TW201604242A - Salt-forming type dye and colored curable resin composition - Google Patents

Abstract

The present invention provides a salt-forming type dye, which comprises a monovalent cationic dye, a bivalent anionic compound and a monovalent cationic compound having no color bases. In the present invention, a monovalent cationic dye and a bivalent anionic compound are reacted to form a monovalent anionic dye. Sometimes the monovalent anionic dye is named as an anionic dye (I-1). The salt-forming type dye can be formed by the anionic dye (I-1) and a monovalent cationic compound having no color bases. The salt-forming type dye provided by the present invention is formed by not only the anionic dye (I-1) but also the monovalent cationic compound having no color bases, so the color strength of the salt-forming dye is higher than the anionic dye (I-1).

Description

Salt-forming dye and color hardening resin composition

The present invention relates to a salt-forming dye and coloring curable resin composition

A dye is used as a coloring agent for a color filter included in a liquid crystal display device or the like, or a solid-state image sensor. As the dye, for example, a compound represented by the formula (A-III-1) (wherein Et represents an ethyl group) is described in WO2012/128318.

The invention includes the following invention.

[1] A salt-forming dye which is formed from a monovalent cationic dye, a divalent anionic compound, and a monovalent cationic compound having no chromogenic group.

[2] The salt-forming dye according to [1], which is formed from a monovalent anionic dye formed of a monovalent cationic dye and a divalent anionic compound, and a monovalent cationic compound having no coloring group.

[3] The salt-forming dye according to [1] or [2] wherein the divalent anionic compound is an aromatic compound having two identical monovalent anions or a heteroaromatic compound having two identical monovalent anions.

[4] The salt-forming dye according to [3], wherein the monovalent anion is a sulfonate anion.

[5] The salt-forming dye according to any one of [1] to [4] wherein the divalent anionic compound is a compound represented by the formula (1-b), ^- O ₃ SR ^1b -SO ₃ ^- (1-b )

(wherein R ^1b represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent).

[6] The salt-forming dye according to any one of [1] to [5] wherein the monovalent cationic dye is a compound represented by the formula (1-a),

[In the formula (1-A), R ^1A to R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms; -CH ₂ - may be substituted with -O-; R ^9A to R ^12A each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a 6 to 20 carbon atom which may have a substituent a hydrocarbon group, -CH ₂ - contained in an alkyl group having 1 to 20 carbon atoms may be substituted with -O-; A represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or may have a substituent a heteroaromatic hydrocarbon group having 2 to 10 carbon atoms].

[7] The salt-forming dye according to any one of [1] to [6] wherein the monovalent cation compound having no chromophore has at least one selected from the group consisting of a polymerizable group, a ruthenium atom and a phosphorus atom. A compound having a substituent in the group and having no chromophore.

[8] A coloring agent comprising the salt-forming dye according to any one of [1] to [7].

[9] A colored curable resin composition comprising the coloring agent according to [8] above, a resin, a polymerizable compound, and a polymerization initiator.

[10] A coating film formed from the color-curable resin composition of the above [9].

[11] A color filter formed of the color-curable resin composition of the above [9].

[12] A display device comprising the color filter of [11] above.

<salt-forming dye (I)>

The dye of the present invention is a salt-forming dye (hereinafter sometimes referred to as a salt-forming dye (I)) which is formed of a monovalent cationic dye, a divalent anionic compound, and a compound having a monovalent cation and having no chromogenic group.

In the present invention, a monovalent anionic dye is usually formed from a monovalent cationic dye and a divalent anionic compound. Hereinafter, the anionic dye may be referred to as "anionic dye (I-1)". The salt-forming dye (I) can be formed from an anionic dye (I-1) and a monovalent cationic compound having no chromogenic group.

The salt-forming dye of the present invention is formed of a monovalent cation compound having no chromogenic group in addition to the anionic dye (I-1), and thus has a higher chroma than the anionic dye (I-1).

Examples of the monovalent cationic dye include cations having two or more phenyl groups. Specific examples of the cationic dye include a compound represented by the formula (1-a) and a tautomer of the compound.

[In the formula (1-a), R ^1A to R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms; -CH ₂ - can be substituted with -O-.

R ^9A to R ^12A each independently represent a hydrogen atom, an alkyl 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, and an alkyl group having 1 to 20 carbon atoms. The contained -CH ₂ - may be substituted with -O-.

A represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a heteroaromatic hydrocarbon group having a substituent of 2 to 10 carbon atoms]

Examples of the halogen atom represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom. Or chlorine atoms.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A include a linear, branched and cyclic alkyl group. Specific examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, and a 2-ethylhexyl group. Octyl, decyl, decyl, undecyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, ring Octyl, cycloheptyl, cyclodecyl, decahydronaphthyl, adamantyl, 2-alkyladamantan-2-yl, 1-(adamantan-1-yl)alkan-1-yl, descending Base, methyl drop Base and difference base.

The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms.

-CH ₂ - contained in the alkyl group having 1 to 20 carbon atoms represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A may be substituted with -O-. In the case where -CH ₂ - contained in the alkyl group having 1 to 20 carbon atoms is substituted with -O-, -O- is not included as the carbon number.

-CH ₂ - contained in the alkyl group having 1 to 20 carbon atoms represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A is substituted with -O- The bases described below can be exemplified. Where * represents a bond key.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ^9A , R ^10A , R ^11A and R ^12A include R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^{8A .} The alkyl groups having the carbon number of 1 to 20 are the same.

-CH ₂ - contained in the alkyl group having 1 to 20 carbon atoms represented by R ^9A , R ^10A , R ^11A and R ^12A may be substituted with -O-. In the case where -CH ₂ - contained in the alkyl group having 1 to 20 carbon atoms is substituted with -O-, -O- is not included in the carbon number.

The group in which -CH ₂ - contained in the alkyl group having 1 to 20 carbon atoms represented by R ^9A , R ^10A , R ^11A and R ^12A is substituted with -O- may be exemplified as R ^1A and R ^{2A .} And a group in which the -CH ₂ - contained in the alkyl group having 1 to 20 carbon atoms represented by R ^3A , R ^4A , R ^5A , R ^6A , R ^5A , R ^6A , R ^5A , R ^6A , R ^7A and R ^8A is substituted with -O- is the same group .

The alkyl group having 1 to 20 carbon atoms represented by R ^9A , R ^10A , R ^11A and R ^12A may have a substituent, and examples thereof include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; Dimethylamino group or the like -NR ¹¹¹ R ¹¹² (R ¹¹¹ and R ¹¹² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).

Examples of the alkyl group having 1 to 20 carbon atoms which may have a substituent represented by R ^9A , R ^10A , R ^11A and R ^12A include the groups described below. * indicates a bond to a nitrogen atom.

Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ^9A , R ^10A , R ^11A and R ^12A include a phenyl group, a naphthyl group and an anthracenyl group.

The aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ^9A , R ^10A , R ^11A and R ^12A may have a substituent, and examples thereof include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or iodine; and a chloromethyl group; a trifluoromethyl group such as a haloalkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group; a hydroxyl group; an amine sulfonyl group; a carbon number such as a methylsulfonyl group; ~6 alkylsulfonyl.

