WO2014002335A1

WO2014002335A1 - Xanthene dye for color filter, and color filter using said dye

Info

Publication number: WO2014002335A1
Application number: PCT/JP2013/001707
Authority: WO
Inventors: 良和服部; 山田　英祐; 泰斗村岡; 規敏鈴木
Original assignee: 保土谷化学工業株式会社
Priority date: 2012-06-26
Filing date: 2013-03-14
Publication date: 2014-01-03
Also published as: TWI623591B; TW201406868A; CN104412134A; JPWO2014002335A1; KR20150035820A; KR102021637B1; JP6246120B2; CN104412134B

Abstract

[Problem] To provide: a xanthene dye for a color filter, which has excellent solubility in an organic solvent and high heat resistance; and a color filter produced using the dye. [Solution] A color filter is constituted using a xanthene dye for a coloring agent for a red color filter, wherein the xanthene dye is represented by general formula (1).

Description

Xanthene dye for color filter and color filter using the dye

The present invention relates to a color filter dye and a color filter using the dye, and more particularly to a red dye having high heat resistance and excellent solubility in an organic solvent, and a color filter using the dye.

Color filters may be used for liquid crystal and electroluminescence (EL) display devices. A color filter is manufactured by laminating a colored layer on a light-transmitting substrate such as glass by a dyeing method, a pigment dispersion method, a printing method, an electrodeposition method, or the like. The materials used for the colored layer are roughly classified into pigments and dyes, and pigments that are generally excellent in heat resistance and light resistance are widely used (for example, Patent Documents 1 and 2). However, it is known that a color filter using a pigment has a depolarizing effect, so that the display contrast ratio of the color liquid crystal display device is deteriorated. In addition, since pigments are generally insoluble in a solvent, it is necessary to form fine particles and disperse them in a dispersion liquid such as a resin. It was.

Measures for solving these problems include a method of using a dye in addition to a pigment as a colorant. Since the dye is soluble in the solvent, the color filter combined with the dye has an excellent spectral characteristic as compared with the case where only the pigment is used as the colorant and has a depolarizing effect. As dyes used for color filters, xanthene dyes (for example, see Patent Documents 3 to 5) are known from the viewpoint of excellent color developability and heat resistance, and are represented by the following structural formula (I). C. I. Acid Red 289 and C.I. represented by the following structural formula (II) I. It is described that an excellent red color tone can be obtained by using a xanthene dye such as Acid Red 52 in combination with an azopyridone dye. Here, C.I. I. Means a color index.

(I)

(II)

It is also known that a blue color filter with high color contrast and high color purity can be produced by using a xanthene dye together with a phthalocyanine dye (see, for example, Patent Document 5).

Japanese Publication No. 2007-533802 JP 2011-252044 A JP 2002-265834 A JP 2002-302626 A JP-A-8-327811

However, although the conventional xanthene dyes can ensure heat resistance to some extent, the solubility in organic solvents is insufficient, and further improvement in solubility is desired.
The present invention has been made to solve the above-mentioned problems, and has excellent heat resistance and good solubility in organic solvents such as propylene glycol monomethyl ether (PGME) which is generally used in the production of color filters. An object of the present invention is to provide a xanthene dye having both of the above and a method of using it as a colorant for a red color filter.

As a result of intensive investigations to solve the above problems, the present inventors have improved the solubility of an anion having a sulfonate group and an ammonium ion in an organic solvent such as PGME while maintaining heat resistance. The present invention has been completed.

That is, the present invention has been obtained as a result of earnest research to achieve the above-mentioned object, and has the following gist.

1. A xanthene dye for a colorant of a red color filter represented by the following general formula (1).

(1)

In the formula, R ¹ to R ⁵ and R ¹¹ to R ¹⁵ may be the same or different, and may be a hydrogen atom, a hydroxyl group, a sulfonate group, a linear group having 1 to 10 carbon atoms which may have a substituent or A branched alkyl group, an optionally substituted cycloalkyl group having 3 to 10 carbon atoms, an optionally substituted linear or branched alkoxy group having 1 to 10 carbon atoms And a cycloalkoxy group having 3 to 10 carbon atoms which may have a substituent. However, any ^one of R ¹ to R ⁵ and any one of R ¹¹ to R ¹⁵ are sulfonate groups. R ⁶ to R ¹⁰ may be the same or different and each has a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent. An optionally substituted cycloalkyl group having 3 to 10 carbon atoms, an optionally substituted linear or branched alkoxy group having 1 to 10 carbon atoms, and an optionally substituted carbon Represents a cycloalkoxy group having 3 to 10 atoms. R ¹ to R ¹⁵ may be bonded to each other through a single bond between adjacent groups to form a ring. R ¹⁶ to R ¹⁹ represent a hydrogen atom or a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent. M represents an alkali metal atom, and n represents 1 or 2.

