ion representing a valence of r.

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) has at least 1-SO₃ ^-or-SO₂－N^-－SO₂－R^f。]

Ring T¹The aromatic heterocyclic ring may be a single ring or a condensed ring. Ring T¹The aromatic heterocyclic ring preferably has 3 to 10 carbon atoms, more 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,

A 5-membered ring containing a nitrogen atom such as an azole ring, a pyrazole ring, an imidazole ring, or a thiazole ring; a 5-membered ring containing no nitrogen atom, such as a furan ring or a thiophene ring; a 6-membered ring containing a nitrogen atom such as a pyridine ring, a pyrimidine ring, a pyridazine ring, or a pyrazine ring; examples of the condensed ring aromatic heterocyclic 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; and the like.

As a ring T¹The aromatic heterocyclic ring of (A) may have a substituent, and examples thereof include a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a substituted or unsubstituted amino group, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and-SO₃ ^-or-SO₂－N^-－SO₂－R^fAnd the like, preferably a saturated hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted amino group, or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. Ring T¹The amino group is preferably an optionally substituted amino group, and the optionally substituted amino group is preferably an optionally substituted saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, an optionally substituted aralkyl group having 7 to 30 carbon atoms, or the like.

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

Ring T¹The ring represented by formula (t1) is preferred.

[ in the formula (t1),

x2 represents-O-, -N (R)⁵⁷) -or-S-.

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

R⁴⁵And R⁴⁶Each independently representA 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.

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

R is as defined above⁴⁵、R⁴⁶And R⁵⁵Wherein when the number of carbon atoms of the saturated hydrocarbon group is 2 to 20, -CH contained in the saturated hydrocarbon group₂-may be substituted by-O-or-CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent-CH₂-not simultaneously substituted by-O-, terminal-CH₂-is not substituted by-O-or-CO-.

R⁴⁵And R⁴⁶May be bonded and form a ring together with the nitrogen atom to which they are bonded.

Denotes the bonding site to the carbenium ion. ]

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

[ in the formula (t2),

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

R⁵⁸Represents 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, -SO₃ ^-or-SO₂－N^-－SO₂－R^f。

R⁵⁹Represents 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.

k2 represents 0, 1 or 2.

Denotes the bonding site to the carbenium ion. ]

The ring represented by the formula (t2) is more preferably a ring represented by the formula (t 2-1).

[ in the formula (t 2-1),

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

R⁶¹represents-SO₃ ^-or-SO₂－N^-－SO₂－R^f。

R⁵⁹The same as above.

Denotes the bonding site to the carbenium ion. ]

As a ring T¹The ring represented by the formula (t1) or the formula (t2) is preferable, and the ring represented by the formula (t1) is more preferable.

R⁴¹～R⁵⁵And R⁵⁸～R⁶⁰A saturated hydrocarbon group having 1 to 20 carbon atoms, a ring T¹Optionally a saturated hydrocarbon group having 1 to 20 carbon atoms, and a ring T¹The saturated hydrocarbon group having 1 to 20 carbon atoms which may have an amino group may be any of linear, branched 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.

The cyclic saturated hydrocarbon group may be monocyclic or polycyclic, and examples of the cyclic saturated hydrocarbon group include alicyclic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and adamantyl. The number of carbon atoms of the cyclic saturated hydrocarbon group is preferably 3 to 10, more preferably 6 to 10.

As R⁴¹～R⁵⁵And R⁵⁸～R⁶⁰Saturated hydrocarbon group, ring T¹Saturated hydrocarbon group which may have, and a ring T¹The saturated hydrocarbon group which may have an amino group is preferably a methyl group, an ethyl group, an isopropyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isobutyl group, a 2-ethylhexyl group, a cyclohexyl group, an adamantyl group, or the like.

R⁴¹～R⁵⁵And R⁵⁸～R⁶⁰Saturated hydrocarbon group, ring T¹Saturated hydrocarbon group which may have, and a ring T¹The saturated hydrocarbon group which the amino group which may be present may have a substituted or unsubstituted amino group, or a halogen atom as a substituent. Examples of the substituted amino group include alkylamino groups such as dimethylamino group and diethylamino group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. When the halogen atom is a fluorine atom, the saturated hydrocarbon group having a fluorine atom as a substituent is preferably a perfluoroalkyl group such as a trifluoromethyl group, a perfluoroethyl group, or a perfluoropropyl group.

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

R⁴¹～R⁵⁵When the number of carbon atoms of the saturated hydrocarbon group is 2 to 20, the saturated hydrocarbon group contains-CH₂-may be substituted by-O-or-CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent-CH₂-not simultaneously substituted by-O-, terminal-CH₂-is not substituted by-O-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). -CH₂The number of carbon atoms of the saturated hydrocarbon group which may be substituted by-O-or-CO-is preferably 2 to 10, more preferably 2 to 8. In addition, -CH₂-carbon atoms between the terminal and-O-or-CO-or-O-or-CO-and-O-or-CO-when the substitution is-O-or-CO-)The number is 1 or more, preferably 1 to 5, more preferably 2 to 3, and further preferably 2.

In addition, R⁴¹～R⁴⁶、R⁵⁵And R⁵⁸～R⁶⁰An aromatic hydrocarbon group, ring T¹Optionally having aromatic hydrocarbon group, and ring T¹The number of carbon atoms of the aromatic hydrocarbon group which may have an amino group 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. The aromatic hydrocarbon 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; 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^f(ii) a Etc., may also be-SO₃ ^-or-SO₂－N^-－SO₂－R^f. However, -SO is preferred₃ ^-and-SO₂－N^-－SO₂－R^fAn aromatic hydrocarbon ring directly bonded to an aromatic hydrocarbon group, that is, a hydrogen atom bonded to an aromatic hydrocarbon ring is substituted. As R⁵⁵The substituent in the aromatic hydrocarbon group is preferably a halogen atom.

Specific examples of the aromatic hydrocarbon group which may have a substituent include groups represented by the following formulae. The group represented by the formula may further have at least 1-SO₃ ^-or-SO₂－N^-－SO₂－R^f. In the following formulae, a represents a bonding site to a nitrogen atom or a carbon atom.

As R⁴¹～R⁴⁶、R⁵⁹Aralkyl and ring T¹Examples of the aralkyl group which may have an amino group include groups in which an alkanediyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms) such as a methylene group, an ethylene group, and a propylene group is bonded to the group described as the above aromatic hydrocarbon group. The number of carbon atoms of the aralkyl group is preferably 7 to 30, more preferably 7 to 20, and still more preferably 7 to 17. In addition, the aralkyl 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; 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^f(ii) a And the like.

As R⁴¹And R⁴²Bonded and forming a ring together with the nitrogen atom to which they are bonded, R⁴³And R⁴⁴A ring bonded and formed together with the nitrogen atom to which they are bonded, and R⁴⁵And R⁴⁶The ring bonded to form together with the nitrogen atom bonded to the ring includes nitrogen-containing non-aromatic 4 to 7-membered rings such as a pyrrolidine ring, morpholine ring, piperidine ring, and piperazine ring, and preferably includes 4 to 7-membered rings having only 1 nitrogen atom as a heteroatom such as a pyrrolidine ring and piperidine ring.

Wherein, as R⁴¹～R⁴⁴、R⁵⁵、R⁵⁸～R⁶⁰The aromatic hydrocarbon group is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having a substituent, and more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms or a group represented by the following formula. In particular, R⁴¹And R⁴³The hydrocarbon group is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, and more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms. R⁴²And R⁴⁴Preferably each independently an optionally substituted aromatic hydrocarbon group, more preferably each independently an optionally substituted benzene groupA tolyl group which may have a substituent, a xylyl group which may have a substituent. R⁵⁵Further preferred is an aromatic hydrocarbon group which may have a substituent.

R⁵⁵、R⁵⁸～R⁶⁰More preferably, the group represented by the following formula is used. The group represented by the formula may further have at least 1-SO₃ ^-or-SO₂－N^-－SO₂－R^f. In the following formulae, a represents a bonding site to a nitrogen atom or a carbon atom.

R⁴⁵～R⁴⁶Preferably, each independently represents a saturated hydrocarbon group having 1 to 20 carbon atoms or at least 1-CH constituting an alkyl group having 2 to 20 carbon atoms₂A group which is substituted by-O-or-CO-, or an aromatic hydrocarbon group which may have a substituent, or R⁴⁵And R⁴⁶Bonded and form a ring together with the nitrogen atom to which they are bonded. R⁴⁵～R⁴⁶More preferably, each of the groups is independently a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, a group represented by the following formula, or R⁴⁵And R⁴⁶Bonded to form a 4-to 7-membered ring having only 1 nitrogen atom as a heteroatom, and further preferably each independently a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or a group represented by the following formula. The group represented by the formula may further have at least 1-SO₃ ^-or-SO₂－N^-－SO₂－R^fAs a substituent. In the following formula, a represents a bonding site to a nitrogen atom.

Among them, R is preferred⁴⁵Is a saturated hydrocarbon group of 1 to 4 carbon atoms, R⁴⁶Is an o-tolyl group.

R⁴⁷～R⁵⁴The hydrocarbon group is preferably a hydrogen atom, a halogen atom or a linear or branched saturated hydrocarbon group having 1 to 8 carbon atoms, more preferably a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom, and still more preferably a hydrogen atom.

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

As R⁶¹Preferably a hydrogen atom.

As 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 ion, magnesium ion, calcium ion, strontium ion, barium ion, etc.; 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 preferably 1 or more, more preferably 2 or more, preferably 5 or less, more preferably 4 or less, and further preferably 3 or less.

As M^r+More preferred are alkaline earth metal ions, typical metal ions and the like, still more preferred are alkaline earth metal ions and zinc ions, and still more preferred are alkaline earth metal ions.

In the formula (a), M^r+The number of (a) is more than-SO of the compound (a)₃ ^-Number of and-SO₂－N^-－SO₂－R^fThe sum (k) of the numbers of (A) and (B) is less than 1. Therefore, the valence of the compound (a) is 0, i.e., it is an electrically neutral compound.