The aromatic hydrocarbon group having 6 to 20 carbon atoms represented by A may, for example, be a phenyl group or a naphthyl group, and preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms.

The heteroaromatic hydrocarbon group having 2 to 10 carbon atoms represented by A may have at least one hetero atom as a constituent element of the ring.

Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.

Examples of the heteroaromatic hydrocarbon group having 2 to 10 carbon atoms represented by A include a pyridyl group, an imidazolyl group, and a pyrazolyl group. Azolyl, different An azole group, a thiazolyl group, an isothiazolyl group, a benzothiazolyl group, a benzisothiazolyl group, a thienyl group, a benzothienyl group, preferably a heteroaromatic hydrocarbon group having 2 to 8 carbon atoms, more preferably at least 1 The heteroaromatic hydrocarbon group having 2 to 8 carbon atoms of the nitrogen atom is more preferably a heteroaromatic hydrocarbon group having 2 to 8 carbon atoms (for example, a thiazolyl group) having a nitrogen atom and a sulfur atom.

Examples of the substituent in the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by A include a halogen atom, an amine group which may have a substituent, and an alkyl group having 1 to 6 carbon atoms.

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

Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, a third butyl group, a pentyl group, a neopentyl group, and Heji.

Examples of the substituent in the amine group include an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, and an aromatic hydrocarbon group having a substituent.

In the case of A, the alkyl group having 1 to 20 carbon atoms is a linear, branched or cyclic alkyl group, and specific examples thereof include a methyl group, an ethyl group, a n-propyl group, and an isopropyl group. n-Butyl, t-butyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, decyl, decyl, undecyl, dodecyl, cyclopropyl , cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cycloheptyl, cyclodecyl, decahydronaphthyl, adamantyl, 2- Alkyl adamantyl-2-yl, 1-(adamantan-1-yl)alkan-1-yl, descending Base, methyl drop Base and difference base.

Examples of the aromatic hydrocarbon group which is a substituent in the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by A include a phenyl group and a naphthyl group.

Examples of the substituent in the aromatic hydrocarbon group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an alkoxy group having 1 to 4 carbon atoms such as a methoxy group or an ethoxy group; and a methyl group and an ethyl group; An alkyl group having 1 to 4 carbon atoms such as a propyl group, an isopropyl group, a butyl group, a second butyl group and a third butyl group.

Examples of the amine group having a substituent include an alkylamino group such as a methylamino group and an ethylamino group; a phenylamino group, a 2-fluorophenylamino group, a 2-chlorophenylamino group, and Phenylamino group such as oxyphenyl)amino group or (o-methylphenyl)amino group; dialkylamino group such as dimethylamino group or diethylamino group; N-phenyl-N-methylamino group , an alkylphenyl group such as N-(o-methylphenyl)-N-methylamino, N-(o-methylphenyl)-N-ethyl, N-phenyl-N-isopropylamino Amine.

The heteroaromatic hydrocarbon group having 2 to 10 carbon atoms represented by A may have a substituent, and examples thereof include a halogen atom, an alkyl group having 1 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent. And an amine group which may have a substituent.

As a halogen atom, an alkyl group having 1 to 20 carbon atoms, and a carbon number 6 to 20 which may have a substituent Specific examples of the aromatic hydrocarbon group and the amine group which may have a substituent include those exemplified as the substituent which the aromatic hydrocarbon group may have.

Examples of the group represented by A include a group represented by the formula (A1-1) and a group represented by the formula (A1-13), preferably a group represented by the formula (A1-2), and a formula (A1-7). The group represented by the formula, the group represented by the formula (A1-8) and the group represented by the formula (A1-9) are further preferably a group represented by the formula (A1-8) and a formula (A1-9). The base of expression.

The monovalent cationic dye represented by the formula (1-a) is preferably a compound represented by the formula (1-a-1) and a tautomer thereof.

In the formula (1-a-1), X represents an oxygen atom or a sulfur atom.

R ⁴⁵ and R ⁴⁶ each independently represent a hydrogen atom, an alkyl 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, and the carbon number which may have a substituent -CH ₂ - contained in the alkyl group of ~20 may be substituted with -O-.

R ⁵⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

R ^1A ~ R ^12A respectively represent the same meaning as above]

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁴⁵ and R ⁴⁶ include a linear, branched, and cyclic alkyl group. Specific examples thereof include a methyl group, an ethyl group, and a n-propyl group. Isopropyl, n-butyl, t-butyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, decyl, decyl, undecyl, dodecyl , cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cycloheptyl, cyclodecyl, decahydronaphthyl, adamantane Base, 2-alkyladamantan-2-yl, 1-(adamantan-1-yl)alkan-1-yl, lower Base, methyl drop Base and difference base.

The alkyl group having 1 to 20 carbon atoms represented by R ⁴⁵ and R ⁴⁶ may have a substituent, and examples thereof include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an amine group and a dimethylamino group- NR ¹¹¹ R ¹¹² (R ¹¹¹ and R ¹¹² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).

The alkyl group having 1 to 20 carbon atoms which may have a substituent represented by R ⁴⁵ and R ⁴⁶ may have an alkyl group having 1 to 20 carbon atoms represented by R ^9A , R ^10A , R ^11A and R ^12A . The substituents are the same.

Examples of the aromatic hydrocarbon group represented by R ⁴⁵ and R ⁴⁶ include a phenyl group, a tolyl group, and a naphthyl group.

Examples of the substituent which the aromatic hydrocarbon group represented by R ⁴⁵ and R ⁴⁶ may have include a C 1 to 4 alkyl group such as a methyl group or an ethyl group; and a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; Alkoxy group having a carbon number of 1 to 6 such as a methoxy group or an ethoxy group; a haloalkyl group having 1 to 6 carbon atoms such as a chloromethyl group or a trifluoromethyl group; a hydroxyl group; an aminesulfonyl group; a methylsulfonyl group; An alkylsulfonyl group having 1 to 6 carbon atoms.

Examples of the aromatic hydrocarbon group which may have a substituent represented by R ⁴⁵ and R ⁴⁶ include the groups described below. * indicates a bond to a nitrogen atom.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁵⁵ include carbon numbers 1 to 20 represented by R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A . The same alkyl group.

The aromatic hydrocarbon group which may have a substituent represented by R ⁵⁵ may be the same as the aromatic hydrocarbon group which may have a substituent represented by R ⁴⁵ and R ⁴⁶ .

R ^1A , R ^2A , R ^3A , R ^4A , R ^5A , R ^6A , R ^7A and R ^8A are each independently a hydrogen atom, a halogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably independently A hydrogen atom, a methyl group, a fluorine atom or a chlorine atom.

R ^9A , R ^10A , R ^11A and R ^12A are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and more preferably independently The aromatic hydrocarbon group having 6 to 20 carbon atoms or an alkyl group having 1 to 8 carbon atoms which may have a halogen atom, a halogen alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a hydroxyl group.

