KR101836355B1 - Salts for dyes - Google Patents

Abstract

A salt containing a cation (A) derived from a cyanine compound and an anion (B) derived from a phthalocyanine compound has a high molar extinction coefficient and is useful as a colorant for use in a color filter of a display device such as a liquid crystal display.

Description

{SALTS FOR DYES}

The present invention relates to a salt containing an anion derived from a cyanine compound and an anion derived from a phthalocyanine compound, a dye containing the salt as an active ingredient, and a coloring composition comprising the dye.

Color filters are used in display devices such as liquid crystal panels, electroluminescence panels, and plasma display panels.

As a phthalocyanine dye to be used for a color filter, as described in Japanese Patent Application Laid-Open No. Hei 8-146215, C.I. Direct Blue 86 is known.

CI. Direct Blue 86 does not necessarily satisfy the molar extinction coefficient.

The present invention provides the following [1] to [9].

[1] A salt comprising a cation (A) derived from a cyanine compound and an anion (B) derived from a phthalocyanine compound.

[2] A salt according to [1], wherein (A) is a cation represented by the formula (1) or (2).

[In the formula (1), the ring Z ¹ and the ring Z ² independently represent an aromatic ring which may have a substituent. R ¹ and R ² independently represent an aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom which may have a substituent. R ³ and R ⁴ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ³ and R ⁴ combine to form an alkanediyl group. R ⁵ and R ⁶ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ⁵ and R ⁶ combine to form an alkanediyl group. R ⁷ and R ⁸ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ⁷ and R ⁸ combine to form an alkanediyl group. X ¹ and X ² independently represent a hydrogen atom or a halogen atom. n < ₁ > represents 0 or 1;

[In the formula (2), the ring Z ³ , the ring Z ⁴ , the ring Z ⁵ and the ring Z ⁶ independently represent an aromatic ring which may have a substituent. R ⁹ and R ¹⁶ represent an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent or a hydrogen atom. R ¹⁰ and R ¹¹ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ¹⁰ and R ¹¹ combine to form an alkanediyl group. R ¹² and R ¹³ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ¹² and R ¹³ combine to form an alkanediyl group. R ¹⁴ and R ¹⁵ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ¹⁴ and R ¹⁵ combine to form an alkanediyl group. R ¹⁷ and R ¹⁸ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ¹⁷ and R ¹⁸ combine to form an alkanediyl group. R ¹⁹ and R ²⁰ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ¹⁹ and R ²⁰ combine to form an alkanediyl group. R ²¹ and R ²² independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ²¹ and R ²² combine to form an alkanediyl group. L ₁ represents an alkanediyl group having 1 to 12 carbon atoms which may have a substituent. X ³ , X ⁴ , X ⁵ and X ⁶ independently represent a hydrogen atom or a halogen atom. n ₂ and n ₃ independently represent 0 or 1;

[3] The salt according to [1], wherein (A) is a cation represented by the formula (1).

[4] The salt according to [3], wherein the ring Z ¹ and the ring Z ² are a naphthalene ring which may have a substituent independently of each other.

[5] The salt according to [3] or [4], wherein R ¹ and R ² are both n-butyl groups.

[6] The salt according to any one of [3] to [5], wherein all of R ³ to R ⁶ are methyl groups.

[7] An anion derived from a phthalocyanine compound (B) Direct Blue 86, C.I. Direct Blue 87 or C.I. A salt according to any one of [1] to [6], which is an anion derived from Acid Blue 249.

[8] A dye comprising the salt according to any one of [1] to [7] as an active ingredient.

[9] A coloring composition comprising the dye according to [8].

The anion derived from the phthalocyanine compound and the salt of the cation derived from the cyanine compound according to the present invention have a good molar extinction coefficient.

The salt of the present invention is a salt in which a cation (A) derived from a cyanine compound [hereinafter sometimes referred to as "cation (A)") and an anion derived from a phthalocyanine compound (hereinafter referred to as "anion In some cases.

The cation (A) can be selected in accordance with the color of the target color filter.

It is preferable that the cation (A) is sufficiently dissolved in a solvent. Furthermore, the cation (A) is preferably dissolved to such an extent that a pattern can be formed in a developer used for pattern formation. The cation (A) may be a cation represented by the formula (1) (hereinafter sometimes referred to as "cation (1)") or a cation represented by the formula (2) .