2. In the xanthene dye represented by the general formula (1), any one of R ¹ to R ⁵ and any one of R ¹¹ to R ¹⁵ is a sulfonate group, and the remaining R ¹ to R ⁵ and R ¹¹ to R ¹⁵ are each a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, or a carbon atom having 3 to 3 carbon atoms which may have a substituent. 1. a group selected from 10 cycloalkyl groups; The xanthene dye described in 1.

3. In the xanthene dye represented by the general formula (1), R ¹¹ is a sulfonate group. The xanthene dye described in 1.

4). In the xanthene dye represented by the general formula (1), at least one of R ¹⁶ to R ¹⁹ may be a linear or branched group having 4 to 20 carbon atoms which may have a substituent. Wherein the alkyl group is 1. The xanthene dye described in 1.

5. In the xanthene dye represented by the general formula (1), R ¹⁶ and R ¹⁷ are hydrogen atoms. The xanthene dye described in 1.

6). In the xanthene dye represented by the general formula (1), n is 1. The xanthene dye described in 1.

7). 1 above. Or 6. A red color filter using the xanthene dye according to any one of the above.

The xanthene dye of the present invention has high heat resistance and is excellent in solubility in an organic solvent such as PGME, and thus is useful as a colorant used for a red color filter.

Hereinafter, although embodiments of the present invention will be described in detail, the present invention is not limited to the following.

“An optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms” represented by R ¹ to R ¹⁵ in the general formula (1), “having a substituent. An optionally substituted cycloalkyl group having 3 to 10 carbon atoms ”,“ an optionally substituted linear or branched alkoxy group having 1 to 10 carbon atoms ”or“ having a substituent. A “C1-C10 linear or branched alkyl group”, “C3-C10 cycloalkyl group” in the “C3-C10 cycloalkoxy group” which may be Specific examples of the “linear or branched alkoxy group having 1 to 10 carbon atoms” or “cycloalkoxy group having 3 to 10 carbon atoms” include a methyl group, an ethyl group, a propyl group, a butyl group, and pentyl. Group Linear alkyl groups such as syl group, heptyl group, octyl group, nonyl group, decyl group; branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isooctyl group, etc .; cyclopropyl Group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, etc .; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy Linear alkoxy groups such as octyloxy group, nonyloxy group, decyloxy group; branched alkoxy groups such as isopropoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, isooctyloxy group; cyclopropoxy group , Cyclopentylo Shi, cyclohexyloxy, cycloalkoxy groups such as cyclopropylmethyl group, and the like. R ¹ to R ¹⁵ may be bonded to each other through a single bond between adjacent groups to form a ring.

“An optionally substituted linear or branched alkyl group having 1 to 10 carbon atoms” represented by R ¹ to R ¹⁵ in the general formula (1), “having a substituent. An optionally substituted cycloalkyl group having 3 to 10 carbon atoms ”,“ an optionally substituted linear or branched alkoxy group having 1 to 10 carbon atoms ”or“ having a substituent. The “substituent” in the “optionally substituted cycloalkoxy group having 3 to 10 carbon atoms” includes a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and 3 to 10 carbon atoms. A cycloalkyl group, an alkoxy group having 1 to 10 carbon atoms or a cycloalkoxy group having 3 to 10 carbon atoms, and the alkyl group or alkoxy group is a fluorine atom, a chlorine atom, a bromine atom, A haloalkyl group having 1 to 10 carbon atoms, a haloalkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 20 carbon atoms substituted with a halogen atom such as a boron atom, or Examples thereof include a condensed polycyclic aromatic group. Specifically, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; direct methyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc. Chain alkyl group; branched alkyl group such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isooctyl group; cycloalkyl group such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group; Group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group and the like linear alkoxy group; isopropoxy group, isobutoxy group, sec-butoxy Group, tert-butoxy group, isooctyloxy Branched alkoxy groups such as a group; cycloalkoxy groups such as a cyclopropoxy group, a cyclopentyloxy group, a cyclohexyloxy group, and a cyclopropylmethyloxy group; a trifluoromethyl group, a pentafluoroethyl group, a nonafluorobutyl group, and a trifluoromethoxy group Haloalkyl groups or haloalkoxy groups such as; aromatic hydrocarbon groups such as phenyl group, methoxyphenyl group, naphthyl group, biphenyl group, and anthracenyl group; and condensed polycyclic aromatic groups.