R ⁴⁵ and R ⁴⁶ are each independently an alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and more preferably independently may have a halogen atom and have a carbon number of 1 to 2; 6 haloalkyl, alkoxy having 1 to 6 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms or an alkyl group having 1 to 8 carbon atoms.

R ^{55 is} preferably an alkyl group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, more preferably a halogen atom having 1 to 6 carbon atoms and a carbon number of 1 An alkoxy group of ~6 or an aromatic hydrocarbon group having a carbon number of 6 to 20 or an alkyl group having 1 to 8 carbon atoms.

The monovalent cationic dye may, for example, be a compound represented by the formula (1-a-2), and a compound represented by the formula (1-a-14), preferably a compound represented by the formula (1-a-2). a compound represented by the formula (1-a-3), a compound represented by the formula (1-a-5), and a compound represented by the formula (1-a-6).

The divalent anionic compound means a compound having a valence of a total of two in the compound, preferably a compound having two monovalent anions, more preferably a compound having two identical monovalent anions.

The monovalent anion may, for example, be a sulfonate anion [-SO ₃ ^- ] or a carboxylate anion [-COO ^- ], preferably a sulfonate anion.

The divalent anion compound is preferably an aromatic compound having two monovalent anions or a heteroaromatic compound having two monovalent anions, more preferably an aromatic compound having two monovalent anions, and further preferably having at least An aromatic compound of a sulfonate anion is particularly preferably a compound represented by the formula (1-b).

^- O ₃ SR ^1b -SO ₃ ^- (1-b)

(wherein R ^1b represents an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent)

Examples of the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ^1b include a phenyl group, a naphthyl group and an anthracenyl group, and a phenyl group or a naphthyl group is preferred.

The aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ^1b may have a substituent, and examples thereof include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; a nitro group; a hydroxyl group; an amine group; a methyl group and an ethyl group; Alkyl groups having 1 to 4 carbon atoms such as propyl, isopropyl, butyl, t-butyl and t-butyl; or methoxy, ethoxy, propoxy, isopropoxy or butoxy And an alkoxy group having 1 to 4 carbon atoms such as a second butoxy group and a third butoxy group; preferably a hydroxyl group or an amine group.

In the case where the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ^1b is a phenyl group, it is preferably one position or the ortho position relative to one monovalent anion.

In the case where the aromatic hydrocarbon group having 6 to 18 carbon atoms represented by R ^1b is a naphthyl group, it is preferred that one monovalent anion is bonded to a carbon atom which is not adjacent to a carbon atom to which another anion is bonded.

The compound represented by the formula (1-b-1) and the compound represented by the formula (1-b-13) are exemplified as the divalent anion compound.

The divalent anion compound is preferably a compound represented by the formula (1-b-1), a compound represented by the formula (1-b-2), a compound represented by the formula (1-b-3), or a formula (1- B-9) The compound represented by the formula (1-b-10).

Examples of the anionic dye (I-1) include an anionic dye represented by the formula (I-1a), an anionic dye represented by the formula (I-9a), and an anionic dye represented by the formula (I-4a). An anionic dye represented by the formula (I-6a).

The monovalent cation compound having no chromogenic group (hereinafter sometimes referred to as "monovalent cation compound") preferably has at least one group selected from the group consisting of a polymerizable group, a ruthenium atom and a phosphorus atom. A monovalent cationic compound having a substituent and having no chromogenic group.

Examples of the polymerizable group include a group having an ethylenically unsaturated bond, and specific examples thereof include an alkenyl group, an acryloyl group, and a methacryloyl group.

The monovalent cation preferably has an ammonium ion [-NH ₄ ⁺ ].

The monovalent cation compound having a polymerizable group may, for example, be a compound represented by the formula (Z-1).

[In the formula (Z-1), R ¹ represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ - contained in the alkanediyl group may be substituted with -O-, -CO-, -NR ¹¹ - , -OCO-, -COO-, -OCONH-, -CONH- or -NHCO-.

R ¹¹ represents an alkyldiyl group having 1 to 10 carbon atoms]

Examples of the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ and R ¹¹ include a linear, branched, and cyclic alkanediyl group, and specific examples thereof include a methylene group and an ethyl group. Propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octyl Alkan-1,8-diyl, ethane-1,1-diyl, propane-1,1-diyl, propane-1,2-diyl, propane-2,2-diyl, pentane-2 ,4-diyl, 2-methylpropane-1,3-diyl, 2-methylpropane-1,2-diyl, pentane-1,4-diyl, 2-methylbutane-1 , 4-diyl, cyclobutane-1,3-diyl, cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, descending Alkane-1,4-diyl, descending The alkane-2,5-diyl, adamantane-1,5-diyl, adamantane-2,6-diyl group is preferably an alkanediyl group having 1 to 8 carbon atoms.

The group in which -CH ₂ - contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ is substituted with -O- includes the group described below (* represents a bonding bond).

The group in which -CH ₂ - contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ is substituted with -CO- includes a group described below (* represents a bonding bond).

The group in which -CH ₂ - contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ is substituted with -NR ¹¹ - includes the group described below (* represents a bonding bond). .

The group in which -CH ₂ - contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ is substituted with -OCO- includes a group described below (* represents a bond).

The group in which -CH ₂ - contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ is substituted with -COO- includes a group described below (* represents a bonding bond).

The group in which -CH ₂ - contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ is substituted with -OCONH- includes the group described below (* represents a bonding bond).

The group in which -CH ₂ - contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ is substituted with -CONH- includes the group described below (* represents a bonding bond).

The group in which -CH ₂ - contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ is substituted with -NHCO- includes a group described below (* represents a bond bond).

The cationic compound having a polymerizable group may, for example, be a compound represented by the formula (Z-1-1) and represented by the formula (Z1-1-3), and is preferably represented by the formula (Z-1-1). Combination Things.

The cationic compound having a halogen atom may, for example, be a compound represented by the formula (Z-2).

[In the formula (Z-2), R ² represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ - contained in the alkanediyl group may be substituted with -O-, -CO-, -NR ²¹ - , -OCO-, -COO-, -OCONH-, -CONH- or -NHCO-.

R ⁴⁰ , R ⁴¹ and R ⁴² each independently represent a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

q represents an integer from 1 to 10]

The alkanediyl group having 1 to 10 carbon atoms represented by R ² and R ²¹ may be the same as the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ and R ¹¹ .

The -CH ₂ - contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ² is substituted with -O-, -CO-, -NR ²¹ -, -OCO-, -COO-, -OCONH- The group of -CONH- or -NHCO- can be exemplified by -CH ₂ - contained in the alkanediyl group having 1 to 10 carbon atoms represented by R ¹ is substituted with -O-, -CO-, - NR ¹¹ -, -OCO-, -COO-, -OCONH-, -CONH- or -NHCO- are the same.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁴⁰ , R ⁴¹ and R ⁴² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group and a t-butyl group. It is preferably a methyl group or an ethyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ⁴⁰ , R ⁴¹ and R ⁴² include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a second butoxy group. The base and the third butoxy group are preferably a methoxy group or an ethoxy group.

