TW201936796A - Coloring composition containing salt forming compound containing xanthene-based cationic dye and anionic dye, coloring agent for color filter, and color filter capable of maintaining color rendering properties and improving light resistance - Google Patents

Abstract

The invention provides a salt forming compound which includes a xanthene-based dye and has an improved solubility in organic solvents (propylene glycol monomethyl ether acetate (PGMEA) or the like) or is excellent in heat resistance. Moreover, the invention provides a coloring agent for a color filter having excellent hue adjustment for enlarging color gamut, and a color filter having excellent color rendering properties (color gamut, brightness, contrast ratio) by using a coloring composition containing the salt forming compound. The invention includes a salt forming compound including a xanthene-based cationic dye represented by the following formula (1) and an anionic dye.

Description

A coloring composition containing a salt-forming compound containing a dibenzopiperan-based cationic dye and an anionic dye, a colorant for a color filter, and a color filter

The present invention relates to a coloring composition containing a dibenzopiperan-based dye, a colorant for a color filter using the composition, and a color filter using the colorant.

In liquid crystal or electroluminescence (EL) display devices, a color filter is sometimes used. The 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, or an electrodeposition method. The coloring agent used for the colored layer is roughly classified into pigments and dyes, but pigments which are generally considered to be excellent in heat resistance and light resistance are widely used (for example, refer to Patent Documents 1 to 3). However, since pigments are generally insoluble in solvents, they exist in the form of fine particles in color filters containing resins and the like. Therefore, with regard to color filters using pigments, it is known that the transparency or color purity is affected by the reflection and scattering of the surface of pigment particles transmitted through the filter, and that they have a depolarization effect caused by reflection. The contrast ratio of the liquid crystal display device is reduced.

In order to improve the above-mentioned problem of lowering the contrast ratio, a method using only a dye as a colorant or a method using a dye and a pigment in combination has been proposed. Dyes are soluble in solvents, so color filters using dyes can suppress depolarization and have superior spectral characteristics compared to the case where only pigments are used as colorants. As a dye used for a color filter, a dibenzopiperan-based dye and the like are known in terms of having excellent color rendering properties, heat resistance, and light resistance (for example, refer to Patent Documents 4 to 8). In addition, it is described that dibenzopiperan-based dyes such as CI Acid Red 289 represented by the following formula (D-1) or CI Acid Red 52 represented by the following formula (D-2) and azopyridine are described. A ketone dye is used in combination to obtain an excellent red hue (for example, refer to Patent Document 4). Here, C.I. means color index.

[Chemical 1]

[Chemical 2]

It is also known that by using these dibenzopiperan-based dyes or derivatives thereof together with a phthalocyanine-based dye, a blue color filter having a high contrast ratio and color purity can be produced (for example, refer to Patent Documents) 6, 7). It is considered that such a color filter that uses a combination of dyes and pigments is formed by mixing two different colors to form agglomerates, and charges are caused to move immediately between light-excited dye molecules and nearby pigment molecules. The effect of mutually suppressing oxidative decomposition can maintain the color rendering property and improve the light resistance compared with a color filter made by using a dye alone.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2001-220520
[Patent Document 2] Japanese Patent Publication No. 2007-533802
[Patent Document 3] Japanese Patent Laid-Open No. 2012-12498
[Patent Document 4] Japanese Patent Laid-Open No. 2002-265834
[Patent Document 5] Japanese Patent Laid-Open No. 2012-207224
[Patent Document 6] Japanese Patent Laid-Open No. 2010-254964
[Patent Document 7] Japanese Patent Laid-Open No. 2014-12814
[Patent Document 8] Japanese Patent Laid-Open No. 2014-59538
[Patent Document 9] Japanese Patent Laid-Open No. 2015-190987

[Problems to be solved by the invention]

Generally, the display displays various colors by controlling the mixing ratio of the three primary colors of red (R), green (G), and blue (B). However, the color displayed on the display can only reproduce the color (color gamut) of the area inside the triangle surrounded by the three primary color points on the chromaticity diagram coordinates. Therefore, with the evolution of the display, the wide range of faithful colors can be reproduced The requirements for color gamut displays are high. Among the methods for expanding the color gamut, there are a method of increasing the color purity of the primary colors and a method of increasing the number of primary colors to perform multi-primary colorization. The former is a person who wants to expand the size of the triangle of the status quo and expand the area, and the latter is a person who wants to polygonize the color gamut of the triangle containing the status quo to expand the area.

In a liquid crystal display or an organic EL display, most of the RGB light is extracted from the light source of the backlight device through a color filter. At this time, by transmitting only wavelength light in a desired color gamut and cutting off (absorption) in other ranges, light of a primary color with high color purity can be obtained. Regarding the previous red pigment containing only one kind of pigment such as dibenzopiperan-based pigment, the transmittance on the long wavelength side is sufficiently large with respect to the absorption maximum wavelength, but the absorption on the short wavelength side is low and there are more, which results in Reduced color purity. Therefore, in order to improve the color purity, it is expected to develop a pigment having improved absorption from the absorption maximum wavelength to the short wavelength side (for example, Patent Document 9).

The present invention has been made in order to solve the above-mentioned problems, and an object thereof is to provide a coloring composition, a colorant for a color filter containing the coloring composition, and color rendering properties (colors) using the colorant for the color filter. Color filter with excellent color gamut, brightness, contrast ratio, etc.), wherein the coloring composition contains a dibenzopiperan dye excellent in color hue adjustment for expanding the color gamut, as a colorant for color filters, A dibenzopiperan-based dye exhibiting good solubility or dispersibility in an organic solvent (such as propylene glycol monomethyl ether acetate (PGMEA)) contained in the manufacturing process of a color filter.
[Technical means to solve the problem]

The inventors have found that by using a salt-forming compound containing a dibenzopiperan-based cationic dye and an anionic dye as a dye for a wide color gamut suitable for a color filter, the same as the previous dibenzo Compared with piperan dyes, the absorption on the short wavelength side of the absorption maximum wavelength can be improved. Furthermore, it has been found that a coloring composition containing a salt-forming compound containing the dye can synergistically improve the physical properties of each component, and has the heat resistance or solubility required for the manufacture of a color filter. It was found that a color filter having excellent color reproducibility can be obtained by using such a coloring composition, and completed the present invention.

That is, the present invention has been obtained as a result of diligent research in order to achieve the above-mentioned objects, and the following contents are the gist thereof.

A salt-forming compound comprising a dibenzopiperan-based cationic dye represented by the following general formula (1), and an anionic dye:

[Chemical 3]