R ¹ to R ⁵ and R ¹¹ to R ¹⁵ in the general formula (1) are each a linear or branched alkyl having 1 to 10 carbon atoms which may have a hydrogen atom, a sulfonate group, or a substituent. It is preferably a linear or branched alkoxy group having 1 to 10 carbon atoms which may have a group or a substituent. However, any ^one of R ¹ to R ⁵ and any one of R ¹¹ to R ¹⁵ are sulfonate groups.

R ⁶ to R ¹⁰ in the general formula (1) have a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, or a substituent. It is preferably a linear or branched alkoxy group having 1 to 10 carbon atoms.

“The number of carbon atoms” in the “optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms” represented by R ¹⁶ to R ¹⁹ in the general formula (1) Specific examples of the 1 to 20 linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, Examples thereof include linear alkyl groups such as dodecyl group and tridecyl group; branched alkyl groups such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and isooctyl group.

As a “substituent” in “an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms” represented by R ¹⁶ to R ¹⁹ in the general formula (1) Is a hydroxyl group, a halogen atom, a linear or branched alkoxy group having 1 to 10 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms; a substituted or unsubstituted aromatic carbon atom having 6 to 20 carbon atoms Examples thereof include a hydrogen group and a condensed polycyclic aromatic group. Specifically, hydroxyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom; methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group Linear alkoxy groups such as nonyloxy group and decyloxy group; branched alkoxy groups such as isopropoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group and isooctyloxy group; cyclopropoxy group, cyclopentyloxy group, Examples include cycloalkoxy groups such as cyclohexyloxy group and cyclopropylmethyloxy group; aromatic hydrocarbon groups such as phenyl group, methoxyphenyl group, naphthyl group, biphenyl group and anthracenyl group, or condensed polycyclic aromatic groups. .

In the general formula (1), at least one of R ¹⁶ to R ¹⁹ may have a substituent from the viewpoint of solubility in a nonpolar organic solvent such as a hydrocarbon solvent. It is preferably 20 to 20 linear or branched alkyl groups.

As the alkali metal represented by M in the general formula (1), sodium or potassium is preferable, and sodium is particularly preferable.

N in the general formula (1) is 1 or 2, but 1 is more preferable.

When the xanthene dye of the present invention is used as a colorant for a red color filter, it can be used in combination with a known red pigment. The red pigment is not limited as long as it is a known pigment. I. Pigment red 177, C.I. I. Pigment red 209, C.I. I. Pigment red 242, C.I. I. Pigment red 254 and the like.

The xanthene dye represented by the general formula (1) can be synthesized by a known method such as counter ion exchange. Specifically, it can be synthesized by adding an aqueous solution of a salt composed of an amine compound and an acid to an aqueous solution of a dye whose sulfonate group is an alkali metal salt. In addition, in the case where the precipitated xanthene pigment strongly adheres and hinders stirring, an organic solvent may be mixed in order to eliminate or alleviate it. The organic solvent is not particularly limited as long as the corresponding xanthene dye has sufficient solubility, and is an aromatic hydrocarbon such as toluene and xylene; acetone, 2-butanone, 2-pentanone, 3-pentanone, etc. Ketones; esters such as ethyl acetate and butyl acetate; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, and hexanol.

Specific examples of preferred compounds as anions or ammonium ions in the xanthene dye of the present invention represented by the general formula (1) are the following (A-1) to (A-17) or (B-1) to (B- As shown in 20), the present invention is not limited to these compounds.

[Anions in xanthene dyes]

(A-1)

(A-2)

(A-3)

(A-4)

(A-5)

(A-6)

(A-7)

(A-8)

(A-9)

(A-10)

(A-11)

(A-12)

(A-13)

(A-14)

(A-15)

(A-16)

(A-17)

[Ammonium ions in xanthene dyes]

(B-1)

(B-2)

(B-3)

(B-4)

(B-5)

(B-6)

(B-7)

(B-8)

(B-9)

(B-10)

(B-11)

(B-12)

(B-13)

(B-14)

(B-15)

(B-16)

(B-17)

(B-18)

(B-19)

(B-20)

The xanthene dye of the present invention is excellent in solubility in an organic solvent, particularly in PGME. For example, the solubility in PGME is preferably 2% by weight or more, more preferably 5% by weight or more. It is particularly preferably 10% by weight or more. When considering application to a color filter, the higher the solubility, the better.