As R^fExamples of the fluoroalkyl group having 1 to 12 carbon atoms include a monofluoromethyl group, a difluoromethyl group, a perfluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a tetrafluoroethyl group, a perfluoroethyl group, a monofluoropropyl group, a difluoropropyl group, a trifluoropropyl group, a tetrafluoropropyl group, a pentafluoropropyl group, a hexafluoropropyl group, a perfluoropropyl group, a monofluorobutyl group, a difluorobutyl group, a trifluorobutyl group, a tetrafluoro-propyl groupButyl, pentafluorobutyl, hexafluorobutyl, heptafluorobutyl, octafluorobutyl, perfluorobutyl, and the like. Wherein, as R^fThe fluoroalkyl group is preferably a perfluoroalkyl group. In addition, R^fThe number of carbon atoms of the fluoroalkyl group is preferably 1 to 10, more preferably 1 to 5, and further preferably 1 to 3.

In the formula (a), R⁴¹～R⁴⁴、R⁴⁷～R⁵⁴And ring T¹Having at least 1-SO₃ ^-or-SO₂－N^-－SO₂－R^f。R⁴¹～R⁴⁴、R⁴⁷～R⁵⁴And ring T¹having-SO of₃ ^-and-SO₂－N^-－SO₂－R^fThe sum (k) of the number of (a) is 1 or more, preferably 1 to 7, more preferably 2 to 7, further preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.

－SO₃ ^-or-SO₂－N^-－SO₂－R^fPreferably, at least 1 or more condition selected from the following (Ia) to (Id) is satisfied, and more preferably, at least 1 or more condition selected from the following (Ia) and (Ib) is satisfied.

(Ia) as the above R⁴⁷～R⁵⁴And any one of them contains

(Ib) bound to R⁴¹～R⁴⁴Any one of the aromatic hydrocarbon groups having 6 to 20 carbon atoms which may have a substituent(s)

(Ic) bound to R⁴¹～R⁴⁴Any one of the aralkyl groups having 7 to 30 carbon atoms which may have a substituent(s) represented by (a)

(Id) bound to substituted T¹Any one of the aromatic heterocyclic ring represented by (A) has a hydrogen atom of an aromatic hydrocarbon group having 6 to 20 carbon atoms

Wherein an aromatic hydrocarbon group or an aralkyl group is bonded with-SO₃ ^-or-SO₂－N^-－SO₂－R^fWhen is in the state of-SO₃ ^-or-SO₂－N^-－SO₂－R^fPreferably aromatic hydrocarbon directly bonded to aromatic hydrocarbon group or aralkyl groupA hydrocarbon ring. Namely, -SO₃ ^-or-SO₂－N^-－SO₂－R^fIt is preferable to substitute a hydrogen atom bonded to an aromatic hydrocarbon ring.

－SO₃ ^-or-SO₂－N^-－SO₂－R^fPreferably in the formula R⁴¹～R⁴⁴The C6-20 aromatic hydrocarbon group which may have a substituent or R⁴¹～R⁴⁴The aromatic hydrocarbon ring (e.g., benzene ring) in the aralkyl group having 7 to 30 carbon atoms which may have a substituent(s) is bonded at a para-position with respect to a bonding position with a nitrogen atom.

The compound (a) contains a plurality of-SO₃ ^-or-SO₂－N^-－SO₂－R^fWhen plural of-SO₃ ^-or-SO₂－N^-－SO₂－R^fMay be bonded to the same aromatic hydrocarbon ring, preferably to different aromatic hydrocarbon rings.

The compound (a) preferably has no ethylenically unsaturated bond.

Compound (a) is preferably R⁴¹And R⁴³Each independently a saturated hydrocarbon group having 1 to 10 carbon atoms (the 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 carbon number of the saturated hydrocarbon group is 2 to 10, — CH contained in the saturated hydrocarbon group₂-may be substituted by-O-or-CO-), R⁴²And R⁴⁴Each independently may be a phenyl group which may have a substituent, a tolyl group which may have a substituent, or a xylyl group which may have a substituent (the phenyl group, the tolyl group, and the xylyl group may have a substituent of-SO₃ ^-or-SO₂－N^-－SO₂－R^f)，R⁴⁷～R⁵⁴Is a hydrogen atom, a ring T¹Is a 5-membered ring containing a nitrogen atom (the 5-membered ring may have a saturated hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted amino group, or an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, the optionally substituted substituent of the aromatic hydrocarbon group may be-SO₃ ^-Or-SO₂－N^-－SO₂－R^f) (ii) a Or a compound represented by the formula (a-1) (hereinafter, may be referred to as "compound (a-1)").

[ in the formula (a-1),

R^47A～R^54Aeach independently represents a hydrogen atom, -SO₃ ^-Or a saturated hydrocarbon group having 1 to 10 carbon atoms.

R^41AAnd R^43AEach independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 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 ^-。

R^11A～R^20AEach independently represents-SO₃ ^-A hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom.

R^45A、R^46AAnd R^55AEach independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and the substituent which may be present in the aromatic hydrocarbon group may be-SO₃ ^-。

R is as defined above^47A～R^54A、R^41A、R^43A、R^11A～R^20A、R^45A、R^46AAnd R^55AWherein when the number of carbon atoms of the saturated hydrocarbon group is 2 to 10, the saturated hydrocarbon group contains-CH₂-may be substituted by-O-or-CO-. However, in the saturated hydrocarbon group having 2 to 10 carbon atoms, adjacent-CH₂-not simultaneously substituted by-O-, terminal-CH₂-is not substituted by-O-or-CO-.

M^r+And (b) a metal ion representing a valence of r.

k representsSO contained in the compound represented by the formula (a-1)₃ ^-The number of bases.

Wherein the compound represented by the formula (a-1) has at least 2 SO₃ ^-And (4) a base.

r represents an integer of 2 or more. ]

As R^47A～R^54A、R^41A、R^43A、R^11A～R^20A、R^45A、R^46AAnd R^55AThe saturated hydrocarbon group having 1 to 10 carbon atoms is represented by R⁴¹The saturated hydrocarbon group mentioned in (1) above has 1 to 10 carbon atoms.

R^45A、R^46AAnd R^55AA substituent which the saturated hydrocarbon group having 1 to 10 carbon atoms may have and R⁴¹The substituents which the saturated hydrocarbon group may have are the same as those exemplified above.

R^41A、R^43A、R^45A、R^46AAnd R^55AAn aromatic hydrocarbon group having 6 to 20 carbon atoms and R⁴¹The aromatic hydrocarbon group having 6 to 20 carbon atoms is the same as the above-mentioned group.

R^41AAnd R^43AAn aralkyl group having 7 to 30 carbon atoms and R⁴¹Examples of the aralkyl group having 7 to 30 carbon atoms are the same.

As R^41A、R^43A、R^45A、R^46AAnd R^55AAn aromatic hydrocarbon group having 6 to 20 carbon atoms and R^41AAnd R^43AExamples of the substituent which the aralkyl group having 7 to 30 carbon atoms may have include a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom; 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 ^-(ii) a And the like.

As R^11A～R^20AExamples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the likePreferably a fluorine atom.

R^47A～R^54AMore preferably each independently a hydrogen atom, -SO₃ ^-Or a methyl group, and further preferably each independently a hydrogen atom or a methyl group.

R^41AAnd R^43APreferably a saturated hydrocarbon group having 1 to 10 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,

more preferably, each is independently a saturated hydrocarbon group having 1 to 8 carbon atoms; a phenyl group; tolyl; a naphthyl group; a methyl naphthyl group; unsubstituted aralkyl; or an aralkyl group substituted with 1 or more, particularly 1, selected from a halogen atom, a methoxy group, an ethoxy group, a sulfamoyl group, a methanesulfonyl group, a methoxycarbonyl group and an ethoxycarbonyl group,

more preferably, each of the alkyl groups is independently a linear alkyl group having 1 to 4 carbon atoms.

From the aspects of heat resistance and light resistance, R^11A～R^12APreferably at least one of the alkyl groups is a halogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably at least one of the alkyl groups is a halogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms, and still more preferably at least one of the alkyl groups is a fluorine atom or a saturated hydrocarbon group having 1 to 4 carbon atoms.

From the aspects of heat resistance and light resistance, R^13A～R^14APreferably at least one of the alkyl groups is a halogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably at least one of the alkyl groups is a halogen atom or a saturated hydrocarbon group having 1 to 8 carbon atoms, and still more preferably at least one of the alkyl groups is a fluorine atom or a saturated hydrocarbon group having 1 to 4 carbon atoms.

From the aspect of easy synthesis, R^15A～R^20AEach independently preferably being a hydrogen atom, -SO₃ ^-Or a saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom, -SO₃ ^-Or a saturated hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrogen atom, -SO₃ ^-Or a methyl group.

R^45A、R^46AAnd R^55AEach independently preferably a saturated hydrocarbon group having 1 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent,

more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with a halogen atom, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group or a methanesulfonyl group; or a saturated hydrocarbon group having 1 to 8 carbon atoms,

more preferably a saturated hydrocarbon group having 1 to 8 carbon atoms or an aromatic hydrocarbon group represented by the following formula.

In particular, R⁴⁵And R⁴⁶Preferably, one is a saturated hydrocarbon group having 1 to 6 carbon atoms, and the other is an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent; more preferably, one is a saturated hydrocarbon group having 1 to 6 carbon atoms, and the other is an aromatic hydrocarbon group represented by the following formula. R⁵⁵The aromatic hydrocarbon group having 6 to 20 carbon atoms and containing a halogen atom is preferable, and the aromatic hydrocarbon group having 6 to 20 carbon atoms and containing 2 or more halogen atoms is more preferable. R⁵⁵The number of halogen atoms in the aromatic hydrocarbon group is preferably 1 to 6, more preferably 1 to 4, and further preferably 2 to 3. The halogen atom is preferably a fluorine atom.

R⁵⁵Preferred is an aromatic hydrocarbon group represented by the following formula. In the following formulae, a represents a bonding site to a carbon atom.