[Wherein R ¹ to R ⁴ each independently represent a hydrogen atom,
A linear or branched alkyl group having 1 to 25 carbon atoms, preferably 1 to 20 carbon atoms, which may have a substituent,
A cycloalkyl group having 3 to 25 carbon atoms, preferably 3 to 20 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 25 carbon atoms, preferably 2 to 20 carbon atoms, which may have a substituent,
An aromatic hydrocarbon group having 6 to 25 carbon atoms, which may have a substituent, preferably 6 to 20 carbon atoms, or a heterocyclic group having 2 to 25 carbon atoms, preferably 2 to 20 carbon atoms, which may have a substituent,
R ¹ and R ² , or R ³ and R ⁴ may be bonded to each other to form a ring;
R ⁵ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group,
A linear or branched alkyl group having 1 to 25 carbon atoms, preferably 1 to 20 carbon atoms, which may have a substituent,
A cycloalkyl group having 3 to 25 carbon atoms, preferably 3 to 20 carbon atoms which may have a substituent,
A linear or branched alkoxy group having 1 to 25 carbon atoms, preferably 1 to 20 carbon atoms, which may have a substituent,
A cycloalkoxy group having 3 to 25 carbon atoms, preferably 3 to 20 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 25 carbon atoms, preferably 2 to 20 carbon atoms, which may have a substituent,
A fluorenyl group having 1 to 25 carbon atoms, preferably 1 to 20 carbon atoms which may have a substituent,
An amino group having 0 to 25 carbon atoms, preferably 0 to 20 carbon atoms, which may have a substituent,
An aromatic hydrocarbon group having 6 to 25 carbon atoms, which may have a substituent, preferably 6 to 20 carbon atoms, or a heterocyclic group having 2 to 25 carbon atoms, preferably 2 to 20 carbon atoms, which may have a substituent,
R ⁵ to R ⁸ may also form a ring by bonding adjacent groups to each other;
R ⁹ and R ¹⁰ each independently represent a linear or branched alkyl group having 1 to 25 carbon atoms, and preferably 1 to 20 carbon atoms, which may have a substituent;
A cycloalkyl group having 3 to 25 carbon atoms, preferably 3 to 20 carbon atoms which may have a substituent,
A linear or branched alkenyl group having 2 to 25 carbon atoms, preferably 2 to 20 carbon atoms, and an aromatic group having 6 to 25 carbon atoms, preferably 6 to 20 carbon atoms, which may have substituents A group hydrocarbon group or a heterocyclic group having 2 to 25 carbon atoms, preferably 2 to 20 carbon atoms, which may have a substituent,
R ⁹ and R ¹⁰ may be bonded to each other to form a ring;
X represents an anionic dye,
a represents an integer from 1 to 6, and b represents an integer from 1 to 6;
Among them, a and b are selected so that the general formula (1) becomes charge-neutral as a whole].

2. A salt-forming compound, wherein in the general formula (1), X is an anionic dye having a sulfonic acid group.

3. A salt-forming compound, wherein in the general formula (1), X is an anionic dye having two or more sulfonic acid groups.

4. A salt-forming compound, wherein in the general formula (1), X is an azo dye.

5. A salt-forming compound, wherein in the general formula (1), X is an azo dye having two or more sulfonic acid groups.

6. A salt-forming compound, wherein a decomposition initiation temperature of the salt-forming compound is in a range of 250 to 400 ° C.

7. A salt-forming compound, wherein the solubility of the salt-forming compound in propylene glycol monomethyl ether acetate (PGMEA) at 25 ° C ± 2 ° C is 2% by weight or more.

8. A salt-forming compound, wherein the ratio of the transmitted light in the ultraviolet-visible transmission spectrum of the above-mentioned salt-forming compound to the maximum absorption wavelength to 300 nm is 60% or less.

9. A coloring composition comprising the salt-forming compound described above.

10. A colorant for a color filter, comprising the coloring composition.

A color filter using the colorant for a color filter described above.
[Effect of the invention]

The coloring composition containing a salt-forming compound containing a dibenzopiperan-based cationic dye and an anionic dye of the present invention is excellent in heat resistance or solubility and is useful as a colorant for a color filter. In addition, a color filter can be produced by using this colorant to increase the color gamut by increasing the color purity.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the gist thereof.

The salt-forming compound containing a dibenzopiperan-based cationic dye represented by the general formula (1) and an anionic dye includes a dibenzopiperan-based cationic dye represented by the following general formula (2), and An anionic dye. In the general formula (1), a represents the number of dibenzopiperan-type cationic dyes represented by the following general formula (2), and represents an integer of 1 to 6. In the general formula (1), b represents the number of anionic dyes represented by X, and represents an integer of 1 to 6. In the case where X is a monovalent anionic dye, a and b are equal, or a = b = 1. When X is a divalent anionic dye, as a = 2, b = 1, etc., a is twice the value of b. In the case where X is an anionic dye having a trivalent or higher value, a is a value of 3 or more, and b is 1 or 2 so that the whole becomes a charge neutrality. It is important that a and b are selected so that the general formula (1) becomes charge-neutral as a whole. The dibenzopiperan-based cationic dye may be a cationic dye or a plurality of cationic dyes having different structures from each other. Similarly, X may be a monovalent anionic dye, a mixture of a plurality of monovalent anionic dyes, or a mixture of anionic dyes having different valences. In this way, even in the case where the dibenzopiperan-based cationic dye and the cationic dye represented by X are a mixture, the charge becomes neutral as a whole, a represents an integer of 1 to 6, and b represents 1 to 6 Integer.

Hereinafter, the compound of the dibenzopiperan-type cationic dye represented by General formula (2) is demonstrated.

[Chemical 4]

In the general formula (2), as the "linear or branched alkyl group having 1 to 25 carbon atoms, preferably 1 to 20 carbon atoms which may have a substituent" represented by R ¹ to R ¹⁰ , "A linear or branched alkyl group having 1 to 25 carbon atoms, preferably 1 to 20 carbon atoms", specifically, methyl, ethyl, propyl, butyl, pentyl, and hexyl , Heptyl, octyl, nonyl, decyl and other linear alkyl groups; isopropyl, isobutyl, second butyl, third butyl, isooctyl and other branched alkyl groups.

In the general formula (2), the "cyclic carbon number of 3 to 25, preferably 3 to 20 carbon atoms which may have a substituent" represented by R ¹ to R ¹⁰ represents a "carbon number of 3 to 25, A cycloalkyl group of 3 to 20 is preferable ", and specific examples include cycloalkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.

In the general formula (2), as the "linear or branched alkenyl group having 2 to 25 carbon atoms, preferably 2 to 20 carbon atoms which may have a substituent" represented by R ¹ to R ¹⁰ , "A linear or branched alkenyl group having 2 to 25 carbon atoms, preferably 2 to 20 carbon atoms" includes vinyl, 1-propenyl, allyl, 1-butenyl, 2- Butenyl, 1-pentenyl, 1-hexenyl, isopropenyl, isobutenyl, or a linear or branched alkenyl group formed by a plurality of these alkenyl bonds.

In the general formula (2), as the "aromatic hydrocarbon group having 6 to 25 carbon atoms, preferably 6 to 20 carbon atoms which may have a substituent" represented by R ¹ to R ¹⁰ , or "carbon atoms which may have a substituent""Aromatic hydrocarbon group having 6 to 25 carbon atoms, preferably 6 to 20" in the "heterocyclic group having 2 to 25, preferably 2 to 20" or "2 to 25 carbon atoms, preferably 2""A heterocyclic group of 20" includes, specifically, phenyl, naphthyl, biphenyl, anthryl, phenanthryl, fluorenyl, indenyl, fluorenyl, bitriphenyl, fluorenyl, and the like Aromatic hydrocarbon group (or condensed polycyclic aromatic group);
Pyridyl, pyrimidinyl, tris Base, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, quinolinyl, isoquinolyl, naphthyridinyl, indolyl, benzimidazolyl, carbazolyl, carbolinyl, acrylyl Morpholinyl, furyl, benzofuranyl, dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, Oxazolyl, benzo Heterocyclic groups (or heteroaromatic hydrocarbon groups) such as oxazolyl, thiazolyl, and benzothiazolyl.