[In the formula (1), the ring Z ¹ and the ring Z ² independently represent an aromatic ring which may have a substituent. R ¹ and R ² independently represent an aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom which may have a substituent. R ³ and R ⁴ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ³ and R ⁴ combine to form an alkanediyl group. R ⁵ and R ⁶ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ⁵ and R ⁶ combine to form an alkanediyl group. R ⁷ and R ⁸ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ⁷ and R ⁸ combine to form an alkanediyl group. X ¹ and X ² independently represent a hydrogen atom or a halogen atom. n < ₁ > represents 0 or 1;

[In the formula (2), the ring Z ³ , the ring Z ⁴ , the ring Z ⁵ and the ring Z ⁶ independently represent an aromatic ring which may have a substituent. R ⁹ and R ¹⁶ represent an aliphatic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent or a hydrogen atom. R ¹⁰ and R ¹¹ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ¹⁰ and R ¹¹ combine to form an alkanediyl group. R ¹² and R ¹³ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ¹² and R ¹³ combine to form an alkanediyl group. R ¹⁴ and R ¹⁵ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ¹⁴ and R ¹⁵ combine to form an alkanediyl group. R ¹⁷ and R ¹⁸ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ¹⁷ and R ¹⁸ combine to form an alkanediyl group. R ¹⁹ and R ²⁰ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ¹⁹ and R ²⁰ combine to form an alkanediyl group. R ²¹ and R ²² independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ²¹ and R ²² combine to form an alkanediyl group. L ₁ represents an alkanediyl group having 1 to 12 carbon atoms which may have a substituent. X ³ , X ⁴ , X ⁵ and X ⁶ independently represent a hydrogen atom or a halogen atom. n ₂ and n ₃ independently represent 0 or 1;

Furthermore, since the cation (1) and the cation (2) all take a resonance structure, it is assumed that the cation in which the charge moves in each of the formulas (1) and (2) constitutes the salt of the present invention.

The cation (1) has a ring Z ¹ and a ring Z ² .

In the formula (1), Z ¹ and the ring Z ² independently represent an aromatic ring which may have a substituent. The aromatic ring is preferably a benzene ring or a naphthalene ring.

Examples of the substituent of the benzene ring and the naphthalene ring include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, Aliphatic hydrocarbon groups such as a pentyl group and a tert-pentyl group;

Aromatic hydrocarbon groups such as a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumene group, m-

Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy and pentyloxy;

An aryloxy group such as a phenoxy group;

An aralkyloxy group such as a benzyloxy group;

An acyloxy group such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group and benzoyloxy group;

Methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, n-propyl sulfamoyl group, di-n-propyl sulfamoyl group, isopropyl sulfamoyl group, diisopropyl sulfamoyl group, an alkylsulfamoyl group such as an n-butylsulfamoyl group and a di-n-butylsulfamoyl group;

Alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl and tert-butylsulfonyl;

A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom;

A nitro group, and a cyano group.

Furthermore, when such a substituent has a hydrogen atom, the hydrogen atom may be, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy and pentyloxy; An aryloxy group such as a phenoxy group or a benzyloxy group; Aromatic hydrocarbon groups such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumene group, m-cumene group and p- A carboxy group; Cyano; Nitro group or the like.

From the viewpoint of solubility, each of the ring Z ¹ and the ring Z ² is preferably a naphthalene ring which may have a substituent, more preferably a naphthalene ring which does not have a substituent.

In the formula (1), X ¹ and X ² independently represent a hydrogen atom or a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

R ¹ and R ² independently represent an aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom which may have a substituent.

Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a vinyl group, an ethynyl group, a propyl group, an isopropyl group, an isopropenyl group, a 1-propenyl group, a 2-propenyl group, Butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methyl Pentyl group, 2-penten-4-onyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group and octyl group.

Examples of the substituent in the aliphatic hydrocarbon group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a xylyl group, a mesityl group, an o-cumene group, And the like;

Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, phenoxy and benzyloxy;

A halogen group such as a fluoro group, a chloro group, a bromo group or an iodo group;

Even a carboxy group, a nitro group and a cyano group can be mentioned.