In the formula (a-1), -SO₃ ^-The number of (a) is preferably 2 to 6, and more preferably 4 or less.

－SO₃ ^-Preferably (ia) as R^47A～R^54A、R^11A～R^20AAny one of them; (ib) bound to R^41A、R^43AAn optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atomsAnd R^41A、R^43AAny one of the aralkyl groups having 7 to 30 carbon atoms which may have a substituent(s); (ic) bound to R^45A、R^46A、R^55AAny one of the aromatic hydrocarbon groups having 6 to 20 carbon atoms which may have a substituent(s); or a combination of these compounds (ia) to (ic), more preferably (ia), (ib) or a combination of (ia) to (ib), and still more preferably (ia).

In addition, R^47A～R^54A、R^11A～R^20AAmong them, R is particularly preferable^16AAnd R^19AAnd contains-SO₃ ^-。

In the above (ia) to (ic), -SO₃ ^-An aromatic hydrocarbon ring directly bonded to an aromatic hydrocarbon group or an aralkyl group is preferable. Namely, -SO₃ ^-It is preferable to substitute a hydrogen atom bonded to an aromatic hydrocarbon ring.

2 or more-SO₃ ^-May be bonded to the same aromatic hydrocarbon ring, preferably to different aromatic hydrocarbon rings.

As the compound (a), as shown in the following tables 1 to 9, compounds 1 to 514 represented by the formula (a-2) and the like can be exemplified.

Wherein the compound represented by the formula (a-2) has 2-SO groups₃ ^-the-SO₃ ^-Substituted R^h、R^11A～R^14AAny 2 of the hydrogen atoms represented, preferably substituted R^hAny 2 of the hydrogen atoms represented by (A) are more preferably substituted for R in the benzene ring bonded to the nitrogen atom at the para-position relative to the bonding position with the nitrogen atom^h。

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

[ Table 6]

[ Table 7]

[ Table 8]

[ Table 9]

In tables 1 to 9, Me represents a methyl group, Et represents an ethyl group, iPr represents an isopropyl group, Bt represents an n-butyl group, and Ph1 to Ph10 each represent a group represented by the following formula. In Ph1 to Ph10, a indicates a bonding site.

Wherein, as the compound (a),

preferably from compound 31 to compound 90, from compound 121 to compound 180, from compound 211 to compound 334, from compound 365 to compound 424, from compound 455 to compound 514,

more preferably, compounds 46 to 60, compounds 61 to 90, compounds 136 to 150, compounds 226 to 240, compounds 271 to 334, compounds 380 to 394, and compounds 470 to 484,

more preferably, compounds 46 to 60, compounds 61 to 90, compounds 136 to 150, compounds 226 to 240, compounds 271 to 304, compounds 380 to 394, and compounds 470 to 484,

more preferably, compounds 46 to 60, compounds 61 to 90, compounds 136 to 150, compounds 226 to 240, compounds 271 to 294, compounds 380 to 394, and compounds 470 to 484,

particularly, compounds 46 to 60, compounds 61 to 90, compounds 136 to 150, compounds 226 to 240, compounds 279 to 294, compounds 380 to 394, and compounds 470 to 484 are more preferable.

These compounds can particularly achieve both high heat resistance and light resistance, and further improve luminance.

Having a-SO₃ ^-The compound (a) of (a) can be produced, for example, by sulfonating a compound represented by the formula (aC) (hereinafter, may be referred to as compound (aC)), and further reacting the sulfonated compound with a halide (preferably chloride), acetate, phosphate, sulfate, silicate, cyanide, or the like containing a metal ion having a valence of r.

[ in the formula (aC),

R^1c～R^4ceach 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 saturated hydrocarbon group has 2 to 20 carbon atoms, the-CH contained in the saturated hydrocarbon group₂-may be substituted by-O-or-CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent-CH₂-not simultaneously substituted by-O-, terminal-CH₂-is not substituted by-O-or-CO-. R^1cAnd R^2cMay be bonded and form a ring together with the nitrogen atom to which they are bonded, R^3cAnd R^4cMay be bonded and form a ring together with the nitrogen atom to which they are bonded.

R^7c～R^14cEach independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or a saturated hydrocarbon group having 1 to 20 carbon atoms and having a substituent, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, it constitutes-CH of the saturated hydrocarbon group₂-may be substituted by-O-or-CO-. However, in the saturated hydrocarbon group, adjacent-CH₂-not simultaneously substituted by-O-, terminal-CH₂-is not substituted by-O-or-CO-. R^8cAnd R^12cMay be bonded to each other to form-NH-, -S-or-SO₂－。

Ring T¹⁰The aromatic heterocyclic ring has 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon 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.

M^1cRepresents Cl^-Phosphate ion, perchlorate ion, BF₄ ^-Or PF₆ ^-。]

Having a-SO₂－N^-－SO₂－R^fThe compound (a) of (a) can be prepared by reacting a compound having-SO₃ ^-Is not provided with-SO₂－N^-－SO₂－R^fThe compound (a) of (1) is produced by reacting a compound represented by the formula (IB) with a compound, and further reacting with a halide (preferably chloride), acetate, phosphate, sulfate, silicate, cyanide, or the like containing a metal ion having a valence of r.

[ in the formula (IB), R^fThe same as above.]

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

The compound (a) can be dispersed by a dispersing agent to obtain a dispersion liquid in which the compound (a) is uniformly dispersed in a solution.

Examples of the dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These dispersants may be used alone, or 2 or more kinds may be used in combination. Examples of the dispersant include KP (manufactured by shin-Etsu chemical industries, Ltd.), FLOWLEN (manufactured by Kyoho chemical Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (manufactured by CIBA Co., Ltd.), AJISPER (manufactured by Ajinko chemical Co., Ltd.), Disperbyk (manufactured by BYK-Chemie Co., Ltd.), BYK (manufactured by BYK-Chemie Co., Ltd.), and the like.

When a dispersant is used, the amount thereof to be used is preferably 1 to 100% by mass, more preferably 15 to 100% by mass, based on the compound (a). When the amount of the dispersant used is within the above range, a dispersion in a uniformly dispersed state can be obtained.

The content of the compound (a) in the dispersion is preferably 1 to 80% by mass, more preferably 1 to 50% by mass, and still more preferably 1 to 30% by mass.

Xanthene dye

The colorant (a) preferably further contains a xanthene dye. As the xanthene dye, known xanthene dyes can be used, and among them, a compound represented by formula (1) (hereinafter, also referred to as "compound (1)") is preferably contained as a main component. In the present specification, "contained as a main component" means that the content is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, particularly preferably 98% by mass or more, and the upper limit thereof may be 100% by mass.

M⁺To represent⁺N(R¹¹)₄、Na⁺Or K⁺And X represents a halogen atom.

a represents 0 or 1.

R⁹And R¹⁰Independently represent a hydrogen atom or a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by-OH or a halogen atom, and the-CH contained in the saturated aliphatic hydrocarbon group₂May be substituted by-S-, -O-, -CO-, -NH-or-NR⁸-substitution. However, in the saturated hydrocarbon group, adjacent-CH₂-is not simultaneously substituted with-O-.

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

As R¹～R⁴In the above aromatic hydrocarbon group, the 1-valent aromatic hydrocarbon group having 6 to 10 carbon atoms includes, for example, a phenyl group, a tolyl group, a xylyl group, a mesityl group, a propylphenyl group, a butylphenyl group and the like.

As R¹And R²Together form a ring, and R³And R⁴Examples of the ring to be formed together include the following rings. In the following rings, the bond sites are indicated.

As R⁸～R¹¹In the (C1-C20) saturated hydrocarbon group, R is⁴¹The saturated hydrocarbon group having 1 to 20 carbon atoms is the same as the exemplified group.

With respect to R⁸The aromatic hydrocarbon group of 6 to 10 carbon atoms in which a hydrogen atom contained in a 1-valent saturated hydrocarbon group of 1 to 20 carbon atoms may be substituted includes R¹～R⁴The same groups as those exemplified for the 1-valent aromatic hydrocarbon group having 6 to 10 carbon atoms are shown.

As R in formula (1)¹¹Examples of the aralkyl group having 7 to 10 carbon atoms in (A) include benzyl, phenylethyl, phenylbutyl and the like.

M⁺Is composed of⁺N(R¹¹)₄、Na⁺Or K⁺Preferably, it is⁺N(R¹¹)₄。⁺N(R¹¹)₄Preferably 4R¹¹At least 2 of them are C5-20 saturated C1-valent hydrocarbon groups. In addition, 4R¹¹The total number of carbon atoms of (1) is preferably 20 to 80, more preferably 20 to 60.

Preferably, the xanthene dye is contained more preferably with the compound represented by formula (2) as the main component.

[ in the formula (2), R²¹～R²⁴Independently of each other, a hydrogen atom, -R²⁶Or a C6-10 1-valent aromatic hydrocarbon group, wherein hydrogen atoms contained in the aromatic hydrocarbon group may be replaced by-CO₂H、－SO₃ ^-、－SO₃ ^-M^a+、－SO₃H、－SO₃R²⁶or-SO₂NHR²⁶And (4) substitution. X represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

a1 represents 0 or 1. m1 represents an integer of 0 to 5. When m1 is an integer of 2 or more, plural R' s²⁵May be the same or different. M^a ⁺To represent⁺N(R²⁷)₄、Na⁺Or K⁺。

R²⁵represents-SO₃ ^-、－SO₃ ^-M^a+、－SO₃H or-SO₂NHR²⁶。

R²⁶Represents a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms, and hydrogen atoms contained in the saturated hydrocarbon group may be substituted by carboxyl groups. 4R²⁷Independently represents a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.]

As R in formula (2)²¹～R²⁴In the above formula, the 1-valent aromatic hydrocarbon group having 6 to 10 carbon atoms includes¹～R⁴The aromatic hydrocarbon group in (1) is the same as the above-mentioned group.