R ⁴⁰ , R ⁴¹ and R ^{42 are} preferably the same group.

R ⁴⁰ , R ⁴¹ and R ⁴² are each independently a hydroxyl group or an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group.

q is preferably an integer from 1 to 8, more preferably an integer from 1 to 3.

The cationic compound having a ruthenium atom may, for example, be a compound represented by the formula (Z-2-1) and represented by the formula (Z-2-12), and is preferably represented by the formula (Z-2-1). Compound - Compound represented by formula (Z-2-6).

The cationic compound having a phosphorus atom may, for example, be a compound represented by the formula (Z-3).

[In the formula (Z-3), R ⁵⁰ , R ⁵¹ , R ⁵² and R ⁵³ each independently represent an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a phenyl group which may be substituted]

Examples of the alkyl group having 1 to 10 carbon atoms represented by R ⁵⁰ , R ⁵¹ , R ⁵² and R ⁵³ include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group and a second butyl group. Tertiary butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 1-methylbutyl, 1,1,3,3-tetramethylbutyl, 1,5-dimethylhexyl and 2-Ethylhexyl or the like is preferably a methyl group, an ethyl group or a 2-ethylhexyl group.

Examples of the alkenyl group having 2 to 10 carbon atoms represented by R ⁵⁰ , R ⁵¹ , R ⁵² and R ⁵³ include a vinyl group, an isopropenyl group, a pentenyl group and a hexenyl group, and a vinyl group is preferred.

Examples of the substituent of the phenyl group represented by R ⁵⁰ , R ⁵¹ , R ⁵² and R ⁵³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group and a third butyl group. An alkyl group having 1 to 4 carbon atoms; a methoxy group, an ethoxy group, a propoxy group, and an alkoxy group having 1 to 4 carbon atoms.

The cationic compound having a phosphorus atom is a compound represented by the formula (Z-3-1) and represented by the formula (Z-3-6). The cation having a phosphorus atom is preferably a compound represented by the formula (Z-3-1) or a compound represented by the formula (Z-3-2).

The salt-forming dye (I) includes a dye represented by the formula (I-1) and a dye represented by the formula (I-47). The salt-forming dye (I) is preferably a dye represented by the formula (I-16), a dye represented by the formula (I-27), and a dye represented by the formula (I-33), represented by the formula (I-47). The dye is more preferably a dye represented by the formula (I-16), a dye represented by the formula (I-19), a dye represented by the formula (I-27), or a dye represented by the formula (I-33). A dye represented by the formula (I-35).

Next, a method for producing the salt-forming dye (I) will be described.

Salt-forming dye (I) can be obtained by making anionic dye (I-1) and a monovalent cationic compound in water Obtained by carrying out the reaction. The sequence of this reaction is described below.

The anionic dye (I-1) can be obtained by reacting a monovalent cationic dye with a divalent anionic compound in water.

The reaction temperature of the monovalent cationic dye and the divalent anionic compound is preferably from 0 ° C to 120 ° C, more preferably from 10 ° C to 100 ° C. The reaction time is preferably from 1 to 24 hours, more preferably from 3 to 8 hours.

The method of obtaining the anionic dye (I-1) from the reaction mixture can be carried out by various known methods. For example, a method in which the precipitate formed after filtration is taken out and washed with water can be cited. Further purification may be carried out by a known method such as recrystallization as needed.

When the monovalent cationic dye is represented by the formula (I-a), it can be produced, for example, by reacting a compound represented by the formula (C-II) with a compound represented by the formula (C-III). The reaction can be carried out in the presence of an organic solvent or in the absence of a solvent.

[wherein, R ^1A to R ^12A and A are respectively the same as defined above]

The amount of the compound represented by the formula (C-III) in the reaction is preferably 1 to 8 moles, more preferably 1 to 3 moles, per mole of the compound represented by the formula (C-II).

The reaction temperature is preferably from 30 ° C to 180 ° C, more preferably from 80 ° C to 130 ° C. The reaction time is preferably from 1 hour to 12 hours, more preferably from 3 hours to 8 hours.

In terms of yield, the reaction of the compound represented by the formula (C-III) with the compound represented by the formula (C-II) is preferably carried out in the presence of an organic solvent. Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; and nitro hydrocarbon solvents such as nitrobenzene. a ketone solvent such as methyl isobutyl ketone or a guanamine solvent such as 1-methyl-2-pyrrolidone.

The amount of the organic solvent to be used is preferably 1 to 300 parts by mass, more preferably 2 to 200 parts by mass, per part by mass of the compound represented by the formula (C-II).

In terms of yield, the reaction of the compound represented by the formula (C-III) with the compound represented by the formula (C-II) is preferably carried out in the presence of a condensing agent. Examples of the condensing agent include phosphoric acid, polyphosphoric acid, phosphonium chloride, sulfuric acid, and sulfinium chloride.

The amount of the condensing agent to be used is preferably 1 to 20 parts by mass, more preferably 1 to 5 parts by mass, per part by mass of the compound represented by the formula (C-II).

A method of obtaining a monovalent anionic dye from the reaction mixture can be carried out by various known methods. For example, a method in which a reaction mixture is mixed with an alcohol (methanol or the like) and the precipitated crystals are removed by filtration can be mentioned.

The method of obtaining a monovalent anionic dye is preferably a method of adding a reaction mixture to an alcohol. The temperature at which the reaction mixture is added is preferably -100 to 50 ° C, more preferably -80 to 0 ° C. Further, it is preferred to stir it at the same temperature for 0.5 to 2 hours. The crystals removed by filtration are preferably washed with water or the like and then dried. Further, it may be further purified by a known method such as recrystallization as needed.

The salt-forming dye (I) can be obtained by reacting an anionic dye (I-1) with a monovalent cationic compound as described above.

The reaction temperature of the anionic dye (I-1) and the monovalent cationic compound is preferably from 0 to 120 ° C, more preferably from 10 to 100 ° C. The reaction time is preferably from 1 to 24 hours, more preferably from 3 to 8 hours.

The method of obtaining the salt-forming dye (I) from the reaction mixture can be carried out by various known methods. For example, a method in which the precipitate formed after filtration is taken out and washed with water can be cited. Further purification may be carried out by a known method such as recrystallization as needed.

The color-curable resin composition of the present invention comprises a coloring agent (A) containing a salt-forming dye (I), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). Further, a solvent (E) may be contained.

<Colorant (A)>

The colorant (A) contains two or more salt-forming dyes (I).

In addition to the salt-forming dye (I), the coloring agent (A) may contain other dyes (A2), pigments (P), or a mixture thereof for coloring, that is, for adjusting the spectral characteristics.

Examples of the dye (A2) include dyes such as oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes, and are classified as dyes in the dye index (published by The Society of Dyers and Colourists). A known dye as described in the compound or dyeing note (color dyeing company). Further, according to the chemical structure, a coumarin dye; a gold-containing azo dye; a pyridone azo dye; a barbituric azo dye; a quinacridone dye; a methine dye; a cyanine dye; Dye; triphenylmethane dye; Dyes; porphyrazine dyes; phthalocyanine dyes; and mixtures thereof.