R ¹ and R ² are preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms which does not have a substituent, more preferably an alkyl group having 1 to 4 carbon atoms having no substituent, and still more preferably an n-butyl group. R ¹ and R ² are preferably the same group. When R ¹ and R ² are the same group, the molar extinction coefficient tends to be better.

R ³ and R ⁴ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ³ and R ⁴ combine to form an alkanediyl group. R ⁵ and R ⁶ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ⁵ and R ⁶ combine to form an alkanediyl group. R ⁷ and R ⁸ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ⁷ and R ⁸ combine to form an alkanediyl group.

Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a vinyl group, an ethynyl group, a propyl group, an isopropyl group, an isopropenyl group, a 1-propenyl group, a 2-propenyl group, Butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methyl Pentyl group, 2-penten-4-onyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group and octyl group.

Examples of the substituent in the aliphatic hydrocarbon group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, , An alkoxy group such as a benzyloxy group;

A halogen group such as a fluoro group, a chloro group, a bromo group or an iodo group;

Even a carboxy group, a nitro group and a cyano group can be mentioned.

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- , And hexane-1,6-diyl group.

When R ³ to R ⁸ each independently represent an aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom which may have a substituent, it is preferably an alkyl group having 1 to 3 carbon atoms, which may have a substituent, A methyl group which may have a substituent, and still more preferably a methyl group which does not have a substituent. R ³ and R ⁴ , R ⁵ and R ⁶ , and R ⁷ and R ⁸ are preferably the same group.

When R ³ and R ⁴ are bonded to form an alkanediyl group having 1 to 12 carbon atoms, the alkanediyl group is preferably an alkanediyl group having 4 to 7 carbon atoms, more preferably a pentan-1, 5-di to be.

When R ⁵ and R ⁶ are bonded to form an alkanediyl group having 1 to 12 carbon atoms, the alkanediyl group is preferably an alkanediyl group having 4 to 7 carbon atoms, more preferably a pentan-1, 5-di to be.

Examples of the hydrocarbon ring including the alkanediyl group include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring. The hydrocarbon ring may have a substituent. Specific examples of the substituent include an alkyl group having 3 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

When R ⁷ and R ⁸ are bonded to form an alkanediyl group having 1 to 12 carbon atoms, the alkanediyl group is preferably an alkanediyl group having 3 to 5 carbon atoms, more preferably a propan-1, 5-di It is a diary.

Examples of the hydrocarbon ring containing the alkanediyl group include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, and a cycloheptene ring. The hydrocarbon ring may have a substituent. Specific examples of the substituent include alkyl groups having three or more carbon atoms such as methyl, ethyl, n-propyl, and isopropyl groups.

n ₁ is 0 or 1, and preferably 0.

The cation (2) has a ring Z ³ , a ring Z ⁴ , a ring Z ⁵ and a ring Z ⁶ .

In the formula (2), the ring Z ³ , the ring Z ⁴ , the ring Z ⁵ and the ring Z ⁶ independently represent an aromatic ring which may have a substituent. The aromatic ring is preferably a benzene ring or a naphthalene ring.

Examples of the substituent of the benzene ring and the naphthalene ring include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, Aliphatic hydrocarbon groups such as a pentyl group and a tert-pentyl group;

Aromatic hydrocarbon groups such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumene group, m-cumene group and p-

Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy and pentyloxy;

An aryloxy group such as a phenoxy group;

An aralkyloxy group such as a benzyloxy group;

An acyloxy group such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group and benzoyloxy group;

Methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, n-propyl sulfamoyl group, di-n-propyl sulfamoyl group, isopropyl sulfamoyl group, diisopropyl sulfamoyl group, an alkylsulfamoyl group such as an n-butylsulfamoyl group and a di-n-butylsulfamoyl group;

Alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl and tert-butylsulfonyl;

A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom;

A nitro group, and a cyano group.

Furthermore, when such a substituent has a hydrogen atom, the hydrogen atom may be, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy and pentyloxy; An aryloxy group such as a phenoxy group or a benzyloxy group; Aromatic hydrocarbon groups such as phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumene group, m-cumene group and p- A carboxy group; Cyano; Nitro group or the like.