In the general formula (2), R ¹ to R ¹⁰ represent “a linear or branched alkyl group having 1 to 25 carbon atoms, preferably 1 to 20 carbon atoms having a substituent” or “having The "substituent" in the linear or branched alkenyl group having 2 to 25 carbon atoms, preferably 2 to 20 carbon atoms in the substituent, specifically includes:
Halogen atoms such as fluorine, chlorine, bromine, and iodine; nitro; cyano;
Cycloalkyl groups having 3 to 19 carbon atoms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl;
Straight chain with 1 to 19 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decoxy, etc. Alkoxy; isopropoxy, isobutoxy, second butoxy, third butoxy, isooctyloxy and the like; branched alkoxy having 3 to 19 carbon atoms;
Cycloalkoxy having 3 to 19 carbon atoms such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy;
Formamyl, ethylamyl, propylamyl, propenyl, benzamyl and the like having 1 to 19 carbon atoms;
Methylamino, dimethylamino, ethylamino, diethylamino, propylamino, dipropylamino, cyclohexylamino, dicyclohexylamino, phenylamino, diphenyl Amine groups such as amino groups having 1 to 19 carbon atoms;
Amidino groups such as acetamido having 1 to 19 carbon atoms;
Aromatic hydrocarbon groups or condensed polycyclic aromatic groups having 6 to 19 carbon atoms, such as phenyl, naphthyl, biphenyl, anthryl, phenanthryl, fluorenyl, bitriphenyl, indenyl, and fluorenyl;
Pyridyl, pyrimidinyl, tris Base, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, quinolinyl, isoquinolyl, naphthyridinyl, indolyl, benzimidazolyl, carbazolyl, carbolinyl, acridinyl, Morpholinyl, furyl, benzofuranyl, dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, Oxazolyl, benzo A heterocyclic group having 2 to 19 carbon atoms, such as an oxazolyl group, a thiazolyl group, and a benzothiazolyl group, and the like. When the "substituent" includes a carbon atom, its carbon atom is not included in the above-mentioned "carbon number 1 to 25, preferably 1 to 20", "carbon number 2 to 25, preferably 2" -20 "," 3 to 25 carbon atoms, preferably 3 to 20 ", and" 6 to 25 carbon atoms, preferably 6 to 20 ". These "substituents" may include only one or a plurality of them, and when a plurality of "substituents" are included, they may be the same as or different from each other. These "substituents" may further have the substituents exemplified above.

In the general formula (2), "cycloalkyl having 3 to 25 carbon atoms, preferably 3 to 20 carbon atoms having substituents" and "carbon atoms having 6 carbon atoms having substituents" represented by R ¹ to R ¹⁰ "25, preferably 6 to 20 aromatic hydrocarbon groups" or "substituents" in "heterocyclic groups having 2 to 25 carbon atoms, preferably 2 to 20 carbon atoms having substituents", specifically, may be Examples: halogen atoms such as fluorine, chlorine, bromine, and iodine; nitro; cyano;
Methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and other straight-chain alkyl groups having 1 to 18 carbon atoms;
Branched alkyl groups having 3 to 18 carbon atoms such as isopropyl, isobutyl, second butyl, third butyl, and isooctyl;
Cycloalkyl groups having 3 to 18 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl;
1 to 18 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decoxy, etc. Alkoxy groups; isopropyloxy, isobutoxy, second butoxy, third butoxy, isooctyl and other branched alkoxy groups having 3 to 18 carbon atoms;
Cycloalkoxy having 3 to 18 carbon atoms such as cyclopropoxy, cyclobutoxy, cyclopentyloxy and cyclohexyloxy;
Vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, isopropenyl, isobutenyl, or multiple such alkenyl groups A straight or branched alkenyl group having 2 to 18 carbon atoms;
Formamyl, ethylamyl, propylamyl, propenyl, benzamyl and the like having 1 to 18 carbon atoms;
Methylamino, dimethylamino, ethylamino, diethylamino, propylamino, dipropylamino, cyclohexylamino, dicyclohexylamino, phenylamino, diphenyl Amine groups such as amino groups having 1 to 18 carbon atoms;
Amidino groups such as acetamido having 1 to 18 carbon atoms;
Aromatic hydrocarbon groups or condensed polycyclic aromatic groups having 6 to 14 carbon atoms such as phenyl, naphthyl, biphenyl, anthryl, phenanthryl, indenyl, and fluorenyl groups;
Pyridyl, pyrimidinyl, tris Base, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, quinolinyl, isoquinolyl, naphthyridinyl, indolyl, benzimidazolyl, carbazolyl, carbolinyl, acridinyl, Morpholinyl, furyl, benzofuranyl, dibenzofuranyl, thienyl, benzothienyl, dibenzothienyl, Oxazolyl, benzo A heterocyclic group having 2 to 18 carbon atoms, such as an oxazolyl group, a thiazolyl group, and a benzothiazolyl group, and the like. When the "substituent" includes a carbon atom, the carbon atom is not included in the above-mentioned "2 to 25 carbon atoms, preferably 2 to 20", and "3 to 25 carbon atoms, preferably 3""20","6 to 25 carbon atoms, preferably 6 to 20". These "substituents" may include only one or a plurality of them, and when a plurality of "substituents" are included, they may be the same as or different from each other. These "substituents" may further have the substituents exemplified above.

Examples of the "halogen atom" represented by R ⁵ to R ⁸ in the general formula (2) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The "halogen atom" is preferably a fluorine atom or a chlorine atom.

In the general formula (2), "a linear or branched alkoxy group having 1 to 25 carbon atoms, and preferably 1 to 20 carbon atoms which may have a substituent" represented by R ⁵ to R ⁸ ; "A cycloalkoxy group having 3 to 25 carbon atoms which may have a substituent, preferably 3 to 20", a "fluorenyl group having 1 to 25 carbon atoms, which may have a substituent", or "Straight-chain or branched-chain alkoxy group having 1 to 25 carbon atoms, preferably 1 to 20 carbon atoms" which may have a substituent having 0 to 25 carbon atoms, preferably 0 to 20 carbon atoms Group "," cycloalkoxy group having 3 to 25 carbon atoms, preferably 3 to 20 "," fluorenyl group having 1 to 25 carbon atoms, preferably 1 to 20 "or" 0 to 25 carbon atoms " , Preferably an amino group of 0 to 20 ", specifically, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy Straight-chain alkoxy groups such as, nonyloxy, decoxy; etc .; branched-chain alkoxy groups such as isopropoxy, isobutoxy, second butoxy, third butoxy, isooctyloxy base;
Cycloalkoxy, such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, cyclohexyloxy;
Formamyl, ethenyl, propionyl, propenyl, benzyl and the like;
Unsubstituted amino groups; methylamino, dimethylamino, ethylamino, diethylamino, propylamino, methylpropylamino, dipropylamino, di-tert-butyl Amino groups such as aminoamino, cyclohexylamino, dicyclohexylamino, phenylamino, diphenylamino, and the like.

In the general formula (2), R ⁵ to R ⁸ represent “a linear or branched alkoxy group having 1 to 25 carbon atoms, preferably 1 to 20 carbon atoms having a substituent”, and “ "Cycloalkoxy having 3 to 25 carbon atoms having substituents, preferably 3 to 20", "fluorenyl group having 1 to 25 carbon atoms having substituents, preferably 1 to 20", or "may The "substituent" in the "amino group having 0 to 25 carbon atoms, preferably 0 to 20 carbon atoms having a substituent", specifically, includes:
Halogen atoms such as fluorine, chlorine, bromine, and iodine; nitro; cyano;
Cycloalkyl groups having 3 to 19 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, and cyclooctyl;
Straight chain with 1 to 17 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decoxy, etc. Alkoxy; isopropoxy, isobutoxy, second butoxy, third butoxy, isooctyl and other branched alkoxy groups having 1 to 17 carbon atoms;
Cycloalkoxy having 3 to 19 carbon atoms such as cyclopropoxy, cyclobutoxy, cyclopentyloxy, and cyclohexyloxy;
Vinyl, 1-propenyl, allyl, 1-butenyl, 2-butenyl, 1-pentenyl, 1-hexenyl, isopropenyl, isobutenyl, or multiple such alkenyl groups A straight or branched alkenyl group having 2 to 19 carbon atoms;
Formamyl, ethylamyl, propylamyl, propenyl, benzamyl and the like having 1 to 19 carbon atoms;
Methylamino, dimethylamino, ethylamino, diethylamino, propylamino, dipropylamino, cyclohexylamino, dicyclohexylamino, phenylamino, diphenyl Amine groups such as amino groups having 1 to 19 carbon atoms;
Ethylamino groups such as acetamido;
An aromatic hydrocarbon group having 6 to 19 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, or a condensed polycyclic aromatic group having 6 to 19 carbon atoms, and the like. When the "substituent" includes a carbon atom, its carbon atom is not included in the above-mentioned "carbon number 1 to 25, preferably 1 to 20", "carbon number 3 to 25, preferably 3""20","0 to 25 carbon atoms, preferably 0 to 20". These "substituents" may include only one or a plurality of them, and when a plurality of "substituents" are included, they may be the same as or different from each other. These "substituents" may further have the substituents exemplified above.