As R²⁶And R²⁷In the (C1-C20) saturated hydrocarbon group, R is⁸～R¹¹The saturated hydrocarbon group in (1) is the same as the group exemplified above. R in the formula (2)²¹～R²⁴In (1-R)²⁶Independently of each other, a linear alkyl group having 1 to 4 carbon atoms which may be substituted with a carboxyl group is preferable, and a methyl group or an ethyl group is more preferable. In addition, as-SO₃R²⁶and-SO₂NHR²⁶R in (1)²⁶A branched alkyl group having 3 to 20 carbon atoms is preferable, a branched alkyl group having 6 to 12 carbon atoms is more preferable, and a 2-ethylhexyl group is further preferable.

M^a+Is composed of⁺N(R²⁷)₄、Na⁺Or K⁺Preferably, it is⁺N(R²⁷)₄。⁺N(R²⁷)₄Preferably 4R²⁷At least 2 of them are C5-20 saturated C1-valent hydrocarbon groups. In addition, 4R²⁷The total number of carbon atoms of (1) is preferably 20 to 80, more preferably 20 to 60.

In the formula (2), R is preferred²¹And R²³Is a hydrogen atom, and R²²And R²⁴Is a C6-10 valent aromatic hydrocarbon group, and when the hydrogen atom in the aromatic hydrocarbon group is substituted, the substituted group is-SO₃ ^-、－SO₃ ^-M⁺、－SO₃H、－SO₃R²⁶or-SO₂NHR²⁶. Further, R is more preferable²¹And R²³Is a hydrogen atom, and R²²And R²⁴Is a C6-10 valence aromatic hydrocarbon group (preferably phenyl, tolyl or xylyl), and the hydrogen atom in the aromatic hydrocarbon group may be replaced by-SO₃ ^-M⁺or-SO₂NHR²⁶And (4) substitution. R²¹～R²⁴These groups are advantageous in that a color filter having excellent heat resistance can be formed.

In the formula (2), R is preferred²⁵is-SO₃ ^-Or SO₂NHR²⁶。

In the formula (2), a1 is preferably 0.

The xanthene dye is preferably contained as a main component in any one or more of the compounds represented by the formulae (1-1) to (1-39). In the formula, Ra represents a 2-ethylhexyl group.

The compounds represented by the formulae (1-1) to (1-16) may be represented by, for example, -SO₃The pigment or pigment intermediate of H is chlorinated using conventional methods to give a product having-SO₂Pigment or pigment intermediate of Cl and R⁸－NH₂The amine shown is reacted to produce.

The dye produced by the method described in the upper right column to lower left column of page 3 of Japanese patent application laid-open No. 3-78702 can also be produced by a method of chlorination followed by reaction with an amine in the same manner as described above.

The compounds represented by the formulae (1-17) to (1-32) can be produced by the methods described in the upper right column to the lower left column of page 3 of Japanese patent laid-open No. 3-78702. As the above method, for example, a method of reacting a compound represented by formula (1a), a compound represented by formula (1b) and a compound represented by formula (1c) may be mentioned. In the formulae (1b) and (1c), R¹～R⁴Each means the same as described above.

The compounds represented by the formulae (1-33) to (1-39) can be produced by the method described in Japanese patent laid-open publication No. 2017-226814.

Other coloring agent

The colorant (a) may contain one or both of another dye (hereinafter, sometimes referred to as a dye (a1)) and another pigment (hereinafter, sometimes referred to as a pigment (a2)) in addition to the compound (a) and the xanthene dye.

The dye (a1) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of The dye include compounds classified as substances having a color tone other than pigments in The color index (published by The Society of Dyers and Colourists), and known dyes described in dyeing guidelines (color dyeing companies). Further, depending on the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and the like can be cited. Among them, organic solvent-soluble dyes are preferable.

Specifically, the following color index (c.i.) number dyes are exemplified.

For example, c.i. acid yellow 1,3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

c.i. solvent yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;

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

c.i. disperse yellow 51, 54, 76;

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

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

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

c.i. reactive orange 16;

c.i. acid red 1,4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 57, 66, 73, 76, 80, 88, 91, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 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, 382, 383, 394, 401, 412, 417, 418, 422, 349, 426;

c.i. solvent red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247;

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. mordant red 1,2,3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;

c.i. acid violet 34;

c.i. disperse violet 26, 27;

c.i. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

c.i. solvent blue 14, 18, 35, 36, 45, 58, 59: 1. 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

c.i. acid blue 25, 27, 40, 45, 78, 80, 112;

c.i. direct blue 40;

c.i. disperse blue 1, 14, 56, 60;

c.i. solvent green 1,3,5, 28, 29, 32, 33;

c.i. acid green 3,5, 9, 25, 27, 28, 41;

c.i. alkaline green 1;

c.i. vat green 1, etc.

As The pigment, known pigments can be used, and for example, pigments classified as pigments (pigments) in The color index (published by The Society of Dyers and Colourists) can be cited. More than 2 kinds may be combined.

Specifically, there may be mentioned yellow pigments such as 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, 185, 194, 214;

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, 266, 268, 269, 273 and the like;

c.i. pigment blue 15, 15: 3. 15: 4. 15: 6. 60, etc. blue pigments;

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

c.i. pigment green 7, 36, 58, 59.

The pigment (a2) 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 of the pigment surface with a polymer compound or the like, micronization treatment by a sulfuric acid micronization method or the like, cleaning treatment by an organic solvent, water or the like for removing impurities, removal treatment by an ion exchange method or the like for removing ionic impurities, or the like.

The pigment (a2) is preferably uniform in particle size. The pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained by performing a dispersion treatment with the dispersant.

As the dispersant, the dispersant described above can be used. When a dispersant is used, the amount thereof is preferably 1 to 100% by mass, more preferably 5 to 50% by mass, based on the total amount of the pigment (a 2). When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a uniformly dispersed state can be obtained.

The content of the compound (a) in the colorant (a) is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, particularly preferably 80% by mass or more, and may be 100% by mass, 98% by mass or less, and may be 95% by mass or less.

The content of the xanthene dye in the colorant (a) is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less.

The total content of the compound (a) and the xanthene dye in the colorant (a) is preferably 75% by mass or more, more preferably 85% by mass or more, still more preferably 95% by mass or more, particularly preferably 98% by mass or more, and may be 100% by mass.

The content of the colorant (a) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and still more preferably 10 to 50% by mass, based on the total amount of solid components. When the content of the colorant (a) is within the above range, the color density in the formation of a color filter is sufficient, and the desired amounts of the resin (B) and the polymerizable compound (C) can be contained in the composition, so that a pattern having sufficient mechanical strength can be formed.

Here, the "total amount of solid components" in the present specification means an amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of the solid components and the contents of the respective components relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.

< resin (B) >

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [ K1] to [ K6 ].

Resin [ K1 ]: a copolymer having a structural unit derived from at least 1 (a) (hereinafter, sometimes referred to as "(a)") selected from an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, and a structural unit derived from a monomer (b) (hereinafter, sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;

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

resin [ K3 ]: a copolymer having a structural unit from (a) and a structural unit from (c);

resin [ K4 ]: a copolymer having a structural unit derived from (a) to which a structural unit derived from (b) and a structural unit derived from (c) are added;

resin [ K5 ]: a copolymer having a structural unit derived from (b) to which a structural unit derived from (a) and a structural unit derived from (c) are added;

resin [ K6 ]: a copolymer having a structural unit obtained by adding (a) to a structural unit obtained from (b) and further adding a carboxylic anhydride, and a structural unit obtained from (c).

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, and 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 acid 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 them, 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) The monomer preferably contains 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 same meanings are also given to "(meth) acryloyl group" and "(meth) acrylate" and the like.

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

Examples of (b 1-1) include glycidyl (meth) acrylate,. beta. -methylglycidyl (meth) acrylate,. beta. -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether,. alpha. -methyl-o-vinylbenzyl glycidyl ether,. alpha. -methyl-m-vinylbenzyl glycidyl ether,. alpha. -methyl-p-vinylbenzyl glycidyl ether, 2, 3-bis (glycidoxymethyl) styrene, 2, 4-bis (glycidoxymethyl) styrene, 2, 5-bis (glycidoxymethyl) styrene, 2, 6-bis (glycidoxymethyl) styrene, 2,3, 4-tris (glycidoxymethyl) styrene, 2,3, 5-tris (glycidoxymethyl) styrene, 2,3, 6-tris (glycidoxymethyl) styrene, 3,4, 5-tris (glycidoxymethyl) styrene, 2,4, 6-tris (glycidoxymethyl) styrene and the like.

Examples of (b 1-2) include vinylcyclohexene monooxide, 1, 2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000 (manufactured by Daicel Co., Ltd.), (3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer (registered trademark) A400 (manufactured by Daicel Co., Ltd.), (3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer (registered trademark) M100 (manufactured by Daicel Co., Ltd.)), compounds represented by the formula (I), and compounds represented by the formula (II).

[ formula (I) and formula (II) wherein R^aAnd R^bRepresents 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 alkanediyl group having 1 to 6 carbon atoms.

Denotes the bonding site to O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

Examples of the alkyl group in which a 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^bPreferred examples thereof include a hydrogen atom, methyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-The hydroxyethyl group is more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1, 2-diyl group, a propane-1, 3-diyl group, a butane-1, 4-diyl group, a pentane-1, 5-diyl group, and a hexane-1, 6-diyl group.

As X^aAnd X^bPreferred examples thereof include a single bond, methylene, ethylene and-CH₂-O-and-CH₂CH₂More preferably, the group-O-includes a single bond and-CH₂CH₂-O- (. indicates a bonding site to O).

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

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

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of 2 or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the content ratio [ the compound represented by the formula (I): the compound represented by the formula (II) ] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.

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., Viscoat V #150, manufactured by Osaka organic chemical industries, Ltd.), and tetrahydrofurfuryl methacrylate.