From the viewpoint of solubility, the ring Z ³ , the ring Z ⁴ , the ring Z ⁵ and the ring Z ⁶ are each preferably a naphthalene ring which may have a substituent, and more preferably a naphthalene ring which does not have a substituent.

In the formula (2), X ³ , X ⁴ , X ⁵ and X ⁶ independently represent a hydrogen atom or a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

R ⁹ and R ¹⁶ independently represent an aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom which may have a substituent.

Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a vinyl group, an ethynyl group, a propyl group, an isopropyl group, an isopropenyl group, a 1-propenyl group, a 2-propenyl group, Butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methyl Pentyl group, 2-penten-4-onyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group and octyl group.

Examples of the substituent in the aliphatic hydrocarbon group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a xylyl group, a mesityl group, an o-cumene group, And the like;

Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, phenoxy and benzyloxy;

A halogen group such as a fluoro group, a chloro group, a bromo group or an iodo group;

Even a carboxy group, a nitro group and a cyano group can be mentioned.

R ⁹ and R ¹⁶ are preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms which does not have a substituent, more preferably an alkyl group having 1 to 4 carbon atoms having no substituent, and still more preferably an n-butyl group. R ⁹ and R ¹⁶ are preferably the same group. When R ⁹ and R ¹⁶ are the same group, the molar extinction coefficient tends to be better.

R ¹⁰ and R ¹¹ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ¹⁰ and R ¹¹ combine to form an alkanediyl group. R ¹² and R ¹³ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ¹² and R ¹³ combine to form an alkanediyl group. R ¹⁴ and R ¹⁵ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ¹⁴ and R ¹⁵ combine to form an alkanediyl group. R ¹⁷ and R ¹⁸ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ¹⁷ and R ¹⁸ combine to form an alkanediyl group. R ¹⁹ and R ²⁰ independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ¹⁹ and R ²⁰ combine to form an alkanediyl group. R ²¹ and R ²² independently represent an aliphatic hydrocarbon group or a hydrogen atom having 1 to 12 carbon atoms which may have a substituent, or R ²¹ and R ²² are bonded to each other to form an alkanediyl group.

Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, a vinyl group, an ethynyl group, a propyl group, an isopropyl group, an isopropenyl group, a 1-propenyl group, a 2-propenyl group, Butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methyl Pentyl group, 2-penten-4-onyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group and octyl group.

Examples of the substituent in the aliphatic hydrocarbon group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, , An alkoxy group such as a benzyloxy group;

A halogen group such as a fluoro group, a chloro group, a bromo group or an iodo group;

Even a carboxy group, a nitro group and a cyano group can be mentioned.

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- , And hexane-1,6-diyl group.

When R ¹⁰ to R ¹⁵ and R ¹⁷ to R ²² independently represent an aliphatic hydrocarbon group having 1 to 12 carbon atoms or a hydrogen atom which may have a substituent, it is preferably an alkyl group having 1 to 3 carbon atoms which may have a substituent , More preferably a methyl group which may have a substituent, still more preferably a methyl group which does not have a substituent. R ¹⁰ and R ¹¹ , R ¹² and R ¹³ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁹ and R ^20, and R ²¹ and R ²² are preferably the same as each other.

When R ¹⁰ and R ¹¹ are bonded to form an alkanediyl group having 1 to 12 carbon atoms, the alkanediyl group is preferably an alkanediyl group having 4 to 7 carbon atoms, more preferably a pentan-1, 5-di to be.

When R ¹² and R ¹³ combine to form an alkanediyl group having 1 to 12 carbon atoms, the alkanediyl group is preferably an alkanediyl group having 4 to 7 carbon atoms, more preferably a pentan-1, 5-di to be.

When R ¹⁷ and R ¹⁸ are bonded to form an alkanediyl group having 1 to 12 carbon atoms, the alkanediyl group is preferably an alkanediyl group having 4 to 7 carbon atoms, more preferably a pentan-1, 5-di to be.

When R ¹⁹ and R ²⁰ are bonded to form an alkanediyl group having 1 to 12 carbon atoms, the alkanediyl group is preferably an alkanediyl group having 4 to 7 carbon atoms, more preferably a pentan-1, 5-di to be.