In the general formula (2), R ¹ to R ^{4 are} preferably a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, and 5 carbon atoms which may have a substituent. A cycloalkyl group of 12 is more preferably a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent.

In the general formula (2), the combination of R ¹ and R ² may be the same as or different from the combination of R ³ and R ⁴ .

In the general formula (2), R ¹ and R ² each other, R ³ and R ⁴ each other, adjacent groups among R ⁵ to R ⁸ , or R ⁹ and R ¹⁰ may be bonded to each other to form a ring. These rings can also form a ring by a single bond, or by bonding through any of the nitrogen, oxygen, or sulfur atoms. The ring formed in this case is preferably a five-member ring or a six-member ring.

In the general formula (2), R ⁵ to R ^{8 are} preferably a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, or may have The linear or branched alkoxy group having 1 to 20 carbon atoms of the substituent is more preferably a hydrogen atom.

In the general formula (2), R ⁹ and R ^{10 are} preferably a hydrogen atom, a halogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent, and may have a substituent. An aromatic hydrocarbon group having 6 to 20 carbon atoms in the group or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent.

For the compound represented by the general formula (2), for example, a 3,6-dichlorospiro [9H-dibenzopiperan-9,3 '-[3H] [2, 1] Benzanothiol] 1 ', 1'-dioxide (or dichlorosulfurane) derivative is synthesized as a starting material. By the method of reacting an amine compound containing a nitrogen atom, a heterocyclic compound, etc. under an appropriate temperature condition by dissolving a raw material in an arbitrary solvent such as N-methylpyrrolidone (NMP), the following general formula is obtained: The intermediate represented by Formula (4). (For example, refer to Patent Document 8 and the like). Then, by reacting an intermediate represented by the general formula (4) with thionyl chloride in a solvent and then reacting with an amine, a dibenzopiperan-based cationic dye represented by the general formula (2) can be synthesized.

[Chemical 5]

In the general formulae (3) and (4), R ¹ to R ⁸ have the same definitions as those in the general formula (2).

In the method for synthesizing a dibenzopiperan-based cationic dye represented by the general formula (2), in the case where the precipitated dibenzopiperan-based dye is firmly adhered and the stirring is prevented, in order to eliminate or relax it, Can mix organic solvents. The mixed organic solvent is not particularly limited as long as it has sufficient solubility of the corresponding dibenzopiperan-based dyes, and the following solvents can be used alone or in combination: aromatic hydrocarbons such as toluene and xylene; acetone , 2-butanone, 2-pentanone, 3-pentanone and other ketones; ethyl acetate, butyl acetate and other esters; methanol, ethanol, propanol, isopropanol, butanol, pentanol, hexanol, etc. Alcohols, etc.

The dibenzopiperan-based cationic dye represented by the general formula (2) can be obtained by purifying the product obtained by the above-mentioned synthesis method as needed: purification by column chromatography; using silica gel, Adsorption and purification of activated carbon, activated clay, etc .; well-known purification using solvent dispersion or recrystallization, crystallization, salting out, etc. The solvent used for these purification methods is not particularly limited, and the following solvents can be used alone or in combination: alcohols such as water, methanol, ethanol; methane halides such as dichloromethane, chloroform; toluene, etc.

Specific examples of the preferred compounds of the dibenzopiperan-based cationic dye of the present invention represented by the general formula (2) are shown in the following formulae (A-1) to (A-23), but the present invention is not limited to these Such compounds. In addition, in the following structural formula, a part of hydrogen atoms are omitted and described. In addition, even when stereoisomers exist, the planar structural formula is described. Furthermore, the anion part is omitted.

[Chemical 6]

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[Chemical 28]

The dibenzopiperan-based cationic dye represented by the general formula (2) of the present invention may be used alone or in combination (for example, mixed) of two or more different molecular structures. In this case, the Among the weight-to-weight ratios of the piperan-based cationic dyes, the smallest one is a dibenzopiperan-based cation dye having a weight-to-weight ratio of 0.1 to 50% by weight. That is, among the two or more dibenzopiperan-based cationic dyes, the smallest amount of one dibenzopiperan-based cationic dye accounts for 0.1 to 50% by weight of the two or more dibenzopiperan dyes as a whole. The type of the dibenzopiperan-based cationic dye is preferably one or two.

The salt-forming compound containing a dibenzopiperan-based cationic dye represented by the general formula (1) and an anionic dye includes an anionic dye represented by "X". In the general formula (1), as the "X" indicated by the "anionic dye" Specific examples include: having a sulfonic acid group (-SO ₃ ^-), carboxyl (-COO ^-) groups of the anionic dyes and the like, An anionic dye having a sulfonic acid group is preferred.

In the general formula (1), the “anionic dye having a sulfonic acid group” represented by “X” is not particularly limited. In view of the gist of the present invention, a dye that increases the absorption on the short wavelength side of the maximum wavelength, An anionic dye having an absorption maximum wavelength longer than the dibenzopiperan dye represented by the general formula (2) and having an absorption region on the short wavelength side can be used. It is preferable to use an anionic dye having a maximum absorption wavelength at a shorter wavelength side of 10 to 250 nm than the absorption maximum wavelength of the dibenzopiperan-based dye represented by the general formula (2). Furthermore, an anionic dye having an absorption maximum wavelength at a short wavelength side of 20 to 200 nm is preferable.

In the general formula (1), the "anionic dye having a sulfonic acid group" represented by "X" can be used for molecular design and synthesis in such a manner as to obtain an arbitrary absorption spectrum. Synthetic methods can be used to the extent that modern chemical technology can achieve. In the introduction of a sulfonic acid group, sulfuric acid is generally used, but it is not limited to this method and can be used. The number of sulfonic acid groups is not particularly limited as long as it is one or more. However, if an anionic dye having a large number of sulfonic acid groups is used, the ratio of the anionic dye to the dibenzopiperan-based dye represented by the general formula (2) is reduced, and it is difficult to obtain a sufficient effect of short-wavelength side absorption. In order to obtain the synergistic effect of solubility or heat resistance through ionic or hydrogen bonding, the number of sulfonic acid groups is preferably 1 to 3, more preferably 2 or 3, and even more preferably 2.

From the viewpoints of production cost, ease of molecular design, and variety of types, in the general formula (1), as the "anionic dye having a sulfonic acid group" represented by "X", an azo dye can be used. Generally, an azo dye can be obtained by reacting a corresponding amine component with nitrous acid to prepare a diazonium salt and reacting with an arbitrary coupling agent component, but it is not limited to this method and can be used.

In the general formula (1), a commercially available product can be used as the anionic dye of the present invention represented by "X". Specifically, Acid Orange 5, Acid Yellow 3, Acid Yellow 23, Acid Yellow 36, Direct Red 37 (all manufactured by Tokyo Chemical Industry Co., Ltd.) or a composition containing these anionic dyes as a main component are commercially available. These can be used directly to prepare the coloring composition of the present invention, and the coloring composition of the present invention can also be prepared by using the same method as the above-mentioned method for purifying dibenzopiperan dyes.

In the general formula (1), specific examples of the preferable compound of the anionic dye of the present invention represented by "X" are shown in the following formulae (B-1) to (B-27), but the present invention is not limited to Such compounds. In addition, in the following structural formula, a part of hydrogen atoms are omitted and described. In addition, even when stereoisomers exist, the planar structural formula is described. Furthermore, the case of a cationic part shows sodium.

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In the general formula (1), one type of the anionic dye represented by "X" may be used, or two or more types having different molecular structures may be used in combination.