As (b), the one (b1) is preferable in that the obtained color filter can have higher reliability such as heat resistance and chemical resistance. Further, (b 1-2) is more preferable in that the colored curable resin 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 (which is known as "dicyclopentyl (meth) acrylate" as a common name in the art, and may be referred to as "tricyclodecyl (meth) acrylate" in some cases), and tricyclo (meth) acrylate [5.2.1.0^2,6]Decen-8-yl ester (in the art, as(meth) acrylate esters such as dicyclopentenyl (meth) acrylate), "dicyclopentenyloxyethyl (meth) acrylate," (isobornyl (meth) acrylate, "(adamantyl (meth) acrylate," (meth) acrylate propargyl (meth) acrylate, phenyl (meth) acrylate, "(meth) acrylate naphthyl ester 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-unsaturated compounds such as 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 and the like;

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;

styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluenes, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene and the like.

Among them, 2-hydroxyethyl (meth) acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoints of copolymerization reactivity and heat resistance.

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

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

The resin [ K1] can be produced, for example, by referring to the method described in "Experimental method for Polymer Synthesis" (published by Otsuka institute of Engineers, 1 st edition, chemical Co., Ltd., 1972, 3 months and 1 days), and the cited documents described in the above documents.

Specifically, the following methods are mentioned: the reaction vessel is charged with predetermined amounts of (a) and (b), a polymerization initiator, a solvent, etc., and a deoxygenated atmosphere is prepared by replacing oxygen with nitrogen, for example, and heating and heat-maintaining are carried out while stirring. The polymerization initiator and the solvent used herein are not particularly limited, and polymerization initiators and solvents generally used in this field can be used. Examples of the polymerization initiator include azo compounds (e.g., 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), and organic peroxides (e.g., benzoyl peroxide), and examples of the solvent include solvents that dissolve the monomers, and solvents described below as the solvent (E) of the colored curable resin composition of the present invention.

The copolymer obtained may be used as it is, as a solution after the reaction, as a solution after concentration or dilution, or as a substance taken out as a solid (powder) by a method such as reprecipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent in the polymerization, the solution after the reaction can be directly used for preparing the colored curable resin composition of the present invention, and therefore, the production process of the colored curable resin composition of the present invention can be simplified.

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

When the ratio of the structural units of the resin [ K2] is in the above range, the colored curable resin composition can be excellent in storage stability, developability in forming a colored pattern, and solvent resistance, heat resistance, and mechanical strength of the obtained color filter.

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

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

The resin [ K3] can be produced, for example, in the same manner as described for the production method of 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, a copolymer of (a) and (c) was produced in the same manner as in the method described for producing resin [ K1 ]. In this case, the ratio of the structural units derived from each unit is preferably the same as the ratio recited in resin [ K3 ].

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

After the production of the copolymer of (a) and (c), the atmosphere in the flask is subsequently replaced with air from nitrogen, and (b), a reaction catalyst for a carboxylic acid or a carboxylic anhydride and a cyclic ether (e.g., tris (dimethylaminomethyl) phenol) and a polymerization inhibitor (e.g., hydroquinone) are placed in the flask and reacted at 60 to 130 ℃ for 1 to 10 hours, whereby a resin [ K4] can be produced.

(b) The amount of (b) is preferably 5 to 80 moles, more preferably 10 to 75 moles, based on 100 moles of (a). When the content is within this range, the storage stability of the colored curable resin composition, the developability in forming a pattern, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern can be well balanced. The cyclic ether is highly reactive and (b) used for the resin [ K4] is preferably (b1), more preferably (b 1-1) in view of the difficulty in leaving unreacted (b).

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 charging method, the reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like. Similarly to the polymerization conditions, the charging 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.

As the first stage of the resin [ K5], a copolymer of (b) and (c) was obtained in the same manner as in the above-described method for producing the resin [ K1 ]. As described above, the copolymer obtained 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 substance taken out as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c) is preferably 5 to 95 mol% of the structural unit derived from (b), 5 to 95 mol% of the structural unit derived from (c), more preferably 10 to 90 mol% of the structural unit derived from (b), and 10 to 90 mol% of the structural unit derived from (c), respectively, based on the total mole number of all the structural units constituting the copolymer.

Further, the resin [ K5] can be obtained by reacting the carboxylic acid or carboxylic anhydride contained in (a) with the cyclic ether derived from (b) contained in the copolymer of (b) and (c) under the same conditions as in the process for producing the resin [ K4 ].

The amount of (a) to be used in the reaction with the copolymer is preferably 5 to 80 mol based on 100 mol of (b). The cyclic ether has high reactivity and is not likely to remain as unreacted (b), and (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 produced by the reaction of the cyclic ether and the carboxylic acid or carboxylic anhydride.

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 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid copolymer, and 3, 4-epoxytricyclo [5.2.1.0 ] acrylate^2,6]Resins such as decyl ester/(meth) acrylic acid copolymers [ K1]](ii) a Glycidyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, acrylic acid 3, 4-epoxy tricyclo [5.2.1.0 ]^2,6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, acrylic acid 3, 4-epoxytricyclo [5.2.1.0^2,6]Resins such as decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane/(meth) acrylic acid/styrene copolymer [ K2](ii) a Resins such as benzyl (meth) acrylate/(meth) acrylic acid copolymer and styrene/(meth) acrylic acid copolymer [ K3](ii) a Reacting glycidyl (meth) acrylate with (meth) acrylic acidResins obtained by adding a benzyl ester/(meth) acrylic acid copolymer, resins obtained by adding glycidyl (meth) acrylate and tricyclodecyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, and resins obtained by adding glycidyl (meth) acrylate and tricyclodecyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid copolymer [ K4]](ii) a Resins obtained by reacting a copolymer of (meth) acrylic acid and tricyclodecyl (meth) acrylate/(glycidyl (meth) acrylate), and resins obtained by reacting a copolymer of (meth) acrylic acid and 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.

Among them, as the resin (B), the resin [ K1] and the resin [ K2] are preferable, and the resin [ K1] is particularly 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 color filter has high hardness, a high residual film ratio, and an unexposed portion has good solubility in a developer, and the resolution of a colored pattern can 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) is preferably 50 to 170 mg-KOH/g, more preferably 60 to 150 mg-KOH/g, and still more preferably 70 to 135 mg-KOH/g in terms of solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin (B), and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass, based on the total amount of solid components. When 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 can 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 has a hydroxyl value of 100mgKOH/g or more. The colored curable resin composition of the present invention containing the polymerizable compound (C) can realize a thin film of the obtained cured film. In a preferred embodiment, the cured film obtained can have good brightness.

The polymerizable compound (C) may be composed of 1 or more polymerizable compounds having a hydroxyl value of 100mgKOH/g, or may contain 2 or more polymerizable compounds having a hydroxyl value of 100mgKOH/g or more. The polymerizable compound (C) may be a mixture of 1 or 2 or more polymerizable compounds having a hydroxyl value of 100mgKOH/g or more and 1 or 2 or more polymerizable compounds having a hydroxyl value of less than 100 mgKOH/g. When 2 or more polymerizable compounds are contained as the polymerizable compound (C), the hydroxyl value of the polymerizable compound (C) means the hydroxyl value of the mixture. The hydroxyl value of the polymerizable compound (C) is measured according to the description of examples described below.

The hydroxyl value of the polymerizable compound (C) is preferably 110mgKOH/g or more, more preferably 180mgKOH/g or more, still more preferably 200mgKOH/g or more, and particularly preferably 250mgKOH/g or more. When the hydroxyl value of the polymerizable compound (C) is within the above range, the obtained cured film can be made thin, and in a preferred embodiment, the brightness of the obtained cured film can be improved. From the viewpoint of availability, the hydroxyl value of the polymerizable compound (C) is preferably 500mgKOH/g or less, more preferably 450mgKOH/g or less, still more preferably 400mgKOH/g or less, yet more preferably 350mgKOH/g or less, and particularly preferably 300mgKOH/g or less.

Examples of the polymerizable compound (C) include compounds having a polymerizable ethylenically unsaturated bond and a hydroxyl group. The average number of double bonds of the polymerizable compound (C) is 1.0 or more, preferably 2.0 or more, more preferably 2.5 or more, and preferably 4.0 or less, more preferably 3.5 or less, and more preferably 3.0 or less. The average number of double bonds of the polymerizable compound (C) can be measured by an analytical method such as HPLC (high performance liquid chromatography).

Specific examples of the polymerizable compound having a hydroxyl value of 100mgKOH/g or more include pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol mono (meth) acrylate, ethylene glycol-modified pentaerythritol tri (meth) acrylate, propylene glycol-modified pentaerythritol triacrylate, trimethylolpropane di (meth) acrylate, ethylene glycol-modified glycerol di (meth) acrylate, propylene glycol-modified glycerol di (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ethylene glycol-modified ditrimethylolpropane tri (meth) acrylate, propylene glycol-modified ditrimethylolpropane triacrylate, dipentaerythritol pentaacrylate, and the like. The polymerizable compound (C) preferably contains at least pentaerythritol tri (meth) acrylate, and more preferably contains pentaerythritol triacrylate. When the polymerizable compound (C) contains pentaerythritol tri (meth) acrylate (preferably pentaerythritol triacrylate), the content thereof in the polymerizable compound (C) is preferably 10% by mass or more, more preferably 25% by mass or more, further preferably 40% by mass or more, and may be 100% by mass, 90% by mass or less, or 80% by mass or less.

The content of the polymerizable compound having a hydroxyl value of 100mgKOH/g or more in the polymerizable compound (C) is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and may be 100% by mass, or may be 98% by mass or less, or may be 93% by mass or less.

When the polymerizable compound (C) is a mixture of 2 or more polymerizable compounds, the polymerizable compound (C) may contain a polymerizable compound having a hydroxyl value of less than 100mgKOH/g as long as the hydroxyl value of the mixture is not less than 100 mgKOH/g. Specific examples of the polymerizable compound having a hydroxyl value of less than 100mgKOH/g include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol deca (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 caprolactone-modified dipentaerythritol hexa (meth) acrylate.