Examples of the hydrocarbon ring including the alkanediyl group include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring. The hydrocarbon ring may have a substituent. Specific examples of the substituent include an alkyl group having 3 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

When R ¹⁴ and R ¹⁵ are bonded to form an alkanediyl group having 1 to 12 carbon atoms, the alkanediyl group is preferably an alkanediyl group having 3 to 5 carbon atoms, more preferably a propan-1,5-diyl group to be.

When R ²¹ and R ²² are bonded to form an alkanediyl group having 1 to 12 carbon atoms, the alkanediyl group is preferably an alkanediyl group having 3 to 5 carbon atoms, more preferably a propane-1,5-diyl group to be.

Examples of the hydrocarbon ring containing the alkanediyl group include a cyclobutene ring, a cyclopentene ring, a cyclohexene ring, and a cycloheptene ring. The hydrocarbon ring may have a substituent. Specific examples of the substituent include an alkyl group having 3 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

L ₁ represents a hydrocarbon group which may have a substituent.

Examples of the L ₁ include aliphatic hydrocarbon groups such as methylene, ethylene, vinylene, trimethylene, propylene, propenylene, tetramethylene, pentamethylene,

Aliphatic cyclic hydrocarbon groups such as cyclopentylene group, cyclohexenylene group and cyclohexadienylene group;

aromatic hydrocarbon groups such as o-phenylene group, m-phenylene group, p-phenylene group and naphthylene group; And the like.

Further, in L ₁ , when the brightness of the color filter obtained from the coloring composition containing the salt of the present invention is in a range not impaired, one or more hydrogen atoms may be replaced by an amino group, a carboxyl group, a cyano group, a nitro group, Lock period, or the like.

The above-mentioned L ₁ is preferably an alkanediyl group having 1 to 16 carbon atoms, more preferably an alkanediyl group having 1 to 10 carbon atoms, and more preferably an alkanediyl group having 3 to 8 carbon atoms, from the viewpoints of ease of synthesis and solubility in organic solvents Is more preferable.

n ₂ and n ₃ independently represent 0 or 1, preferably 0.

The cation (A) represents the cation (1) or the cation (2), but the cation (1) is preferable.

Examples of the cation (A) include the following cations.

The negative ion (B) can be selected in accordance with the color of the target color filter.

The anion (B) is preferably dissolved sufficiently in a solvent. Furthermore, it is preferable that the negative ion (B) is dissolved in a developer used for pattern formation to the extent that a pattern can be formed.

The anion (B) is preferably an anion represented by the formula (3) (hereinafter sometimes referred to as "anion (3)").

[Formula (3) indicates that n hydrogen atoms contained in the compound represented by formula (4) are substituted with -SO ₃ ^- . n is an integer of 1 or more and 4 or less]

Examples of the salt containing anion (3) include C.I. Direct Blue 86, C.I. Direct Blue 87, C.I. Acid Blue 249, and the like. Direct Blue 86 is preferred.

Examples of the anion (B) include the following anions.

Examples of the salt comprising the cation (A) and the anion (B) include the following salts.

The salt according to the present invention can be prepared by contacting the cation (A) with the anion (B) in a solvent. Specifically, the salt containing the anion (B) and the salt containing the cation (A) may be subjected to a salt exchange reaction in a solvent. At this time, it is preferable to react the salt containing the anion (B) and the salt containing the cation (A) in a molar ratio of 1: 1 to 1: 4.

The method for obtaining the target compound from the reaction mixture is not particularly limited, and various known methods may be employed. For example, the reaction mixture can be obtained by mixing the reaction mixture with an inorganic salt (e.g., salt, etc.) and water, and filtering out the precipitated crystals. It is preferable that the inorganic salt is prepared in advance of an aqueous solution of an inorganic salt, and then the reaction mixture is added to the aqueous solution. The temperature at the time of adding the reaction mixture is preferably 10 ° C to 50 ° C, more preferably 10 ° C to 40 ° C, and still more preferably 10 ° C to 25 ° C. It is also preferred that the reaction mixture is added to an aqueous solution of an inorganic salt and then stirred at the same temperature for about 0.5 to 2 hours. The crystals obtained by filtration are preferably washed with water or the like and then dried. Further, if necessary, it may be further purified by a known method such as recrystallization.