By performing thermogravimetric / differential thermal analysis (TG-DTA) of the salt-forming compound of the present invention, the decomposition initiation temperature can be analyzed. The decomposition initiation temperature is preferably 250 ° C or higher, more preferably 300 ° C or higher, and even more preferably 360 ° C or higher. When applied to a color filter, the higher the decomposition starting temperature, the better. In addition, as the temperature corresponding to the decomposition initiation temperature, a temperature at a point in time when a sample is reduced in weight (%) after heating (for example, a 5% weight reduction temperature) may be used.

The solubility of the powder of the salt-forming compound, the coloring composition, or the colorant for a color filter of the present invention is expressed in terms of solubility, and the solubility is the ratio of the entirety of the largest amount that can dissolve the powdery substance in a specific solvent. , For example, expressed in units such as "% by weight (solvent name, temperature)". Solubility is obtained, for example, by mixing a sample in a specific solvent, stirring the solvent at a certain temperature for a certain time, and measuring the concentration of the prepared saturated solution, or by using liquid chromatography (LC) in the dissolution section. ) Or concentration measurement such as absorbance measurement.

The coloring composition contained in the coloring agent for color filters must be well dissolved or dispersed in an organic solvent containing a resin or the like in the manufacturing steps of the coloring agent for color filters and the color filter, and is therefore used as coloring. The salt-forming compound of the present invention as the pigment component contained in the composition preferably has high solubility in an organic solvent. The organic solvent is not particularly limited. Specific examples include esters such as ethyl acetate and n-butyl acetate; ethers such as diethyl ether and propylene glycol monomethyl ether (PGME); and propylene glycol monomethyl ether acetate ( PGMEA) and other ether esters; ketones such as acetone and cyclohexanone; alcohols such as methanol and ethanol; diacetone alcohol (DAA) and the like; aromatic hydrocarbons such as benzene, toluene, and xylene; N, N-dimethyl Formamides such as formamidine (DMF), N-methylpyrrolidone (NMP), and dimethylsulfinamide (DMSO). These solvents may be used alone or as a mixture of two or more. Among these, the salt-forming compound of the present invention preferably has excellent solubility in PGMEA or PGMEA, and particularly preferably has excellent solubility in PGMEA. The solubility of the salt-forming compound of the present invention in PGMEA at 25 ° C ± 2 ° C is preferably 2% by weight or more, more preferably 4% by weight or more, and even more preferably 7% by weight. In other words, at any temperature between 23 ° C and 27 ° C, the solubility of the salt-forming compound of the present invention in PGMEA is preferably 2% by weight or more, more preferably 4% by weight or more, and even more preferably 7% by weight.

As the evaluation of the color characteristics of the salt-forming compound of the present invention, ultraviolet-visible transmission spectroscopy is mainly used for the measurement. Specifically, the UV-visible transmission or absorption spectrum of a sample (which may be any of a solution, a dispersion, and a coating film) can be measured to obtain its absorption maximum wavelength. Generally, the maximum absorption wavelength in the visible region (in the range of about 400 to 700 nm) can be used. In the case of common dyes such as dyes and pigments, one or a plurality of absorption peaks are observed, and the wavelength at which the transmittance of the peak becomes the minimum value (the absorbance is the maximum value) is set as the absorption maximum wavelength. The salt-forming compound of the present invention is preferably in a region where the self-absorption maximum wavelength of the ultraviolet-visible transmission spectrum is toward the short-wavelength side to a wavelength of 300 nm, and the absorption is sufficiently large, that is, the transmittance of the wavelength region is preferably small. A specific example of the ultraviolet-visible transmission spectrum (300-700 nm) of the salt-forming compound of the present invention is shown in FIG. 1 in a schematic diagram. In the figure, at the absorption maximum wavelength to 300 nm, the amount of absorbed light (A) (equivalent to the area covered by the oblique line) and the amount of transmitted light (B) (equivalent to the area of the white portion) are used. The ratio of transmitted light in the region of the wavelength range is expressed by the formula B / (A + B). It can also be referred to as the ratio of the total amount of light transmission in the range from 300 nm to the absorption maximum wavelength to the total amount of light exposure in that range. The smaller the area of B, the better, that is, the smaller the ratio of the transmitted light of the ultraviolet-visible transmission spectrum to 300 nm, the better, and specifically, it is preferably 60% or less.

Hereinafter, the coloring composition containing the salt-forming compound containing the dibenzopiperan-type cationic dye and anionic dye represented by General formula (1) of this invention is demonstrated in detail.

The dibenzopiperan-based cationic dye, anionic dye, or a salt-forming compound containing a dibenzopiperan-based cationic dye and an anionic dye, and a coloring composition containing these compounds further include a solvent molecule, Moisture, components of molecular structure other than the dye of the present invention, and other components. Any of these can be used directly, but it is preferable to perform a refining treatment. However, no matter which purification method is used, there may be a certain percentage of impurities, but as long as it is a dye that can be manufactured in the current technical level, it can be used.

As other components in the coloring composition of the present invention, in order to improve the performance as a coloring agent for color filters, surfactants, dispersants, defoamers, leveling agents, and other coloring agents for color filters may be added. Additives mixed during the manufacture of the agent. Among them, the content rate of the additives in the coloring composition is preferably a proper amount, and it is preferably not to reduce or increase the solubility in the solvent of the coloring composition of the present invention to more than necessary, and it does not affect the manufacture of color filters. The content rate of the range of effects of other additives of the same kind used at the time. These additives can be used at any timing of the preparation of the coloring composition.

Regarding the state of the powder of the salt-forming compound, the coloring composition, or the colorant for a color filter of the present invention, the shape can be observed using an optical microscope, a scanning electron microscope (SEM), or the like. The shape of the coloring composition of the present invention is generally used in the state of a solid powder having a shape such as crystalline, microcrystalline, micropowder, flake, needle-like, granular, and the like, and is not particularly limited.

By measuring the particle size distribution, surface area, pore size distribution, and powder density of the powder of the salt-forming compound, coloring composition, or colorant for color filters of the present invention, the overall and average shape of the powder can be obtained in more detail. Information. For example, the Coulter method using resistance measurement of the electrolyte solution in which the powder is dispersed, the centrifugal sedimentation method for obtaining the Stokes effective diameter by measuring the absorbance of the powder dispersion solution, and the It is measured by laser diffraction, scattering method analysis, etc. of the radiation scattering pattern. The powder of the salt-forming compound, the coloring composition, or the colorant for a color filter of the present invention is preferably in a particle size range of 0.1 μm to several mm, but the shape of the particles depends on the manufacturing conditions or the recovery of the powder after drying. The method varies, so the specific particle size is not limited. In order to achieve higher solubility, the particle size is preferably smaller, and the central value of the particle size distribution is preferably in the range of 0.1 to 100 μm.

The spectral characteristics (transmittance, reflectance) of the salt-forming compound or the powder of the coloring composition containing the salt-forming compound of the present invention are used when a pigment is used alone as a coloring agent for a color filter, or mixed with other pigments. All situations are important, and have a direct impact on the color characteristics of the color filter. The measuring method includes a method for measuring an absorption and transmission spectrum of a solution or a dispersion, or an absorption and transmission spectrum of a film coated on a glass or a transparent resin substrate. There is also a method of directly irradiating the powder with light to measure light reflected or scattered on the surface of the particle or near the surface of the particle.

The colorant for a color filter of the present invention includes a coloring composition containing a salt-forming compound containing a dibenzopiperan-based cationic dye and an anionic dye represented by the general formula (1), and a color filter generally used Made of ingredients. A general color filter is obtained, for example, in the case of a method using a photolithography method in which a pigment such as a dye or a pigment and a resin component (including a monomer and an oligomer) are used, or The liquid prepared by solvent mixing is coated on a substrate such as glass or resin, and photopolymerized using a photomask to produce a colored pattern of a pigment-resin composite film that is soluble / insoluble in the solvent, and then heated after cleaning. In addition, in the electrodeposition method or the printing method, a coloring pattern may be produced using a mixture of a pigment and a resin or other components. Therefore, specific components in the colorant for color filters of the present invention include salt-forming compounds containing dibenzopiperan dyes and anionic dyes represented by general formula (1), other dyes, pigments, and the like. Pigments, resin components, organic solvents, and other additives such as photopolymerization initiators. In addition, you can choose from these ingredients, and you can add other ingredients as needed.