The content of the polymerizable compound (C) is preferably 7% by mass or more, more preferably 13% by mass or more, and still more preferably 20% by mass or more, and further preferably 65% by mass or less, more preferably 55% by mass or less, and still more preferably 45% by mass or less, based on the total amount of the solid content. When the content of the polymerizable compound (C) is within the above range, the obtained cured film can be made thin, and the residual film ratio at the time of forming a colored pattern and the chemical resistance of the color filter can 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 under the action of light or heat to initiate polymerization, and a known polymerization initiator can be used. As the polymerization initiator generating active radicals, for example, an alkylbenzene ketone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a bisimidazole compound can be cited.

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

Examples of the O-acyloxime compound 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, N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxocyclopentylmethoxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, and N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-imine 1-imine, N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine. Commercially available products such as Irgacure OXE01, OXE02 (both of which are available from BASF corporation), N-1919 (available from ADEKA corporation), and PBG-327 (available from Changzhou powerful electron new material Co., Ltd.) can also be used. Among them, the O-acyloxime compound is preferably at least 1 selected from the group consisting of 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, and N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine, and more preferably at least 1 selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine and N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine. When these O-acyloxime compounds are used, a color filter having high luminance can be obtained.

The above-mentioned alkylphenone compound has a partial structure represented by the formula (d2) or a partial structure represented by the formula (d 3). In the partial structure of these, 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 (all of which are manufactured by BASF corporation) may be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 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, and benzildimethylketal.

In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d 2).

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) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (4-diethylamino-2-methylphenyl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 2- (3, 4-dimethoxyphenyl) vinyl ] -1, 3, 5-triazine.

Examples of the acylphosphine oxide compound include 2,4, 6-trimethylbenzoyldiphenylphosphine oxide and the like. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

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' -bis (2-chlorophenyl) -4, 4 ', 5, 5' -tetrakis (trialkoxyphenyl) biimidazole (for example, refer to Japanese patent application laid-open No. 48-38403 and Japanese patent application laid-open No. 62-174204), and biimidazole compounds in which the phenyl group at the 4,4 ', 5, 5' -position is substituted with a carboalkoxy group (カルボアルコキシ group) (see, for example, Japanese patent application laid-open No. 7-10913).

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 and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, 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 acid generator include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyltoluenesulfonate and benzoin toluenesulfonate.

As the polymerization initiator (D), a polymerization initiator containing at least 1 selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a bisimidazole compound is preferable, and a polymerization initiator containing an O-acyloxime compound is more preferable.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and 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). When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time can be shortened, so that the productivity of the color filter is improved.

< polymerization initiation assistant (D1) >)

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

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

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4 '-bis (dimethylamino) benzophenone (commonly known as michelson), 4' -bis (diethylamino) benzophenone, and 4,4 '-bis (ethylmethylamino) benzophenone, and among them, 4' -bis (diethylamino) benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Baotu chemical industries, Ltd.) may also 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 phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid and the like.

When the polymerization initiating assistant (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). When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be further formed with high sensitivity, and the productivity of the color filter can be improved.

< 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-in the molecule and not containing-O-), ether solvents (solvents containing-O-in the molecule and not containing-COO-), ether ester solvents (solvents containing-COO-and-O-in the molecule), ketone solvents (solvents containing-CO-in the molecule and not containing-COO-), alcohol solvents (solvents containing OH in the molecule and not containing-O-, -CO-and-COO-), 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 and ethylene glycol bisAlcohol 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-diethylene glycol

Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 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 monoethylether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethylether acetate, diethylene glycol monobutyl 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.

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

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

Among the above solvents, organic solvents having a boiling point of 120 to 180 ℃ at 1atm are preferable from the viewpoint of coatability and drying property. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, and N, N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, and 4-hydroxy-4-methyl-2-pentanone are more preferable.

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 colored curable resin composition of the present invention. In other words, the total content of the solid content in the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color density is not insufficient at the time of forming a color filter, so that the display characteristics can become good.

< leveling 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, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: Toray Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by shin-Etsu chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF 46, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan contract Co., Ltd.) may be mentioned.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, examples thereof include FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC (Co., Ltd.), F-top (registered trademark) EF301, F-top EF303, F-top EF351, F-top EF352 (manufactured by Mitsubishi electro chemical Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Nitron (Co., Ltd.), and E5844 (manufactured by King Kogyo chemical Co., Ltd.).

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, there may be mentioned MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477 and MEGAFAC F443 (manufactured by DIC Co., Ltd.).

The content of the leveling agent (F) is preferably 0.001 to 0.2% by mass, more preferably 0.002 to 0.2% by mass, and still more preferably 0.01 to 0.2% by mass, based on the total amount of the colored curable resin composition. The content does not include the dispersant. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

< other ingredients >

The colored curable resin composition of the present invention may contain additives known in the art, such as a filler, another polymer compound, an adhesion promoter, a light stabilizer, and a chain transfer agent, as required.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-isocyanatoethyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-methyldimethoxysilane, 3-methacryloxysilane, 3-2-methacryloxysilane, 3-isocyanatoethylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-3-aminopropyltrimethoxysilane, and the like, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane and the like.

< method for producing colored curable resin composition >

The colored curable resin composition of the present invention can be prepared, for example, by mixing the colorant (a), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and, if necessary, the solvent (E), the leveling agent (F), the polymerization initiation aid (D1), and other components.

The colorant (A) may be used in a state where it is mixed with a part or all of the solvent (E) in advance and dispersed by a bead mill or the like as necessary until the average particle diameter becomes about 0.2 μm or less. In this case, a part or all of the above-mentioned dispersant and resin (B) may be blended as necessary. The objective coloring composition is preferably prepared by mixing the remaining ingredients to the thus obtained dispersion liquid so as to reach a prescribed concentration. When a bead mill is used, the diameter of the beads is preferably 0.05mm to 0.5mm, and examples of the material of the beads include glass, ceramics, metals, and the like.

< method for manufacturing color filter >

Examples of the method for producing a colored pattern from the colored curable resin 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 curable resin composition is applied to a substrate and dried to form a composition layer, and the 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 composition layer can be formed without using a photomask and/or without performing development at the time of exposure.

The film thickness of the color filter (cured film) 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, or polyethylene terephthalate, a substrate of silicon, a substrate having a thin film of aluminum, silver/copper/palladium alloy formed on the substrate, or the like can be used. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates. In addition, a substrate subjected to HMDS treatment on a silicon substrate may be used.

The formation of each color pixel by photolithography can be performed by using a known or conventional apparatus and conditions. For example, the following can be used. 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, thereby drying to obtain a smooth composition layer. Examples of the coating method include a spin coating method, a slit coating method, and a slit spin coating method. The temperature for the heat drying is preferably 30 to 120 ℃ and 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, the drying is preferably carried out under a pressure of 50 to 150Pa and at a temperature of 20 to 25 ℃. The film thickness of the composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the composition layer is exposed through a photomask for forming a target colored pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use is used. In addition, exposure is performed without using a photomask in order to form a colored coating film. The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350nm may be cut off using a filter that cuts off the wavelength region, or light near 436nm, near 408nm, or near 365nm may be selectively extracted using a band-pass filter that extracts these wavelength regions. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like can be given. In order to uniformly irradiate parallel light to the entire exposure surface and perform precise alignment of the photomask and the substrate, a reduction projection exposure apparatus such as a mask aligner and a stepper or a proximity exposure apparatus is preferably used.

The exposed composition layer is brought into contact with a developer to develop the composition layer, thereby forming a colored pattern on the substrate. The unexposed portion of the composition layer is dissolved in a developing solution and removed by development. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. 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. In addition, the developer may contain a surfactant. The developing method may be any of spin immersion, spraying, and the like. Further, the substrate can be inclined at an arbitrary angle during development.

After development, washing with water is preferred.

The obtained colored pattern and colored coating film are preferably subjected to post-baking. The postbaking temperature is preferably from 80 ℃ to 250 ℃ and more preferably from 100 ℃ to 245 ℃. The postbaking time is preferably from 1 minute to 120 minutes, more preferably from 2 minutes to 30 minutes.

The colored pattern and the colored coating film obtained by the above method are useful as a color filter, and the color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, or the like), electronic paper, a solid-state imaging device, or the like.

Examples

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

Hereinafter, the structure of the compound was confirmed by MASS analysis (LC; model 1200 by Agilent, MASS; LC/MSD by Agilent).

[ colorant Synthesis example 1]

The following reaction was carried out under nitrogen atmosphere. 26.4 parts of potassium thiocyanate and 156 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. 40.0 parts of 2, 6-difluorobenzoyl chloride (manufactured by Tokyo chemical Co., Ltd.) was added dropwise to the flask over 30 minutes, followed by stirring at room temperature for 1 hour. 30.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo chemical Co., Ltd.) was added dropwise to the flask over 30 minutes, and then the mixture was stirred at room temperature for 1 hour. Into the flask were charged an aqueous solution of 79.2 parts of sodium monochloroacetate dissolved in 120 parts of ion-exchanged water, and 60.4 parts of a 30% aqueous sodium hydroxide solution, followed by stirring at room temperature for 18 hours. 600 parts of ion-exchanged water was further added to the flask, followed by stirring for 1 hour, and the precipitated yellowish white solid was collected by filtration. The obtained yellowish white solid was washed with 120 parts of acetonitrile and then with 560 parts of ion-exchanged water. The washed off-white solid, 156 parts of ion-exchanged water, 35.0 parts of 99% acetic acid (manufactured by Wako pure chemical industries, Ltd.) and 156 parts of toluene were put into a flask equipped with a stirrer, and stirred at room temperature for 2 hours. 80.8 parts of a 30% aqueous sodium hydroxide solution was added dropwise thereto over 10 minutes, followed by stirring for 5 minutes, and the aqueous layer was removed by a liquid separation operation. To the obtained organic layer, 156 parts of ion-exchanged water was added for liquid-separation washing, and then 156 parts of ion-exchanged water and 0.1 part of 35% hydrochloric acid were added for liquid-separation washing. The obtained organic layer was concentrated by an evaporator and then dried at 35 ℃ under reduced pressure to obtain a compound represented by the formula (B-I-1) as a white solid. The yield was 43.4 parts, and the yield was 58.0%.