The content of the salt-forming dye (I) is preferably from 3 to 99.9% by mass, more preferably from 4 to 80% by mass, even more preferably from 5 to 30% by mass, based on the total amount of the coloring agent (A). When the content of the salt-forming dye (I) is within the above range, the brightness when the color filter is formed is high, which is preferable.

As the pigment (P), a known pigment can be used, and a pigment classified as a pigment in the dye index (published by The Society of Dyers and Colourists) can be cited.

For example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, Yellow pigments such as 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; C.I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigment; C.I. Pigment green 7, 36, 58 and other green pigment.

As the pigment (P), preferably CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, Yellow pigments such as 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI pigment green 7, 36, 58 and other green pigments, more preferably CI pigment yellow 150 , 185 and CI Pigment Green 58. By containing the above pigment, the optimization of the transmission spectrum is easy, and the light resistance and chemical resistance of the color filter become good.

The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, even more preferably from 10 to 50% by mass, based on the total amount of the solid content component. When the content of the coloring agent (A) is within the above range, the color density when the color filter is formed is sufficient, and the necessary amount of the resin (B) or the polymerizable compound (C) can be contained in the composition. A pattern with sufficient mechanical strength can be formed.

The total amount of the solid content component means the amount obtained by removing the solvent from the total amount of the colored curable resin composition. The total amount of the solid content component and the content of each component relative thereto can be measured, for example, by a known analytical method such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].

Resin [K1]: at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (Ba) (hereinafter sometimes referred to as "(Ba)") and a ring having a carbon number of 2 to 4 a copolymer of an ether structure and an ethylenically unsaturated bond monomer (Bb) (hereinafter sometimes referred to as "(Bb)"); a resin [K2]: (Ba), (Bb), and may be co-linked with (Ba) Polymerized monomer (Bc) (which is different from (Ba) and (Bb)) (hereinafter sometimes referred to as "(Bc)") copolymer; resin [K3]: copolymerization of (Ba) and (Bc) Object Resin [K4]: a resin obtained by reacting (Bb) and a copolymer of (Ba) and (Bc); a resin [K5]: reacting a copolymer of (Ba) and (Bb) with (Bc) Resin; Resin [K6]: a resin obtained by reacting a copolymer of (Ba) and (Bb) with (Bc) and further reacting with a carboxylic anhydride.

Examples of (Ba) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; and maleic acid and reversed Arogate, 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, 1,4-cyclohexene dicarboxylic acid, etc., unsaturated dicarboxylic acid; methyl-5-lower Alkene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-A Bicyclo[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 - a bicyclic unsaturated compound containing a carboxyl group such as a olefin, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl neighbor Phthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyl Unsaturated dicarboxylic acid anhydride such as tetrahydrophthalic anhydride or 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; succinic acid mono [2-(methyl) propylene oxyl An unsaturated mono[(meth)acryloxyalkylalkyl] ester of a polyvalent carboxylic acid having two or more members such as an ester or a mono[2-(methyl)acryloxyethyl) phthalate; An unsaturated acrylate or the like containing a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable in terms of the aspect of the copolymerization reactivity or the solubility of the obtained resin in an aqueous alkaline solution.

(Bb) means a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and ethylenic unsaturation A polymerizable compound of a bond. (Bb) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

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

(Bb), a monomer having an oxirane group and an ethylenically unsaturated bond; a monomer having an oxetane group and an ethylenically unsaturated bond; having a tetrahydrofuranyl group and an ethylenically unsaturated bond; Monomers, etc.

As (Bb), it is preferable to further improve the reliability of heat resistance and chemical resistance of the obtained color filter, and it is preferable that the monomer having an oxirane group and an ethylenically unsaturated bond .

Examples of (Bc) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and third (meth)acrylic acid. Butyl ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentane (meth)acrylate Ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate (in this technique) In the field, it is called "dicyclopentanyl (meth) acrylate" as a conventional name. Also, it is sometimes called "tricyclodecyl (meth) acrylate"), tricyclo(meth) acrylate [5.2.1.0 ^2,6 ]nonene-8-yl ester (referred to as "dicyclopentenyl (meth) acrylate)" in the technical field, dicyclopentyloxyethyl (meth)acrylate, (meth)acrylic acid Ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (methyl) (meth) acrylate such as benzyl acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. (hydroxy)-containing (meth) acrylate; maleic acid diethyl a dicarboxylic acid diester such as ester, diethyl fumarate or diethyl itaconate; bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo[2.2.1] hept-2- Alkene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1] Hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6- Bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo [2.2.1] Hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene 5-hydroxymethyl-5-methyl Bicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis ( a bicyclic unsaturated compound such as cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenyl maleimide, N-cyclohexylmethyleneimine, N-benzyl Isobutyleneimine, N-butylenediamine-3-butylimide imide benzoate, N-butylenediamine-4-butyleneimine Butyrate, N-butylenedimino-6-m-butyleneimine hexanoate, N-butylenediamine-3-oxenimide propionate, N- (9-acridinyl) dicarbonyl ruthenium imide such as maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, pair 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 these, in terms of copolymerization reactivity and heat resistance, styrene, vinyl toluene, N-phenyl maleimide, N-cyclohexylbutylene oxide are preferred. Amine, N-benzyl maleimide, bicyclo [2.2.1] hept-2-ene, and the like.

Examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate. Resin such as /(meth)acrylic copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/styrene /(Meth)acrylic acid copolymer, 3,4-epoxytricyclo[?.1.0 ^2.6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmethylene iodide copolymer, 3-methyl Resin such as 3-(meth)acryloxymethyloxybutane/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth)acrylate/(meth)acrylic acid copolymer Resin such as styrene/(meth)acrylic acid copolymer [K3]; resin obtained by adding (meth)acrylic acid copolymer/(meth)acrylic acid copolymer to glycidyl (meth)acrylate, A resin obtained by adding a tricyclodecyl methacrylate/styrene/(meth)acrylic acid copolymer to a glycidyl (meth)acrylate, a tricyclodecyl (meth)acrylate/(methyl) Benzyl acrylate/(meth)acrylic acid copolymer addition (methyl) a resin such as a resin obtained from glycidyl acrylate [K4]; a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate with (meth)acrylic acid; a resin such as a resin obtained by reacting a copolymer of tricyclodecyl methacrylate/styrene/glycidyl methacrylate with (meth)acrylic acid [K5]; a tricyclodecyl (meth) acrylate a resin such as a resin obtained by reacting a copolymer of glycidyl (meth)acrylate with (meth)acrylic acid and further reacting the obtained resin with tetrahydrophthalic anhydride; [K6].

As the resin (B), a resin [K1] and a resin [K2] are preferable.

Resin (B) can be referred to the method described in the "Experimental Method for Polymer Synthesis" (Dazu Takashi Publishing Co., Ltd., Chemicals, 1st Edition, 1st Printing, March 1, 1972) and in the literature. Manufactured from the cited references.