When the coloring composition containing a salt-forming compound of the present invention is used as a colorant for a color filter, it can also be used for a color filter for each color, and is preferably used as a colorant for a red color filter.

Regarding the colorant for color filters containing the coloring composition containing the salt-forming compound of the present invention, in order to adjust the color tone, other known dyes or pigments may be mixed. When it is used for a colorant for a red color filter, it is not particularly limited, and examples thereof include red pigments such as CI Pigment Red 177, CI Pigment Red 209, CI Pigment Red 242, and CI Pigment Red 254; other red colors Lake pigments; CI acid red 88, CI basic violet 10 and other red dyes. When it is used for a colorant for a blue color filter, it is not particularly limited, and examples include: CI Basic Blue 3, 7, 9, 54, 65, 75, 77, 99, 129 and other basic dyes; CI acid blue 9, 74 and other acid dyes; disperse blue 3, 7, 377 and other disperse dyes; spiro dyes; cyanine, indigo, phthalocyanine, anthraquinone, methine, triarylmethane, Yin Dan Shilin Department, Department, two Blue dyes or pigments such as dibenzopiperans; other blue dyes and lake pigments.

The mixing ratio of other pigments in the coloring composition containing the salt-forming compound or the colorant for color filters containing the coloring composition of the present invention is preferably 5 to 2000% by weight relative to the dibenzopiperan-based cationic dye. It is more preferably set to 10 to 1000% by weight. The mixing ratio of the pigment components such as dyes in the liquid color filter colorant is preferably 0.5 to 70% by weight, and more preferably 1 to 50% by weight, relative to the entire colorant.

As the resin component in the colorant for a color filter containing a coloring composition of the present invention, a known method can be used as long as it has a manufacturing method of the color filter resin film formed therefrom or properties required during use. By. Examples include acrylic resins, olefin resins, styrene resins, polyimide resins, urethane resins, polyester resins, epoxy resins, vinyl ether resins, phenol (novolac) resins, and other transparent resins. The photocurable resin or the thermosetting resin can be used in appropriate combination with these monomer or oligomer components. Moreover, it can also be used in combination with the copolymer of these resins. Regarding the content of the resin in these color filters, in the case of a liquid coloring agent, it is preferably 5 to 95% by weight, and more preferably 10 to 50% by weight.

Examples of the other additives in the colorant for a color filter containing a coloring composition of the present invention include components necessary for polymerization or hardening of a resin such as a photopolymerization initiator or a cross-linking agent, and also include: Surfactant or dispersant required to stabilize the properties of the components in the colorant for liquid color filters. These are all known to be used for manufacturing color filters, and are not particularly limited. The total amount of these additives in the solid matter component of the color filter for color filters is preferably 5 to 60% by weight, and more preferably 10 to 40% by weight.
[Example]

Hereinafter, the embodiments of the present invention will be specifically described with examples, but the present invention is not limited to the following examples. In addition, the compounds obtained in the examples were identified by ¹ H-NMR (hydrogen-1 NMR, one-dimensional nuclear magnetic resonance spectrum) analysis (nuclear magnetic resonance apparatus manufactured by Japan Electronics Co., Ltd., JNM-ECA-600 ).

[Synthesis Example 1]
In the reaction vessel, 3,6-dichlorospiro [9H-dibenzopiperan-9,3 '-[3H] [2,1] benzoxanethiol] 1', 1'-di Oxide (DCSF) 40.0 g (98.7 mmol), diethylamine 28.9 g (395 mmol), n-methylpyrrolidone (NMP) 400 mL, and stirred at 120 ° C for 5 hours. The reaction solution was put into 1200 mL of water, and concentrated hydrochloric acid was added until the pH value became 2. Furthermore, 100 g of sodium chloride was added, and salting out was performed. After the supernatant was discarded, 500 mL of chloroform was added to dissolve it, and saturated saline was added to separate the liquid. The organic layer was extracted, and after cleaning with water, the organic layer was extracted again. After adding sodium sulfate for drying, filtration was performed, and the filtrate was concentrated under reduced pressure to obtain a purple viscous oil. Hexane was added to the oil, and the mixture was refluxed under heating, and the precipitated solid was collected by filtration. The obtained solid was dried under reduced pressure to obtain 42.5 g (yield 90%) of a brown solid (A-1 intermediate).
Next, in a reaction vessel replaced with nitrogen, add 10.0 g (A-1 intermediate), N, N-dimethylformamide (DMF) 1.85 g (25.4 mmol), 100 mL of chloroform, 8.04 g of thionine chloride was heated at reflux temperature for 2 hours. The reaction solution was concentrated and placed in a reaction vessel replaced with nitrogen, dissolved in 100 mL of chloroform, and 1.24 g (16.9 mmol) of diethylamine and 3.42 g (33.8 mmol) of triethylamine were added. The reaction was continued for 4 hours. The reaction solution was washed with saturated brine, and the organic layer was extracted. Sodium sulfate was added, and it was filtered after drying. The filtrate was concentrated under reduced pressure, and the obtained purple oil was purified by column chromatography (carrier: silicone, solvent: chloroform → chloroform: methanol = 9: 1). The target component was recovered, concentrated, cleaned with hexane, and filtered to obtain a solid. The obtained solid was dried under reduced pressure to obtain a complex of a compound represented by the following formula (A-1) and a chloride anion (4.8 g, yield 40%) as a brown solid.

[Chemical 56]

[Synthesis Example 2]
Except changing the diethylamine used in Synthesis Example 1 to 51.0 g (395 mmol) of dibutylamine, the same operation was performed to obtain 54.0 g (yield 92%) of (A-2 intermediate).
Next, using (A-2 intermediate), the same reaction with thionyl chloride as in Synthesis Example 1 was performed to obtain 3.5 g of a complex of a compound represented by the following formula (A-2) and a chloride anion ( 30% yield).

[Chemical 57]

[Synthesis Example 3]
Except changing the diethylamine used in Synthesis Example 1 to 95.3 g (395 mmol) of di-2-ethylhexylamine, the same operation was performed to obtain 50.7 g (A-4 intermediate) (product (63%).
Next, using (A-4 intermediate), the same reaction with thionyl chloride as in Synthesis Example 1 was performed to obtain 5.6 g of a complex of a compound represented by the following formula (A-4) and a chloride anion ( Yield 50%).

[Chem 58]

[Synthesis Example 4]
In a reaction vessel, 0.8 g (0.89 mmol) of a complex of the compound represented by the above formula (A-4) and a chloride anion obtained in Synthesis Example 3 and 12.0 mL of methanol were added, and the mixture was heated at 60 ° C. Dissolve. In the solution, a mixed solution of 0.30 g (0.44 mmol) of anionic dye Direct Red 37 (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the following formula (B-22) and 12 mL of water was slowly added dropwise. After the dropwise addition, the mixture was stirred at the reflux temperature for 2 hours. After cooling to 25 ° C, 60 mL of water was added to the reaction solution, and the supernatant was removed. Add water to the contents and filter to obtain the solidified contents. The solid was dried under reduced pressure at 80 ° C. to obtain a salt-forming compound (0.74 g, including a dibenzopiperan-based cationic dye (A-4) and an anionic dye (B-22) as a brown solid. Yield 71%).

[Chemical 59]

[Synthesis Example 5]
Except that the anionic dye (B-22) used in Synthesis Example 4 was replaced with the anionic dye represented by the above formula (B-4), the same operation as in Synthesis Example 4 was carried out in the form of a brown solid A salt-forming compound (1.0 g, yield 85%) containing a dibenzopiperan-based cationic dye (A-4) and an anionic dye (B-4) was obtained.