The following reaction was carried out under nitrogen atmosphere. 13.2 parts of the compound represented by the formula (B-I-1), 19.0 parts of the compound represented by the formula (C-I-1) and 38 parts of toluene were charged into a flask equipped with a cooling tube and a stirrer, and then 9.2 parts of phosphorus oxychloride was added thereto and the mixture was stirred at 100 ℃ for 7 hours. Next, the reaction mixture was cooled to room temperature, and then diluted with 29 parts of methyl ethyl ketone. Next, a mixed solution of 114 parts of ion-exchanged water and 10 parts of 35% aqueous hydrochloric acid was poured into the diluted reaction mixture, and the aqueous layer was removed by a liquid separation operation. The obtained organic layer was evaporated in an evaporator, and then dried at 60 ℃ under reduced pressure, whereby the compound represented by the formula (X-II-1) was obtained as a bluish-purple solid. The yield of the bluish violet solid was 39.4 parts.

The following reaction was carried out under nitrogen atmosphere. A flask equipped with a cooling tube and a stirrer was charged with 38.4 parts of the compound represented by the formula (X-II-1) and 112 parts of methylene chloride, and stirred for 30 minutes. The reaction solution was cooled with ice, 31.6 parts of chlorosulfonic acid (manufactured by Tokyo chemical Co., Ltd.) was added while maintaining the internal temperature at 10 ℃ and the reaction solution was then stirred at room temperature for 9 hours. Subsequently, the reaction solution was cooled with ice and diluted with a mixed solution of 64 parts of N, N-dimethylformamide and 4.9 parts of ion-exchanged water while maintaining the internal temperature at 10 ℃. After the diluted reaction solution was poured into 1120 parts of toluene, a viscous solid precipitated when stirred for 30 minutes. After the oil layer was drained by decantation, 320 parts of toluene was added to the obtained viscous solid and stirred for 30 minutes. The oil layer was drained by decantation, 832 parts of 20% saline solution was added to the obtained viscous solid, and after stirring for 1 hour, the blue solid was filtered off by filtration. The obtained blue solid was washed with 576 parts of 20% saline solution and dried at 35 ℃ under reduced pressure. The obtained solid and 128 parts of methanol were put into a flask equipped with a stirrer, stirred for 30 minutes, and then filtered to separate the solid and the filtrate. The filtrate was designated as filtrate A3. The filtered solid was washed with 192 parts of methanol, and separated into a solid and a filtrate by filtration. This filtrate was used as filtrate B3. The filtrate A3 and the filtrate B3 were mixed, the solvent was removed by an evaporator, and the mixture was dried under reduced pressure at 40 ℃ to obtain a compound represented by the formula (X-I-1) as a bluish-purple solid.

The yield of the bluish violet solid was 38.3 parts.

28.0 parts of the compound represented by the formula (X-I-1), 43.2 parts of barium chloride dihydrate and 356 parts of ion-exchanged water were added to a flask equipped with a cooling tube and a stirrer, and the mixture was stirred at 40 ℃ for 2 hours, followed by filtration of the reaction suspension. The filtered solid and 350 parts of ion-exchanged water were put into a flask equipped with a stirrer, and after stirring for 30 minutes, the suspension was filtered. The obtained solid was washed with 280 parts of ion-exchanged water and then dried at 60 ℃ under reduced pressure to obtain a compound represented by the formula (A-I-1) as a bluish-purple solid. The yield was 24.5 parts, and the yield was 81.7%.

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

(Mass analysis) ionization mode ESI-M/z 949.5[ M-Ba +2H ]]^-

Accurate molecular weight [ M-Ba ] 947.28

[ colorant Synthesis example 2]

40.5 parts of the compound represented by the formula (1a) and 60.5 parts of 2, 6-xylidine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were mixed under light-shielding conditions, and the mixture was stirred at 150 ℃ for 8 hours in 200 parts of N-methylpyridone.

The obtained reaction solution was cooled to room temperature, and then added to a mixture of 1200 parts of water and 75 parts of 35% hydrochloric acid, and the mixture was stirred at room temperature for 1 hour, whereby crystals were precipitated. The precipitated crystals were collected as a residue by suction filtration, washed with 100 parts of methanol, and dried under reduced pressure at 60 ℃ for 1 hour to obtain 49 parts of a compound represented by the formula (1-32). The yield thereof was found to be 85%.

[ resin Synthesis example 1]

A suitable amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was changed to 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 added dropwise over 5 hours^2,6]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0² ^,6]A mixed solution of 289 parts of a mixture of decane-9-yl esters (containing 1:1 ratio in terms of molar ratio) and 125 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution prepared by dissolving 33 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was held at 80 ℃ for 4 hours and then cooled to room temperature to obtain a copolymer (resin B1) solution containing 35.1% of a solid content and having a viscosity of 125mPas as measured by a type B viscometer (23 ℃). The weight-average molecular weight Mw of the resulting copolymer was 9.2X 10³The dispersion degree was 2.08, and the acid value in terms of solid content was 77 mg-KOH/g. The resin B1 has the following structural units.

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.

A device; HLC-8120 GPC (manufactured by Tosoh corporation)

A column; TSK-GELG 2000HXL

Column temperature; 40 deg.C

A solvent; THF (tetrahydrofuran)

A flow rate; 1.0mL/min

Detecting the concentration of the solid component in the liquid; 0.001 to 0.01% by mass

The injection amount; 50 μ L

A detector; RI (Ri)

A calibration standard substance; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

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 colorant Dispersion 1]

23.1 parts of the compound represented by the formula (A-I-1), 28.8 parts of a dispersant (BYKLPN-6919 manufactured by BYK-Chemie; a 60% propylene glycol monomethyl ether acetate solution), 5.8 parts of a resin B1 (in terms of solid content), 28.9 parts of 4-hydroxy-4-methyl-2-pentanone, and 202 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and the mixture was shaken for 1 hour by a Paint Conditioner (manufactured by LAU). Thereafter, the zirconia beads were removed by filtration to obtain a colorant dispersion liquid 1.

[ comparative example 1]

[ preparation of colored curable resin composition 1]

The coloring agent dispersion 1, the compound represented by the formula (1-32), the resin, the polymerizable compound, the polymerization initiator, the solvent, and the leveling agent were mixed so as to have the following composition, thereby obtaining a colored curable resin composition 1. The colored curable resin composition 1 is a colored curable resin composition comprising,

2.5 parts of a compound represented by the formula (A-I-1) and 0.2 part of a compound represented by the formula (1-32) as a colorant (A);

1.9 parts (as solid content) of BYKLPN-6919 (BYK-Chemie) as a dispersant;

resin B1 in an amount of 7.8 parts (in terms of solid content) of resin (B);

5.2 parts of KAYARAD (registered trademark) DPHA (manufactured by Nippon Kagaku K.K., dipentaerythritol hexaacrylate, hydroxyl value: 10mgKOH/g) as a polymerizable compound (C);

0.4 part of PBG-327 (N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine, oxime compound, available from Changzhou powerful new electronic material Co., Ltd.) as a polymerization initiator (D);

78.9 parts of propylene glycol monomethyl ether acetate, 3.1 parts of 4-hydroxy-4-methyl-2-pentanone as solvent (E);

0.01 part (in terms of solid content) of Toray Silicone SH8400 (polyether-modified Silicone oil, manufactured by Dow Corning Toray Co., Ltd.) as a leveling agent (F).

[ comparative example 2]

[ preparation of colored curable resin composition 2]

The coloring agent dispersion liquid 1, the compound represented by the formula (1-32), the resin, the polymerizable compound, the polymerization initiator, the solvent, and the leveling agent were mixed so as to have the following composition, thereby obtaining a colored curable resin composition 2. The colored curable resin composition 2 is a colored curable resin composition comprising,

1.9 parts (as solid content) of BYKLPN-6919 (BYK-Chemie) as a dispersant;

resin B1 in an amount of 7.8 parts (in terms of solid content) of resin (B);

3.8 parts of KAYARAD (registered trademark) DPHA (manufactured by Nippon Kagaku K.K., dipentaerythritol hexaacrylate, hydroxyl value: 10mgKOH/g) and 1.5 parts of ARONIX (registered trademark) M-933 (manufactured by Toyo Seisaku K.K., hydroxyl value: 280mgKOH/g) as the polymerizable compound (C);

0.4 part of PBG-327 (N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-imine, oxime compound, manufactured by Changzhou powerful new electronic material Co., Ltd.) as a polymerization initiator (D);

The hydroxyl value of the mixture of the polymerizable compound (C) was 86 mgKOH/g.

[ comparative example 3]

[ preparation of colored curable resin composition 3]

The coloring agent dispersion liquid 1, a resin, a polymerizable compound, a polymerization initiator, a solvent, and a leveling agent were mixed so as to have the following composition, thereby obtaining a colored curable resin composition 3. The colored curable resin composition 3 is a colored curable resin composition comprising,

2.7 parts of a compound represented by the formula (A-I-1) as a colorant (A);

2.0 parts (as solid content) of BYKLPN-6919 (BYK-Chemie) as a dispersant;

resin B1 in an amount of 7.7 parts (in terms of solid content) of resin (B);

78.6 parts of propylene glycol monomethyl ether acetate, 3.4 parts of 4-hydroxy-4-methyl-2-pentanone as solvent (E);

0.01 part (in terms of solid content) of Toray Silicone SH8400 (polyether-modified Silicone oil, manufactured by Dow Corning Toray Co., Ltd.) as a leveling agent (F); .