The salt of the present invention thus obtained is useful as a dye. In particular, since the salt of the present invention has a high spectral density, it is useful as a dye used for a color filter or a fiber material of a display device such as a liquid crystal display device which displays a color using reflected light or transmitted light.

The dye of the present invention is a dye containing a salt of a cation (A) and an anion (B) as an active ingredient.

It is preferable that the coloring composition of the present invention contains the dye of the present invention as a coloring agent (hereinafter also referred to as "colorant (C)"), and further contains a resin (D). More preferably, the coloring composition of the present invention further comprises a polymerizable compound (E), a polymerization initiator (F), and a solvent (G).

In addition to the dye of the present invention, the colorant (C) may further contain a dye different from the pigment and / or the dye of the present invention.

Examples of dyes that are different from the dyes of the present invention include Solvent, Acid, Basic, Reactive, Direct in the Color Index [The Society of Dyers and Colourists] , Dyes classified into Disperse or Vat, and the like. More specifically, the dyes of the following color index (CI) numbers may be mentioned, but are not limited thereto.

C.I. Solvent Yellow 25, 79, 81, 82, 83, 89;

C.I. Acid Yellow 7, 23, 25, 42, 65, 76;

C.I. Reactive Yellow 2, 76, 116;

C.I. Direct Yellow 4, 28, 44, 86, 132;

C.I. Dispulse Yellow 54, 76;

C.I. Solvent Orange 41, 54, 56, 99;

C.I. Acid Orange 56, 74, 95, 108, 149, 162;

C.I. Reactive Orange 16;

C.I. Direct Orange 26;

C.I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;

C.I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;

C.I. Acid Violet 102;

C.I. Solvent Green 1, 5;

C.I. Acid Green 3, 5, 9, 25, 28;

C.I. Basic Green 1;

C.I. Bat Green 1st.

Examples of the pigment include organic pigments or inorganic pigments commonly used in pigment-dispersed resists. Examples of the inorganic pigments include metallic compounds such as metal oxides and metal complex salts. Specific examples thereof include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, . Specific examples of the organic pigments and inorganic pigments include those classified in the Color Index (Pigment) by The Society of Dyers and Colourists. More specifically, the pigment of the color index (C.I.) number may be exemplified as follows, but is not limited thereto.

C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173 and 180;

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264;

C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;

C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58, and the like.

The content of the colorant (C) is preferably 5 to 60 mass% with respect to the solid content in the coloring composition. Here, the solid content refers to the sum of components excluding the solvent in the coloring composition.

The content of the dye of the present invention contained in the colorant (C) is preferably 3 to 100 mass%.

The dyes and pigments which are different from the dyes of the present invention may be used alone or in combination with two or more of the dyes of the present invention.

The resin (D) is not particularly limited, and any resin may be used. The resin (D) is preferably an alkali-soluble resin, more preferably a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

Specific examples of the resin (D) include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, Styrene / benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / styrene / glycidyl methacrylate copolymer, and the like.

The weight average molecular weight of the resin (D) in terms of polystyrene is preferably 5,000 to 35,000, more preferably 6,000 to 30,000.

The acid value of the resin (D) is preferably from 50 to 150, more preferably from 60 to 135.

The content of the resin (D) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, based on the solid content of the coloring composition.

The polymerizable compound (E) is not particularly limited so long as it is a compound which can be polymerized by an active radical generated from the polymerization initiator (F), an acid or the like. For example, a compound having a polymerizable ethylenically unsaturated bond and the like.

The polymerizable compound (E) is preferably a polymerizable compound having three or more polymerizable groups. As the polymerizable compound having three or more polymerizable groups, for example, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol pentaacrylate, Dipentaerythritol tetramethacrylate, dipentaerythritol hexamethacrylate, and the like. These polymerizable compounds may be used alone or in combination of two or more.

The content of the polymerizable compound (E) is preferably 5 to 65% by mass, more preferably 10 to 60% by mass, based on the solid content of the coloring composition.

Examples of the polymerization initiator (F) include an active radical generator and an acid generator. The active radical generator generates active radicals by the action of heat or light. Examples of the active radical generator include alkylphenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.

Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2- 2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, etc. have.

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

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis Azine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethynyl] -1,3,5-triazine, 2,4- Yl) ethynyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4- Ethynyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4- dimethoxyphenyl) ethynyl] 5-triazine and the like.

Specific examples of the oxime compounds include O-acyloxime compounds such as N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2- 2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- Yl] -6-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan-1-imine and the like.

Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl 1,2-bimidazole, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphaquinone, methyl phenylglyoxylate, May be used.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluene Sulfonate, benzyl (4-acetoxyphenyl) methylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfate Onium salts such as diphenyliodonium hexafluoroantimonate and diphenyl iodonium hexafluoroantimonate, and nitrobenzyl tosylates and benzoin tosylates.

These polymerization initiators may be used singly or in combination of two or more.

The content of the polymerization initiator (F) 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 (D) and the polymerizable compound (E). When the content of the polymerization initiator is within the above-mentioned range, it is preferable that the exposure time is shortened and the productivity is improved by increasing the sensitivity.

Examples of the solvent (G) include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides and the like.

Examples of the ethers include ethers such as tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, Diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol di Butyl ether, 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 the like can be mentioned ethylene glycol monobutyl ether acetate.

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

Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, Pentanone, cyclopentanone, cyclohexanone, and the like.

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

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, alkyl esters, Methyl ethyl ketone, ethyl lactate, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3- Methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, acetoacetic acid Methyl, ethyl acetoacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylacetic acid and? -Butyrolactone.

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

These solvents may be used alone or in combination of two or more.

The content of the solvent (G) in the coloring composition is preferably 70 to 95 mass%, more preferably 75 to 90 mass%, with respect to the coloring composition.

The coloring composition of the present invention may contain various additives such as a surfactant, a filler, other polymer compounds, an adhesion promoter, an antioxidant, an ultraviolet absorber, a light stabilizer and a chain transfer agent, if necessary.

The salt of the present invention is useful as a dye. Exhibits a high molar extinction coefficient and exhibits solubility in an organic solvent. Therefore, it is particularly useful as a dye used in a color filter of a display device such as a liquid crystal display device.

In addition, the coloring composition containing the salt of the present invention can be used in various display devices (for example, a known liquid crystal display device, an organic EL device, etc.) having a color filter as a part of the components thereof, It can be used in a state known to a device related to an image.

Example

The present invention will be described in more detail with reference to the following examples.

In Examples and Comparative Examples,% and parts indicating the amount of use without content are based on mass unless otherwise specified.

In the following examples, the compounds were analyzed by elemental analysis [VARIO-EL; (Manufactured by Elements Co., Ltd.).

Example 1

C.I. (S1) in which 7.8 g of Direct Blue 86 (manufactured by Tokyo Kasei Co., Ltd.) was dissolved in 20 g of N, N-dimethylformamide. Separately, a solution (t1) in which 12.5 g of the compound represented by the following formula (d-1) was dissolved in 20 g of N, N-dimethylformamide was prepared and completed. At 25 占 폚, the solution of (t1) was added dropwise to (s1) over 1 hour, and then stirred for 2 hours. Thereafter, 100 g of ion-exchanged water was added, and the mixture was further stirred for 1 hour. Subsequently, suction filtration was carried out and the filtrate was washed with 100 g of ion-exchanged water to obtain 10.5 g of a salt represented by the formula (I-1).

Identification of the compound represented by the formula (I-1);

(Elemental analysis) C: 72.3 H: 5.4 N: 9.4 Cu: 3.6 S: 3.6

Example 2

C.I. (S2) in which 7.8 g of Direct Blue 86 (manufactured by Tokyo Kasei Co., Ltd.) was dissolved in 20 g of N, N-dimethylformamide. Separately, a solution (t2) in which 6.2 g of the compound represented by the following formula (d-1) was dissolved in 20 g of N, N-dimethylformamide was prepared and completed. At 25 占 폚, the solution of (t2) was added dropwise over (s2) over 1 hour, and then stirred for 2 hours. Thereafter, 100 g of ion-exchanged water was added, and the mixture was further stirred for 1 hour. Subsequently, suction filtration was carried out and the filtrate was washed with 100 g of ion-exchanged water to obtain 6.9 g of a salt represented by the formula (I-2).