The obtained copolymer may be directly used as a solution after the reaction, and a concentrated or diluted solution may be used, or a solid (powder) may be used by reprecipitation or the like. In particular, by using the solvent contained in the color-curable resin composition of the present invention as a solvent in the polymerization, the solution after the reaction can be directly used for the preparation of the color-curable resin composition of the present invention, so that the present invention can be simplified. A manufacturing step of the inventive color-curable resin composition.

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

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

The acid value of the resin (B) is preferably from 50 to 170 mg-KOH/g, more preferably from 60 to 150 mg-KOH/g, still more preferably from 70 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be obtained, for example, by titration using a potassium hydroxide aqueous solution.

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

<Polymerizable compound (C)>

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

The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, four Pentaerythritol nine (meth) acrylate, tris(2-(methyl) propylene methoxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol Hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone Modified dipentaerythritol hexa(meth) acrylate or the like.

As the polymerizable compound having three or more ethylenically unsaturated bonds, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

The content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, even more preferably from 17 to 55% by mass, based on the total amount of the solid content component. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of formation of the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>

The polymerization initiator (D) may be any known polymerization initiator as long as it is a compound capable of generating a living radical, an acid or the like by light or heat to initiate polymerization. Examples of the polymerization initiator which generates the living radicals include an O-indenyl hydrazine compound, a phenylalkyl ketone compound, and three. A compound, a mercaptophosphine oxide compound, and a biimidazole compound.

As the O-indenyl ruthenium compound, N-benzylideneoxy-1-(4-phenylmercaptophenyl)butan-1-one-2-imine, N-benzylideneoxy group- 1-(4-Phenylnonylphenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylmercaptophenyl)-3-cyclopentylpropane- 1-keto-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethane-1 -imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxe) Pentylmethoxy)benzhydryl}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-(2-A Benzobenzyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylideneoxy-1-[9-ethyl-6-(2- Methyl benzhydryl)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF Corporation), and N-1919 (made by ADEKA Co., Ltd.) can also be used. Wherein, the O-indenyl hydrazine compound is preferably selected from the group consisting of N-benzylideneoxy-1-(4-phenylmercaptophenyl)butan-1-one-2-imine, N-benzyl hydrazine 1-(4-phenylmercaptophenyl)octane-1-one-2-imine and N-benzylideneoxy-1-(4-phenylmercaptophenyl)-3-cyclopentyl At least one of the group consisting of propan-1-one-2-imine, more preferably N-benzylideneoxy-1-(4-phenylmercaptophenyl)octane-1-one-2 - Imine. In the case of these O-fluorenyl ruthenium compounds, there is a tendency to obtain a color filter having high luminance.

As the phenylalkyl ketone compound, 2-methyl-2- Lolinyl-1-(4-methylnonylphenyl)propan-1-one, 2-dimethylamino-1-(4- Phenylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Phenyl)phenyl]butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyl Oligomerization of ethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one , α,α-diethoxyacetophenone, benzoin dimethyl ketal, and the like. Commercial products such as Irgacure (registered trademark) 369, 907, and 379 (above, manufactured by BASF Corporation) can also be used.

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

The fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF Corporation) can also be used.

As the biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-di) Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (refer to Japanese Patent Laid-Open No. Hei 6-75372, Japanese Patent Laid-Open No. Hei 6-75373, etc.), 2, 2'-double (2-Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra Alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'- Bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (refer to Japanese Patent Publication No. Sho 48-38403, Japanese Patent Laid-Open No. 62-174204 The imidazole compound in which the phenyl group of the 4, 4', 5, 5'-position is substituted with an alkoxycarbonyl group (refer to Japanese Patent Laid-Open Publication No. Hei 7-10913, etc.).

Further, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone and methyl benzoyl benzoate; , 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)diphenyl a benzophenone compound such as ketone or 2,4,6-trimethylbenzophenone; an anthracene compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine or camphorquinone; 10-butyl-2- Chloramphenicone, benzoin, methyl phenylglyoxylate, titanocene compound, and the like.

Examples of the polymerization initiator which generates an acid include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylhydrazine hexafluoroantimonate, and 4-ethyloxyl p-toluenesulfonate. Phenyldimethylhydrazine, 4-ethenyloxyphenylmethylbenzylphosphonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl p-toluenesulfonate Anthracene salts such as hydrazine, diphenylphosphonium hexafluoroantimonate, or nitrobenzyl sulfonate toluene, benzoin tosylate, and the like.

As the polymerization initiator (D), it is preferred to contain a compound selected from the group consisting of an O-indenyl hydrazine compound, a phenylalkyl ketone compound, and three A polymerization initiator which is at least one selected from the group consisting of a compound, a mercaptophosphine oxide compound, and a biimidazole compound is more preferably a polymerization initiator containing an O-indenylphosphonium compound.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total 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 high and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

<Solvent (E)>

The solvent (E) can be used as a solvent which is usually used in the field. For example, an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- in the molecule and not containing -COO-), an ether ester solvent (intramolecular inclusion - a solvent for COO- and -O-), a ketone solvent (a solvent containing -CO- in the molecule and not containing -COO-), an alcohol solvent (containing OH in the molecule and not containing -O-, -CO-, and -COO- Solvent), aromatic hydrocarbon solvent, guanamine solvent, dimethyl hydrazine.

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

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and two. Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Tetrahydrofuran, tetrahydropyran, 1,4-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether and Methyl anisole.

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

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

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

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

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

The solvent (E) is preferably an organic solvent having a boiling point of from 120 ° C to 210 ° C at 1 atm in terms 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 monomethyl ether, and diethyl ether are preferred. Glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone and N,N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N, N- Dimethylformamide, N-methylpyrrolidone, and ethyl 3-ethoxypropionate.

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 color-curable resin composition of the present invention.

The total amount of the solid content of the colored curable resin composition is preferably from 5 to 30% by mass, more preferably from 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 when the color filter is formed. The display characteristics tend to be good.

<Other ingredients>

The colored curable resin composition of the present invention may optionally contain a polymerization initiator, a leveling agent, a filler, other polymer compound, adhesion promoter, antioxidant, light stabilizer, and chain transfer agent, etc., in the technical field. Known additives.

<Method for Producing Colored Curable Resin Composition>

The colored curable resin composition of the present invention can be, for example, a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and optionally a solvent (E). The leveling agent, the polymerization starting aid and other components are prepared by mixing.

In the case where the pigment (P) is contained as the coloring agent (A), the pigment (P) is preferably partially or wholly mixed with one of the solvent (E) in advance, and is dispersed by a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. At this time, part or all of the above pigment dispersant and resin (B) may be blended as needed. The target colored curable resin composition can be prepared by mixing the remaining components in a pigment dispersion thus obtained to a specific concentration.

A dye such as a salt-forming dye may be previously dissolved in a part or all of the solvent (E) to prepare a solution.

Preferably, the solution is filtered using a filter having a pore diameter of about 0.01 to 1 μm.

It is preferred to filter the mixed color-curable resin composition by a filter having a pore diameter of 0.1 to 10 μm.