[ example 1]

[ preparation of colored curable resin composition 4]

The coloring agent dispersion liquid 1, the compound represented by the formula (1-32), the resin, the polymerizable compound, the polymerization initiator, the solvent, and the leveling agent were mixed so as to have the following composition, thereby obtaining a colored curable resin composition 4. The colored curable resin composition 4 is a colored curable resin composition comprising,

1.9 parts (as solid content) of BYKLPN-6919 (BYK-Chemie) as a dispersant;

resin B1 in an amount of 7.8 parts (in terms of solid content) of resin (B);

5.2 parts of A-TMM-3 LM-N (New Miura chemical industry Co., Ltd., hydroxyl value: 110mgKOH/g) as a polymerizable compound (C);

[ example 2]

[ preparation of colored curable resin composition 5]

The coloring agent dispersion liquid 1, the compound represented by the formula (1-32), the resin, the polymerizable compound, the polymerization initiator, the solvent, and the leveling agent were mixed so as to have the following composition, thereby obtaining a colored curable resin composition 5. The colored curable resin composition 5 is a colored curable resin composition comprising,

1.9 parts (as solid content) of BYKLPN-6919 (BYK-Chemie) as a dispersant;

resin B1 in an amount of 7.8 parts (in terms of solid content) of resin (B);

5.2 parts of ARONIX (registered trademark) M-933 (available from Toyo chemical Co., Ltd., hydroxyl value: 280mgKOH/g) as a polymerizable compound (C);

[ example 3]

[ preparation of colored curable resin composition 6]

The coloring agent dispersion liquid 1, the compound represented by the formula (1-32), the resin, the polymerizable compound, the polymerization initiator, the solvent, and the leveling agent were mixed so as to have the following composition, thereby obtaining a colored curable resin composition 6. The colored curable resin composition 6 is a colored curable resin composition comprising,

1.9 parts (as solid content) of BYKLPN-6919 (BYK-Chemie) as a dispersant;

resin B1 in an amount of 7.8 parts (in terms of solid content) of resin (B);

2.5 parts of A-TMM-3 LM-N (hydroxyl value: 110mgKOH/g, manufactured by Ninghamu chemical industries, Ltd.) and 2.8 parts of ARONIX (registered trademark) M-933 (hydroxyl value: 280mgKOH/g, manufactured by Toyo Seisakusho Co., Ltd.) as the polymerizable compound (C);

The hydroxyl value of the mixture of the polymerizable compound (C) was 200 mgKOH/g.

[ example 4]

[ preparation of colored curable resin composition 7]

The coloring agent dispersion liquid 1, a resin, a polymerizable compound, a polymerization initiator, a solvent, and a leveling agent were mixed so as to have the following composition, thereby obtaining a colored curable resin composition 7. The colored curable resin composition 7 is a colored curable resin composition comprising,

2.7 parts of a compound represented by the formula (A-I-1) as a colorant (A);

2.0 parts (as solid content) of BYKLPN-6919 (BYK-Chemie) as a dispersant;

resin B1 in an amount of 7.7 parts (in terms of solid content) of resin (B);

[ measurement of hydroxyl value of polymerizable Compound ]

According to JIS K0070-. The measurement results are as described above.

[ production of colored coating film (color Filter) ]

Films obtained by postbaking colored curable resin compositions 1 to 7 by spin coatingThe resultant was coated on a 5 cm-square glass substrate (EAGLE 2000; manufactured by CORNING) to a thickness of 2.5 μm, and then prebaked at 100 ℃ for 3 minutes to form a colored composition layer. After cooling, the resultant was exposed to an exposure apparatus (TME-150 RSK; manufactured by TOPCON, Inc.) at a pressure of 80mJ/cm in an atmospheric atmosphere²The exposure amount (365nm basis) of (b) is irradiated with light to the colored composition layer. Thereafter, the resultant was postbaked in an oven at 230 ℃ for 30 minutes to obtain a colored coating film.

[ measurement of the rate of change of film thickness ]

The chromaticity and the film thickness of the obtained colored coating film were measured, and film thickness 1, x value 1, and Y value 1 were calculated when the Y value was adjusted to 0.092. Then, the colored coating film was heated in an oven at 230 ℃ for 3 hours. The chromaticity and the film thickness of the heated colored coating film were measured, and the film thickness 2, the x value 2, and the Y value 2 were calculated when the Y value was adjusted to 0.092, and the film thickness change rate was calculated according to the following equation. The results are shown in Table 10.

Film thickness change rate (film thickness 2/film thickness 1) × 100

A film thickness measuring instrument (DEKTAK 3; manufactured by Japan vacuum technology, Inc.) was used for measuring the film thickness of the colored coating film. The chromaticity was obtained as xy chromaticity coordinates (x, Y) and stimulus value Y in the XYZ color system of CIE according to the spectral spectrum measured by a colorimeter (OSP-SP-200; manufactured by Olympus corporation) and the characteristic function of a C illuminant.

Further, from the measured chromaticity values before and after heating, the color difference Δ E ab was calculated by the method described in JIS Z8730: 2009(7. method for calculating color difference). The results are shown in Table 10.

[ Table 10]

	Comparative example 1	Comparative example 2	Comparative example 3	Example 1	Example 2	Example 3	Example 4
								x value 2	0.143	0.143	0.139	0.143	0.143	0.143	0.139
Y value 2	10.4	10.5	10.1	10.5	10.7	10.7	10.7
								Rate of change of film thickness	111.9％	111.6％	114.4％	110.4％	108.7％	109.9％	110.6％
ΔE*ab	8.6	8.4	9.6	7.9	6.5	7.2	7.2

From the above results, it is found that the colored curable resin composition of the present invention has a small rate of change in film thickness although the film thickness tends to increase by heating. That is, it can be said that the color is kept dark while suppressing the phenomenon that the color becomes lighter by heating. In addition, color change due to heating is also small, and a color filter with high luminance can be obtained.

Industrial applicability

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

Claims

1. A colored curable resin composition comprising a colorant A, a resin B, a polymerizable compound C and a polymerization initiator D,

the colorant A comprises a compound represented by the formula (a),

the hydroxyl value of the polymerizable compound C is 100mgKOH/g or more,

in the formula (a), the reaction mixture is,

R⁴¹～R⁴⁴each 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 the aromatic hydrocarbon group and the aralkyl group may have a substituent of-SO₃ ^-or-SO₂－N^-－SO₂－R^fWhen the number of carbon atoms of the saturated hydrocarbon group is 2 to 20, -CH contained in the saturated hydrocarbon group₂-CH which is adjacent to the saturated hydrocarbon group having 2 to 20 carbon atoms and which may be substituted by-O-or-CO-₂-not simultaneously substituted by-O-, terminal-CH₂-not substituted by-O-or-CO-, R⁴¹And R⁴²May be bonded and form a ring together with the nitrogen atom to which they are bonded, R⁴³And R⁴⁴May be bonded and 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 a saturated hydrocarbon group having 1 to 20 carbon atoms and optionally having a substituent, wherein when the saturated hydrocarbon group has 2 to 20 carbon atoms, it constitutes-CH of the saturated hydrocarbon group₂-may be substituted by-O-or-CO-, R⁴⁸And R⁵²May be bonded to each other to form-NH-, -S-or-SO₂-, however, in the saturated hydrocarbon group, adjacent-CH₂-not simultaneously substituted by-O-, terminal-CH₂-is not substituted by-O-or-CO-,

ring T¹Represents an aromatic heterocycle having 3 to 10 carbon atoms, which may have a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a substituted or unsubstituted amino group, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, -SO₃ ^-or-SO₂－N^-－SO₂－R^fThe substituent which the aromatic hydrocarbon group may have may be-SO₃ ^-or-SO₂－N^-－SO₂－R^f，

M^r+A metal ion representing the valence of r,

k represents-SO of the compound represented by the formula (a)₃ ^-Number of and-SO₂－N^-－SO₂－R^fThe sum of the number of the first and second groups,

r represents an integer of 1 or more,

R^frepresents a fluoroalkyl group having 1 to 12 carbon atoms,

wherein the compound represented by the formula (a) has at least 1-SO₃ ^-or-SO₂－N^-－SO₂－R^f。

2. The colored curable resin composition according to claim 1, wherein the hydroxyl value of the polymerizable compound C is 200mgKOH/g or more.

3. The colored curable resin composition according to claim 1 or 2, wherein the colorant a further comprises a xanthene dye.

4. The colored curable resin composition according to claim 3, wherein the xanthene dye is a compound represented by formula (1),

in the formula (1), R¹～R⁴Independently of each other, a hydrogen atom, -R⁸Or a C6-10 1-valent aromatic hydrocarbon group, or R¹And R²And R³And R⁴Each together forming a nitrogen atom-containing ring, the hydrogen atoms contained in the aromatic hydrocarbon radical being optionally substituted by halogen atoms, -OH, -OR⁸、－SO₃ ^-、－SO₃H、－SO₃ ^-M⁺、－CO₂H、－CO₂R⁸、－SO₃R⁸or-SO₂NR⁹R¹⁰The substitution is carried out by the following steps,

R⁵represents-OH or-SO₃ ^-、－SO₃H、－SO₃ ^-M⁺、－CO₂H、－CO₂ ^-M⁺、－CO₂R⁸、－SO₃R⁸or-SO₂NR⁹R¹⁰，

m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of R⁵May be the same as, or different from,

R⁶and R⁷Independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,

M⁺to represent⁺N(R¹¹)₄、Na⁺Or K⁺X represents a halogen atom,

a represents a number of 0 or 1,

R⁸represents a C1-20 saturated hydrocarbon group, the hydrogen atom in the saturated hydrocarbon group may be substituted by a C6-10 aromatic hydrocarbon group, a carboxyl group or a halogen atom, and the-CH group in the saturated hydrocarbon group₂May be represented by-S-, -O-, -CO-or-NR¹¹-substituted, however, in the saturated hydrocarbon radical, adjacent-CH₂-not simultaneously substituted by-O-, R¹¹Represents a hydrogen atom, a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms, R¹¹When a plurality of them exist, all or a part of them may be the same,

R⁹and R¹⁰Independently represent a hydrogen atom or a 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by-OH or a halogen atom, and the-CH contained in the saturated hydrocarbon group₂May be substituted by-S-, -O-, -CO-, -NH-or-NR⁸-substituted, however, in the saturated hydrocarbon radical, adjacent-CH₂-is not simultaneously substituted with-O-,

R⁹and R¹⁰May be bonded to each other to form a heterocyclic ring of three to ten membered rings containing a nitrogen atom.

5. A color filter comprising the colored curable resin composition according to any one of claims 1 to 4.

6. A display device comprising the color filter of claim 5.