Hereinafter, embodiments of the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples.

[Synthesis of xanthene dyes]
In the reaction vessel, C.I. I. Acid Red 289 (purity 85%) 500 g, water 3.0 L, toluene 150 mL was added and heated to 80 ° C. I. Acid Red 289 was dissolved. A mixed solution of 209 g of dodecylethanolamine, 94 g of concentrated hydrochloric acid, and 1.5 L of water was added to this solution, and the mixture was stirred at 80 ° C. for 1 hour. The solution part was removed by decantation, and after adding 4.0 L of water and stirring for 30 minutes at 80 ° C., 1.7 L of methanol and 1.0 L of toluene were added to the residue, followed by stirring at 50 ° C. for 1 hour. did. After removing insolubles by filtration, the solvent was distilled off under reduced pressure to obtain 545 g (yield 99%) of xanthene dye (C-1) represented by the following structural formula.

(C-1)

[Dye Evaluation]
About the obtained xanthene dye (C-1), a thermogravimetric-differential thermal analyzer (manufactured by MAC Science, TG-DTA 200S) and a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, U-3000) were used. Then, the decomposition start point and the solubility in PGME at 25 ° C. under normal pressure were measured, and the measurement results are summarized in Table 1.

[Comparative Example 1]
For comparison, commercially available C.I. I. The decomposition start point of Acid Red 289 and the solubility in PGME at 25 ° C. under normal pressure were measured, and the measurement results are shown in Table 1.

As shown in Table 1, the xanthene dye (C-1) of the examples of the present invention has high solubility in PGME while maintaining the same heat resistance as that of the comparative compound (CI Acid Red 289). It can be seen that it is useful as a color filter dye.

The xanthene dye according to the present invention is excellent in heat resistance and solubility in an organic solvent (such as PGME), and is useful as a color filter dye.

Claims

A xanthene dye for a colorant of a red color filter represented by the general formula (1).

(1)
(Wherein R 1 to R 5 and R 11 to R 15 may be the same or different, and may be a hydrogen atom, a hydroxyl group, a sulfonate group, or a linear group having 1 to 10 carbon atoms which may have a substituent) Or a branched alkyl group, an optionally substituted cycloalkyl group having 3 to 10 carbon atoms, an optionally substituted straight chain or branched chain having 1 to 10 carbon atoms Represents an alkoxy group, a cycloalkoxy group having 3 to 10 carbon atoms which may have a substituent, provided that any one of R 1 to R 5 and any one of R 11 to R 15 is a sulfonate; R 6 to R 10 may be the same or different, and may be a hydrogen atom, a hydroxyl group, or a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent. Have a substituent An optionally substituted cycloalkyl group having 3 to 10 carbon atoms, an optionally substituted linear or branched alkoxy group having 1 to 10 carbon atoms, and an optionally substituted carbon cycloalkoxy group represents a, .R 1 ~ R 15 having the number of atoms of 3 to 10, via a single bond at the adjacent groups to each other and bonded to each other, may form a ring .R 16 ~ R 19 is A hydrogen atom or an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms, M represents an alkali metal atom, and n represents 1 or 2.
In the xanthene dye represented by the general formula (1), any one of R 1 to R 5 and any one of R 11 to R 15 is a sulfonate group, and the remaining R 1 to R 5 and R 11 to R 15 are each a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, or a carbon atom having 3 to 3 carbon atoms which may have a substituent. The xanthene dye according to claim 1, wherein the xanthene dye is a group selected from 10 cycloalkyl groups.
The xanthene dye according to claim 1, wherein in the xanthene dye represented by the general formula (1), R 11 is a sulfonate group.
In the xanthene dye represented by the general formula (1), at least one of R 16 to R 19 may be a linear or branched group having 4 to 20 carbon atoms which may have a substituent. The xanthene dye according to claim 1, wherein the xanthene dye is an alkyl group.
2. The xanthene dye according to claim 1, wherein R 16 and R 17 are hydrogen atoms in the xanthene dye represented by the general formula (1).
The xanthene dye according to claim 1, wherein n is 1 in the xanthene dye represented by the general formula (1).
A red color filter using the xanthene dye according to any one of claims 1 to 6.