<Method of Manufacturing Color Filter>

The color filter of the present invention is formed of the above colored curable resin composition.

Examples of the method for producing a color filter from the color-curable resin composition of the present invention include a photolithography method, an inkjet method, a printing method, and the like, and a photolithography method is preferred.

The photolithography method is a method in which a colored curable resin composition is applied onto a substrate, dried, and a colored composition layer is formed, and the colored composition layer is exposed through a photomask, and the colored pattern is developed. .

In the photolithography method, a coloring coating film which is a cured product of the coloring composition layer can be formed by not using a photomask and/or developing without exposure. The color filter of the present invention may be a coating film containing a colored pattern, or may be a colored coating film.

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

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

The formation of the colored pattern by the photolithography method can be carried out using known or conventional devices or conditions. For example, it can be produced as follows.

First, the colored curable resin composition is applied onto a substrate, and dried by heating (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent and drying the mixture to obtain a smooth colored composition layer. .

Examples of the coating method include a spin coating method, a slit coating method, and a slit type-spin coating method.

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

In the case of drying under reduced pressure, it is preferably carried out at a pressure of 50 to 150 Pa at 20 to 25 °C.

The film thickness of the colored composition layer may be appropriately selected depending on the film thickness of the target color filter.

Next, for the colored composition layer, exposure is performed via a photomask for forming a target coloring pattern. The pattern on the reticle can use a pattern that matches the intended use.

As a light source for exposure, light of a wavelength of 250 to 450 nm is preferably generated. source. For example, a filter that cuts the wavelength region may be cut off for light that does not reach 350 nm, or a band pass filter that extracts the same wavelength region may be selectively extracted for light near 436 nm, near 408 nm, and near 365 nm. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

In order to uniformly illuminate the entire surface of the exposure surface with parallel rays or to accurately align the mask with the substrate on which the colored composition layer is formed, it is preferable to use an exposure apparatus such as a photomask alignment machine and a stepper.

The coloring pattern is formed on the substrate by developing the exposed coloring composition layer in contact with the developing solution. By development, the unexposed portion of the colored composition layer is dissolved in the developer to be removed. As the developer, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferred.

The concentration in the aqueous solution of the basic compound is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass. Further, the developer may also contain a surfactant.

The development method may be any one of a liquid coating method, a dipping method, and a spray method. Further, the substrate may be inclined at an arbitrary angle during development.

It is preferred to carry out water washing after development.

It is preferred to post-bake the obtained colored pattern. The post-baking temperature is preferably from 150 to 250 ° C, more preferably from 160 to 235 ° C. The post-baking time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited. In the examples, the % and the parts indicating the content or the amount used are based on mass unless otherwise specified.

In the following synthesis examples, the structure of the compound was confirmed by mass analysis (LC; model 1200 manufactured by Agilent, MASS; LC/MSD type manufactured by Agilent).

Synthesis Example 1

The following reaction was carried out under a nitrogen atmosphere.

After adding 36.3 parts of potassium thiocyanate and 160 parts of acetone to a flask equipped with a condenser and a stirring device, the mixture was stirred at room temperature for 30 minutes. To the obtained mixture, 50 parts of benzamidine chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes, and stirred at room temperature for 2 hours. After the obtained reaction mixture was cooled in an ice bath, 45.7 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise thereto, and the mixture was further stirred at room temperature for 30 minutes. After the obtained reaction mixture was cooled in an ice bath, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise, and the mixture was stirred at room temperature for 30 minutes. 35.3 parts of chloroacetic acid was added dropwise to the obtained reaction mixture at room temperature, and the mixture was heated under reflux for 7 hours. Then, after the reaction mixture was allowed to stand to room temperature, the reaction solution was poured into 120 parts of water, and thereafter, 200 parts of toluene was added and stirred for 30 minutes. The obtained mixture was allowed to stand for 30 minutes, separated into an organic layer and an aqueous layer, and an organic layer was obtained by performing a liquid separation operation. The obtained organic layer was washed with 200 parts of one equivalent of hydrochloric acid, 200 parts of water, and 200 parts of saturated brine. After adding Glauber's salt to the organic layer and stirring for 30 minutes, it was filtered to obtain a dried organic layer. The solvent of the obtained organic layer was distilled off to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C to obtain 52.0 parts of the compound of formula (B-I-1).

The following reaction was carried out under a nitrogen atmosphere.

9.3 parts of the compound represented by the formula (BI-1) and 4,4'-bis(diethylamino)benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 were placed in a flask equipped with a condenser and a stirring device. A portion and 20 parts of toluene were added, and 14.8 parts of phosphonium chloride was added and stirred at 95 to 100 ° C for 3 hours. After the obtained reaction mixture was cooled to room temperature, it was diluted with 170 parts of isopropyl alcohol. Will be diluted After the reaction solution was poured into 300 parts of saturated brine, 100 parts of toluene was added and stirred for 30 minutes. The obtained mixture was allowed to stand for 30 minutes, and as a result, it was separated into an organic layer and an aqueous layer. The organic layer was obtained by performing a liquid separation operation. The obtained organic layer was washed with 300 parts of saturated brine. After adding Glauber's salt to the organic layer and stirring for 30 minutes, it was filtered to obtain a dried organic layer. The solvent of the obtained organic layer was distilled off to obtain a blue-purple solid. The obtained blue-purple solid was dried under reduced pressure at 60 ° C to obtain 19.8 parts of the compound represented by formula (A-II-1).

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

(mass analysis) ionization mode = ESI +: m / z = 601.3 [M-Cl] ⁺

Exact Mass: 636.3

Synthesis Example 2

6.3 parts of the compound represented by the formula (A-II-1) was dissolved in 500 parts of ion-exchanged water. To the obtained mixture, 2.8 parts of 1,5-dinaphthalenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 40 ° C for 12 hours. After cooling the obtained reaction mixture to room temperature, the crystals obtained were removed by filtration, washed with ion-exchanged water, and dried at 60 ° C for 24 hours to obtain a compound represented by the formula (A-II-2). The solid is 8.8 parts.

Example 1

8.8 parts of a solid containing the compound represented by the formula (A-II-2) was dissolved in 500 parts of ion-exchanged water.

To the obtained aqueous solution, 2.2 parts of 3-aminopropylethoxy decane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 30 ° C for 12 hours. After cooling the obtained reaction mixture to room temperature, the resulting crystals were removed by filtration, washed with ion-exchanged water, and dried at 60 ° C for 24 hours to obtain a compound 11.1 represented by the formula (A2-Z2-4). Share.

Example 2

In the same manner as in the first embodiment, the salt of the formula (d-1) was used instead of the 3-aminopropylethoxy decane, and the synthesis was carried out in the same manner to obtain the formula (A2-Z1-1). Compound.

Example 3

In the same manner as in the first embodiment, the salt of the formula (d-2) was used instead of the 3-aminopropylethoxy decane, and the synthesis was carried out in the same manner to obtain the formula (A2-Z3-1). Compound.