[Synthesis Example 6]
Except substituting the anionic dye (B-22) used in Synthesis Example 4 with the anionic dye represented by the above formula (B-21), the same operation was performed to obtain the dibenzo-containing compound as a brown solid. A salt-forming compound (0.8 g, yield 80%) of a piperan-type cationic dye (A-4) and an anionic dye (B-21).

[Synthesis Example 7]
In a reaction vessel replaced with nitrogen, 100 mL of chloroform, 3.55 mL (49.2 mmol) of thionyl chloride, and 10.00 g (12.27 mmol) of the (A-4 intermediate) obtained in the above Synthesis Example 3 were added, and the temperature was raised to Boiling point. After stirring under heating and refluxing for 40 minutes, 0.20 g (2.7 mmol) of DMF was added and stirred for 1 hour. Add 0.38 g of DMF and 1.47 g of thionyl chloride in the middle and stir for 2 hours. The residue obtained by distilling off the solvent under reduced pressure was dried under reduced pressure at room temperature for 5 minutes, and then 50 mL of chloroform and 4.79 g (37.0 mmol) of di-n-butylamine were added, followed by stirring at 50 ° C for 12 hours. Furthermore, 9.58 g of di-n-butylamine was added and stirred for 2.5 hours to stop the reaction. Extraction was performed with dichloromethane, the organic layer was cleaned with water, and dried with anhydrous magnesium sulfate, and then the solvent was distilled off under reduced pressure. The residue was dissolved in 80 mL of tetrahydrofuran (THF), 20 mL of water and 0.5 mL of concentrated hydrochloric acid (36% by mass of HCl) were added, and the mixture was stirred at 25 ° C for 30 minutes, and then extracted with toluene. After the organic layer was cleaned with water (50 mL), the solvent was distilled off under reduced pressure, and dried under reduced pressure at 25 ° C. for 12 hours to obtain a crude product. The crude product was purified by silica gel column chromatography (carrier: silica gel, ethyl acetate / methanol = 20: 1 → 3: 1), and then the solvent was distilled off under reduced pressure, and dried under reduced pressure at 60 ° C for 5 hours. A complex of the compound represented by the above formula (A-22) and a chloride anion (5.03 g, yield 43%) was obtained as a purple viscous solid.

[Synthetic Example 8]
Except substituting the compound (A-4) obtained in Synthesis Example 4 with the complex of the above formula (A-22) and chloride anion, the same operation as in Synthesis Example 4 was performed, and a purple solid A salt-forming compound (0.87 g, yield 80%) containing a dibenzopiperan-based cationic dye (A-22) and an anionic dye (B-22) was obtained.

[Synthesis Example 9]
In a reaction vessel replaced with nitrogen, 6.55 g (55.0 mmol) of thionyl chloride, 0.33 g (4.5 mmol) of DMF, and 50 mL of chloroform were added, and (A-2 intermediate) obtained in Synthesis Example 2 was added at 10.00 g (13.76 mmol), and stirred under heating and refluxing for 1.5 hours. To the residue from which the solvent was distilled off under reduced pressure, 3.51 g (41.3 mmol) of piperidine was added, and the mixture was stirred at 50 ° C. for 12 hours. After cooling to 25 ° C, 300 mL of water was added, and extraction was performed with dichloromethane. The organic layer was cleaned with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography (carrier: silica gel, dichloromethane / methanol = 20: 1 → 10: 1). After the solvent was distilled off under reduced pressure, the residue was dried under reduced pressure at 25 ° C for 3 days to obtain a complex of the compound represented by the above formula (A-23) and a chloride anion (7.58) as a purple amorphous solid. g, yield 66%).

[Synthesis Example 10]
The same operation as in Synthesis Example 4 was performed except that the compound (A-4) used in Synthesis Example 4 was replaced with a complex of a compound represented by the above formula (A-23) and a chloride anion. A salt-forming compound (0.87 g, yield 89%) containing a dibenzopiperan-based cationic dye (A-23) and an anionic dye (B-22) was obtained as a brown solid.

[Synthesis Example 11]
In a reaction vessel, 8.36 g (9.21 mmol) of a complex of the compound (A-4) and a chloride anion, 83.6 mL of methanol, and 30.0 mL of water were added, and the mixture was dissolved and heated to 60 ° C. Thereafter, a mixed solution of 2.50 g (4.61 mmol) of sodium alkyldiphenyl ether disulfonate (Sandet BL manufactured by Sanyo Chemical Industry Co., Ltd.) and 12 mL of water was slowly added dropwise. After the dropwise addition, the mixture was stirred for 1 hour under heating and reflux to terminate the reaction. The reaction solution was concentrated under reduced pressure, and after methanol was distilled off, water was added for cleaning, and the supernatant was removed. Further, water was added to the contents, and dispersion cleaning was performed at 80 ° C. After cooling to 25 ° C., the supernatant was removed, and ethanol was added to the content to dissolve it. This solution was dried under reduced pressure to obtain a salt-forming compound (7.53 g, yield 71.9%) of dibenzopiperan-based cationic dye (A-4) and Sandet BL as a brown solid.

[Synthesis Example 12]
A 10% methanol solution of 20.0 g (2.2 mmol) of the complex of compound (A-4) and chloride anion was added to the reaction vessel, and heated to 55 ° C. 0.77 g (2.2 mmol) of sodium dodecylbenzenesulfonate dissolved in 20 mL of water was added dropwise, and the mixture was stirred under reflux for 2 hours. 100 mL of water was added to remove the supernatant, and then 80 mL of water was added, and the dispersion was cleaned at 80 ° C. The supernatant was removed, and the residue was dissolved in ethanol, and concentrated and dried to obtain a red-purple viscous solid. The obtained viscous solid was dissolved in dichloromethane, heptane was added, and concentrated and dried to obtain a dibenzopiperan cationic dye (A-4) and dodecylbenzenesulfonate as brown solids. Acid salt-forming compound (2.3 g, yield 87.1%).

[Example 1]
A thermogravimetric-differential thermal analysis device (MAC Science Co., Ltd.) was used for the salt-forming compound containing dibenzopiperan-based cationic dye (A-4) and anionic dye (B-22) obtained in Synthesis Example 4. TG-DTA 2000S type manufactured by the company). TG-DTA measurement (sample weight: 5 ± 1.5 mg, heating rate: 20 ° C / min) was performed under a nitrogen gas flow, and a 5% weight reduction temperature was measured. Next, the solubility in a PGMEA solvent at room temperature (25 ± 2 ° C) (PGMEA, 25 ± 2 ° C) was measured.
Furthermore, using a spectrophotometer (U-3000 manufactured by Hitachi, Ltd.) and PGME as a solvent, the ultraviolet-visible absorption spectrum and the ultraviolet-visible transmission spectrum were measured at room temperature. Based on the obtained ultraviolet-visible absorption spectrum, the maximum absorption wavelength in the visible light region was obtained. Secondly, the ultraviolet-visible transmission spectrum is used, with the maximum absorption wavelength as the absorption maximum wavelength, the area of transmitted light in the range of absorption maximum wavelength (577 nm) to 300 nm, and the range of absorption maximum wavelength (577 nm) to 300 nm. The total area is calculated as the ratio (%) of the area of transmitted light. The measurement results are summarized in Table 1.