Identification of the compound represented by formula (I-2);

(Elemental analysis) C: 65.7 H: 5.1 N: 10.5 Cu: 4.7 S: 4.8

Example 3

C.I. (S3) was prepared by dissolving 2.5 g of Direct Blue 86 (manufactured by Tokyo Kasei Co., Ltd.) in 20 g of N, N-dimethylformamide. Separately, a solution (t3) in which 3.5 g of the compound represented by the following formula (d-2) was dissolved in 30 g of N, N-dimethylformamide was prepared and completed. At 25 占 폚, the solution of (t3) was added dropwise over (s3) over 1 hour, and then stirred for 2 hours. Thereafter, 150 g of ion-exchanged water was added and stirred for an additional hour. Thereafter, suction filtration was carried out and the filtrate was washed with 100 g of ion-exchanged water to obtain 3.2 g of a salt represented by the formula (I-3).

Identification of the compound represented by formula (I-3);

(Elemental analysis) C: 71.3 H: 5.4 N: 9.9 Cu: 3.7 S: 3.8

≪ Measurement of absorbance &

0.35 g of the compound was dissolved in ethyl lactate to a volume of 250 cm ³ , and 2 cm ³ of the solution was diluted with ethyl lactate to 100 cm ³ , and the solution was adjusted to a concentration of 0.028 g / L. With respect to the solution, a spectrophotometer [V-650DS; Maximum absorption wavelength (? _Max ) and molar absorptivity were measured using a spectrophotometer (manufactured by Nippon Astron Co., Ltd.) (quartz cell, optical path length: 1 cm) The results are shown in Table 1.

Example 4

[Preparation of coloring composition]

(C) Colorant: Compound (I-1): 20 parts of the compound synthesized in Example 1

(D) Resin: methacrylic acid / benzyl methacrylate copolymer (molar ratio: 30/70, weight average molecular weight: 10700, acid value: 70 mgKOH / g) 70 parts

(E) Polymerizable compound: 30 parts of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

(F) Polymerization initiator: Benzyldimethyl ketal [Irgacure (registered trademark) 651; Manufactured by Chiba Japan Co., Ltd.) 15 parts

(G) Solvent: Ethyl lactate 680 parts

To obtain a coloring composition.

Fabrication of color filters

On the glass, the coloring composition obtained above is applied by a spin coat method and the volatile components are volatilized. After cooling, light is irradiated using a quartz glass photomask having a pattern and an exposure machine. After irradiation with light, the resultant was developed with an aqueous solution of potassium hydroxide and heated in an oven at 200 DEG C to obtain a color filter.

From the results shown in Table 1, it was found that the salt of the present invention has a high molar extinction coefficient and a high spectral density. In addition, the coloring composition comprising the compound has excellent color performance and can be used for producing a high-quality color filter.

The salt of the present invention is useful as a coloring agent. Since the salt of the present invention has a high molar extinction coefficient and a high spectral density, it is useful as a coloring agent used in a color filter of a display device such as a liquid crystal display.

Claims (9)

Equation (1):

(In the formula (1), the ring Z ¹ and the ring Z ² represent naphthalene, R ¹ and R ² independently represent an alkyl group having 1 to 4 carbon atoms, and R ³ , R ⁴ , R ⁵ and R ⁶ represent independently represents an alkyl group having a carbon number of 1 to 3, R ⁷ and R ⁸ denotes a carbon number of 1 to 3 alkyl groups having no substituent, X ¹ and X ² independently represent a hydrogen atom or a halogen atom, n is ₁ 0 or 1.)
(A) represented by the formula (3):

(n represents an integer of 1 to 4).
(B). ≪ / RTI > delete delete delete The method according to claim 1,
R < ¹ > and R < ² > are n-butyl groups. The method according to claim 1,
R ³ to R ⁶ are methyl groups. The method according to claim 1,
Wherein the anion (B) is an anion derived from CI Direct Blue 86, CI Direct Blue 87 or CI Acid Blue 249. A dye comprising the salt of claim 1 as an active ingredient. 9. A coloring composition comprising the dye of claim 8.