Synthesis Example 3

19 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo(5.2.1.0 ^2,6 ]癸A mixture of alkano-9-yl esters (containing 50:50 in molar ratio) (171% by molecular weight "E-DCPA", manufactured by Daicel Co., Ltd.) was dissolved in 40 parts of propylene glycol monomethyl ether acetate. And a solution is obtained (hereinafter sometimes referred to as solution (1)).

26 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 120 parts of propylene glycol monomethyl ether acetate to obtain a solution (hereinafter sometimes referred to as solution (2)).

The flask equipped with a reflux condenser, a dropping funnel, and a stirrer was placed in a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was placed, and the mixture was heated to 85 ° C while stirring. Then, the obtained solution was added dropwise to the flask over about 5 hours. Then, the solution (2) was added dropwise over a period of about 5 hours in the flask.

After completion of the dropwise addition of the solution (2), it was kept at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (B-1)) of 43.5% of a solid content. The obtained resin (B-1) had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value of 53 mg-KOH/g in terms of solid content.

[Preparation of Colored Curable Resin Composition]

Example 4

Coloring hardenability is obtained by mixing the following coloring agent (A), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and leveling agent (F) Resin composition (1).

Coloring agent (A): 20 parts of the dye represented by the formula (A2-Z2-4); resin (B): resin (B-1) (in terms of solid content) 53 parts; polymerizable compound (C): dipentaerythritol Hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) 16 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylmercaptophenyl) octyl Alkan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 4 parts; solvent (E): 120 parts of propylene glycol monomethyl ether acetate; and 480 parts of 4-hydroxy-4-methyl-2-pentanone; and leveling agent (F): polyether modified polyoxyl oil

(Toray Silicone SH8400; manufactured by Dow Corning Toray) 0.15 parts

Example 5

Coloring hardenability is obtained by mixing the following coloring agent (A), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and leveling agent (F) Resin composition (2).

Coloring agent (A): 21 parts of the dye represented by the formula (A2-Z1-1); resin (B): resin (B-1) (in terms of solid content) 50 parts; polymerizable compound (C): dipentaerythritol Hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) 16 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylmercaptophenyl) octyl Alkan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 4 parts; solvent (E): propylene glycol monomethyl ether acetate 120 parts; 480 parts of 4-hydroxy-4-methyl-2-pentanone; and leveling agent (F): polyether modified polyoxylized oil

(Toray Silicone SH8400; manufactured by Dow Corning Toray) 0.15 parts

Example 6

Coloring hardenability is obtained by mixing the following coloring agent (A), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and leveling agent (F) Resin composition (3).

Coloring agent (A): 26 parts of the dye represented by the formula (A2-Z3-1); Resin (B): resin (B-1) (in terms of solid content) 50 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) 20 parts Polymerization initiator (D): N-benzylideneoxy-1-(4-phenylmercaptophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF Company made; O-mercaptopurine compound) 4 parts; solvent (E): propylene glycol monomethyl ether acetate 120 parts; and 4-hydroxy-4-methyl-2-pentanone 480 parts; and leveling agent ( F): Polyether modified polysiloxane oil

(Toray Silicone SH8400; manufactured by Dow Corning Toray) 0.15 parts

Comparative example 1

Coloring hardenability is obtained by mixing the following coloring agent (A), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and leveling agent (F) Resin composition (1').

Coloring agent (A): 26 parts of the dye represented by the formula (A-III-1); resin (B): resin (B-1) (in terms of solid content) 53 parts; polymerizable compound (C): dipentaerythritol Hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemical Co., Ltd.) 16 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylmercaptophenyl) octyl Alkan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 4 parts; solvent (E): propylene glycol monomethyl ether acetate 120 parts; 480 parts of 4-hydroxy-4-methyl-2-pentanone; and leveling agent (F): polyether modified polyoxylized oil

(Toray Silicone SH8400; manufactured by Dow Corning Toray) 0.15 parts

Test case

[Production of color filter]

The colored curable resin composition was applied by a spin coating method on a glass substrate (#1737; manufactured by Corning Co., Ltd.) of 2 inches, and then prebaked at 100 ° C for 3 minutes to form a colored composition layer. . After cooling, exposure was carried out using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) at an exposure amount of 150 mJ/cm ² (365 nm basis) in an atmospheric environment. Furthermore, no reticle is used. The exposed coloring composition layer was baked in an oven at 180 ° C for 20 minutes to prepare a color filter (film thickness: 2.8 μm).

[Heat resistance evaluation]

The color filter was heated at 30 ° C for 20 minutes, and the color difference (ΔEab *) before and after heating of the color filter was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS).

The color difference (ΔEab*) of the coating film obtained from each of the colored photosensitive resin compositions of Example 4, Example 5, Example 6, and Comparative Example 1 was determined. The results are shown in Table 1.

Further, regarding the color difference (ΔEab*), the smaller the value is expressed as a material having higher heat resistance.

[Industrial availability]

The color hardening resin composition containing the salt-forming dye of the present invention can provide a color filter exhibiting good heat resistance. This color filter is useful for display devices (liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.

Claims (12)

A salt-forming dye formed from a monovalent cationic dye, a divalent anionic compound, and a monovalent cationic compound having no chromogenic group. The salt-forming dye according to claim 1, which is obtained from a monovalent anionic dye formed of a monovalent cationic dye and a divalent anionic compound, and a monovalent cationic compound having no chromogenic group. The salt-forming dye according to claim 1 or 2, wherein the divalent anionic compound is an aromatic compound having two monovalent anions or a heteroaromatic compound having two monovalent anions. A salt-forming dye according to claim 3, wherein the monovalent anion is a sulfonate anion. The salt-forming dye according to claim 1 or 2, wherein the divalent anionic compound is a compound represented by formula (1-b), ^- O ₃ SR ^1b -SO ₃ ^- (1-b) (wherein R ^1b represents An aromatic hydrocarbon group having 6 to 18 carbon atoms having a substituent. The salt-forming dye according to claim 1 or 2, wherein the monovalent cationic dye is a compound represented by the formula (1-a), [In the formula (1-A), R ^1A to R ^8A each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms; -CH ₂ - may be substituted with -O-; R ^9A to R ^12A each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a 6 to 20 carbon atom which may have a substituent a hydrocarbon group, -CH ₂ - contained in an alkyl group having 1 to 20 carbon atoms may be substituted with -O-; A represents an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or may have a substituent a heteroaromatic hydrocarbon group having 2 to 10 carbon atoms]. The salt-forming dye according to claim 1 or 2, wherein the monovalent cationic compound having no chromogenic group is a substituent having at least one selected from the group consisting of a polymerizable group, a ruthenium atom and a phosphorus atom and has no significant A chromophore compound. A coloring agent comprising the salt forming dye of claim 1 or 2. A colored curable resin composition comprising the coloring agent according to claim 8, a resin, a polymerizable compound, and a polymerization initiator. A coating film formed from the colored curable resin composition of claim 9. A color filter formed of the colored curable resin composition of claim 9. A display device comprising a color filter as in claim 11.