[Table 1]

[Example 2]
Regarding the salt-forming compound containing the dibenzopiperan-based cationic dye (A-4) and anionic dye (B-4) obtained in Synthesis Example 5, a thermogravimetric-differential thermal analysis device was used (MAC Science Co., Ltd. TG-DTA 2000S type manufactured by the company). TG-DTA measurement (sample weight: 5 ± 1.5 mg, heating rate: 20 ° C / min) was performed under a nitrogen gas flow, and a 5% weight reduction temperature was measured. Next, the solubility in a PGMEA solvent at room temperature (25 ± 2 ° C) (PGMEA, 25 ± 2 ° C) was measured.
Furthermore, a spectrophotometer (U-3000 manufactured by Hitachi, Ltd.) was used, and PGME was used as a solvent to prepare a sample in a concentration range of 0.01 to 0.02 mg / mL, and the ultraviolet-visible absorption spectrum and ultraviolet were measured at room temperature Visible transmission spectrum. Based on the obtained ultraviolet-visible absorption spectrum, the maximum absorption wavelength in the visible light region was obtained. Next, use the ultraviolet-visible transmission spectrum, use the maximum absorption wavelength as the absorption maximum wavelength, use the area of transmitted light in the range of absorption maximum wavelength to 300 nm, and the total area of the range of absorption maximum wavelength to 300 nm to calculate the area of transmitted light. Ratio (%). The measurement results are summarized in Table 2.

[Example 3 to Example 5]
A salt-forming compound containing dibenzopiperan-based cationic dye (A-4) and anionic dye (B-21) obtained in Synthesis Example 6,
A salt-forming compound containing dibenzopiperan-based cationic dye (A-22) and anionic dye (B-22) obtained in Synthesis Example 8,
The same procedure as in Example 2 was performed on the salt-forming compound containing dibenzopiperan-based cationic dye (A-23) and anionic dye (B-22) obtained in Synthesis Example 10. The measurement results are summarized in Table 2.

[Table 2]

[Comparative Example 1]
For comparison, with respect to the dibenzopiperan dye CI Acid Red 289 (manufactured by Sinochem Chemical Co., Ltd.) represented by the following formula (D-1), a 5% weight reduction was measured by the same method as in Example 1. Temperature, solubility (PGMEA, 25 ± 2 ° C), and absorption maximum wavelength in PGME solution, calculate the ratio (%) of transmitted light in the range of absorption maximum wavelength (529 nm) to 300 nm in the ultraviolet-visible transmission spectrum. The results are shown together with the results of Example 1 in Table 1.

[Chemical 60]

[Comparative Example 2]
For comparison, the compound represented by the above formula (A-4) synthesized in Synthesis Example 3 and a chloride anion complex were measured in the same manner as in Example 1 to determine a 5% weight reduction temperature and solubility ( (PGMEA, 25 ± 2 ° C) and the absorption maximum wavelength in the PGME solution. Calculate the ratio (%) of the transmitted light in the range of the absorption maximum wavelength (577 nm) to 300 nm of the ultraviolet visible transmission spectrum. The results are shown together with the results of Example 1 in Table 1.

[Comparative Example 3]
For comparison, with respect to the anionic dye Direct Red 37 (manufactured by Tokyo Chemical Industry Co., Ltd.) represented by the above formula (B-22), a 5% weight reduction temperature and solubility (PGMEA, 25 ± 2 ℃) and the absorption maximum wavelength in the PGME solution, and calculate the ratio (%) of the transmitted light in the range of the absorption maximum wavelength (512 nm) to 300 nm of the ultraviolet visible transmission spectrum. The results are shown together with the results of Example 1 in Table 1.

[Comparative Example 4]
For comparison, a salt-forming compound containing dibenzopiperan cation dye (A-4) and Sandet BL obtained in Synthesis Example 11,
A salt-forming compound containing dibenzopiperan-based cationic dye (A-4) and dodecylbenzenesulfonic acid obtained in Synthesis Example 12,
A salt-forming compound containing a dibenzopiperan-based cationic dye (A-23) obtained in Synthesis Example 9 and a complex with a chloride anion was also subjected to the same operation as in Example 2. The measurement results are summarized in Table 2.

As described above, the salt-forming compound of the present invention containing a dibenzopiperan-based cationic dye and an anionic dye has an absorption maximum wavelength to a short wavelength side (range of absorption maximum wavelength to 300 nm) compared with an existing dye. The ratio is small, and the light of a wavelength other than the required wavelength is cut (absorbed), so that the color purity can be improved. The coloring composition containing the salt-forming compound of the present invention is useful as a colorant for a color filter that expands the color gamut. Furthermore, PGMEA used in the manufacture of color filters has good solubility and has the same heat resistance as conventional dyes.
[Industrial availability]

The salt-forming compound containing a dibenzopiperan-type cationic dye and an anionic dye of the present invention is excellent in solubility or heat resistance in an organic solvent (PGMEA, etc.), and the coloring composition containing the salt-forming compound is used as a color filter. A coloring agent for a sheet is useful, and a color filter can be produced by increasing the color purity by increasing the color purity.

FIG. 1 is a schematic diagram for explaining a specific example of an ultraviolet-visible transmission spectrum and a ratio of transmitted light that absorbs a maximum wavelength to 300 nm in an embodiment of the present invention.

Claims (11)

A salt-forming compound containing a dibenzopiperan cationic dye and an anionic dye represented by the following general formula (1): [Chem 61] [Wherein R ¹ to R ⁴ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 25 carbon atoms that may have a substituent, and 3 to 25 carbon atoms that may have a substituent A cycloalkyl group, a linear or branched alkenyl group having 2 to 25 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 25 carbon atoms which may have a substituent, or an alkyl group which may have a substituent Heterocyclic groups having 2 to 25 carbon atoms, R ¹ and R ² or R ³ and R ⁴ may be bonded to each other to form a ring; R ⁵ to R ⁸ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, and a nitrate Group, cyano group, linear or branched alkyl group having 1 to 25 carbon atoms which may have a substituent, cycloalkyl group having 3 to 25 carbon atoms which may have a substituent, carbon which may have substituent Linear or branched alkoxy group having 1 to 25 atoms, cycloalkoxy group having 3 to 25 carbon atoms that may have substituents, and straight chain alkoxy group having 2 to 25 carbon atoms that may have substituents Or branched alkenyl group, fluorenyl group having 1 to 25 carbon atoms which may have a substituent, amine group having 0 to 25 carbon atoms which may have a substituent, carbon source which may have substituent The aromatic hydrocarbon group having 6 to 25, or a substituent having a carbon atom of the heterocyclic group having 2 to 25, R ⁵ ~ R ⁸ may also consist of adjacent groups bonded to each other to form a ring; R ⁹ and R ¹⁰ Each independently represents a linear or branched alkyl group having 1 to 25 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 25 carbon atoms which may have a substituent, and a carbon atom which may have a substituent A linear or branched alkenyl group of 2 to 25, an aromatic hydrocarbon group of 6 to 25 carbon atoms that may have a substituent, or a heterocyclic group of 2 to 25 carbon atoms that may have a substituent, R ⁹ and R ¹⁰ may also be bonded to each other to form a ring; X represents an anionic dye, a represents an integer of 1 to 6, and b represents an integer of 1 to 6; wherein a and b are in charge as a whole according to the general formula (1) Sexual mode selection]. The salt-forming compound according to claim 1, wherein in the above general formula (1), X is an anionic dye having a sulfonic acid group. The salt-forming compound according to claim 1 or 2, wherein in the general formula (1), X is an anionic dye having two or more sulfonic acid groups. The salt-forming compound according to any one of claims 1 to 3, wherein in the general formula (1), X is an azo dye. The salt-forming compound according to any one of claims 1 to 4, wherein in the above-mentioned general formula (1), X is an azo dye having two or more sulfonic acid groups. The salt-forming compound according to any one of claims 1 to 5, wherein the decomposition starting temperature of the salt-forming compound is in a range of 250 to 400 ° C. The salt-forming compound according to any one of claims 1 to 6, wherein the solubility of the salt-forming compound in propylene glycol monomethyl ether acetate (PGMEA) at 25 ° C ± 2 ° C is 2% by weight or more. The salt-forming compound according to any one of claims 1 to 7, wherein the ratio of the transmitted light having an absorption maximum wavelength to 300 nm in the ultraviolet-visible transmission spectrum of the salt-forming compound is 60% or less. A coloring composition containing a salt-forming compound according to any one of claims 1 to 8. A coloring agent for a color filter, comprising the coloring composition according to claim 9. A color filter using the colorant for a color filter according to claim 10.