JP2012233033A - Salt for dye - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a salt for dye having an excellent molar absorptivity as dye in a colored photosensitive resin composition that becomes a material of a color filter.SOLUTION: This salt includes a cation having a xanthene skeleton as shown in Fig.(I-1) and an anion having a triphenylmethane skeleton, for example. A dye containing the salt as an active ingredient and a colored composition containing the dye are provided.

Description

  The present invention relates to a salt containing a cation having a xanthene skeleton and an anion having a triphenylmethane skeleton, a dye containing the salt as an active ingredient, and a coloring composition containing the dye.

Color filters are used in display devices such as liquid crystal panels, electroluminescence panels, and plasma display panels. Colored photosensitive resin compositions containing dyes are known as color filter materials. As a dye material constituting such a colored photosensitive resin composition, a triphenylmethane compound (0-1) described in Example 1 of Patent Document 1 is known.

Japanese Patent Laid-Open No. 5-229993

  The molar extinction coefficient exhibited by the triphenylmethane compound as described above was not always satisfactory.

［式（１）中、Ｒ^１〜Ｒ^４は、それぞれ独立に、水素原子、−Ｒ^８又は炭素数６〜１０の１価の芳香族炭化水素基を表し、該芳香族炭化水素基に含まれる水素原子は、ハロゲン原子、−Ｒ^８、−ＯＨ、−ＯＲ^８、−ＳＯ_３Ｈ、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^８、−ＳＯ_３Ｒ^８又は−ＳＯ_２ＮＲ^９Ｒ^１０で置換されていてもよい。
Ｒ^５は、−ＯＨ、−ＳＯ_３Ｈ、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^８、−ＳＯ_３Ｒ^８又は−ＳＯ_２ＮＲ^９Ｒ^１０を表す。
ｍは、０〜５の整数を表す。ｍが２以上の整数である場合、複数のＲ^５は同一であるか相異なる。
Ｒ^６及びＲ^７は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表す。
Ｒ^８は、炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｒ^９及びＲ^１０は、それぞれ独立に、水素原子、又は炭素数１〜２０の１価の飽和炭化水素基を表すか、互いに結合して窒素原子を含んだ３〜１０員環の複素環を形成する。該飽和炭化水素基に含まれる水素原子は、−ＯＨ又はハロゲン原子で置換されていてもよく、該飽和脂肪族炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＮＨ−又は−ＮＲ^８−で置き換っていてもよい。］
［３］Ｒ^６及びＲ^７が、いずれも水素原子である［２］記載の塩。
［４］トリフェニルメタン骨格を有するアニオン（Ｂ）が、式（２）で表され、且つ、−ＳＯ_３ ⁻を二つ有するアニオンである［１］〜［３］のいずれか一項記載の塩。

［式（２）中、Ｒ^５３〜Ｒ^５６、Ｒ^６０及びＲ^６１は、それぞれ独立に、水素原子、下記群Ｐ１から選ばれる基を有していてもよい炭素数１〜８のアルキル基又は下記群Ｐ２から選ばれる基を有していてもよい炭素数６〜１０の芳香族炭化水素基を表す。Ｒ^５７及びＲ^５９は、それぞれ独立に、水素原子、炭素数１〜８のアルキル基、−ＳＯ_３ ⁻又は−ＳＯ_３Ｈを表す。
Ｚは、下式（Ｚ１）又は（Ｚ２）で示される基を表す。

（式（Ｚ１）及び（Ｚ２）中、Ｒ^６２及びＲ^６３は、それぞれ独立に、水素原子、炭素数１〜８のアルキル基又は炭素数１〜８のアルコキシ基を表し、＊は、結合手を表す。）
群Ｐ１：−ＳＯ_３ ⁻、−ＳＯ_３Ｈ及び炭素数６〜１０の芳香族炭化水素基（該芳香族炭化水素基は、群Ｐ２から選ばれる基を有していてもよい）
群Ｐ２：−ＳＯ_３ ⁻、−ＳＯ_３Ｈ及び炭素数１〜８のアルコキシ基］
［５］［１］〜［４］のいずれか一項記載の塩を有効成分とする染料。
［６］［５］記載の染料を含む着色組成物。 The present invention provides the following [1] to [6].
[1] A salt comprising a cation (A) having a xanthene skeleton and an anion (B) having a triphenylmethane skeleton.
[2] The salt according to [1], wherein the cation (A) having a xanthene skeleton is a cation represented by the formula (1).

[In Formula (1), R ^{1 to} R ⁴ each independently represents a hydrogen atom, —R ⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and is included in the aromatic hydrocarbon group. The hydrogen atom to be substituted is a halogen atom, —R ⁸ , —OH, —OR ⁸ , —SO ₃ H, —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ R ⁸ or —SO ₂ NR ⁹ R ¹⁰ . May be.
R ⁵ represents —OH, —SO ₃ H, —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ R ^8, or —SO ₂ NR ⁹ R ¹⁰ .
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁵ are the same or different.
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a 3- to 10-membered heterocyclic ring containing a nitrogen atom bonded to each other. Form. The hydrogen atom contained in the saturated hydrocarbon group may be substituted with —OH or a halogen atom, and —CH ₂ — contained in the saturated aliphatic hydrocarbon group is —O—, —CO—, — NH— or —NR ⁸ — may be substituted. ]
[3] The salt according to [2], wherein R ⁶ and R ⁷ are both hydrogen atoms.
[4] The anion (B) having a triphenylmethane skeleton is an anion represented by the formula (2) and having two —SO ₃ ^— , [1] to [3] salt.

[In the formula (2), R ^{53 to} R ⁵⁶ , R ⁶⁰ and R ⁶¹ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a group selected from the following group P1 or The C6-C10 aromatic hydrocarbon group which may have group chosen from the following group P2. R ⁵⁷ and R ⁵⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, —SO ₃ ^— or —SO ₃ H.
Z represents a group represented by the following formula (Z1) or (Z2).

(In the formulas (Z1) and (Z2), R ⁶² and R ⁶³ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and * represents a bond. Represents.)
Group P1: —SO ₃ ^— , —SO ₃ H, and an aromatic hydrocarbon group having 6 to 10 carbon atoms (the aromatic hydrocarbon group may have a group selected from Group P2)
Group P2: —SO ₃ ^— , —SO ₃ H and an alkoxy group having 1 to 8 carbon atoms]
[5] A dye comprising the salt according to any one of [1] to [4] as an active ingredient.
[6] A coloring composition containing the dye according to [5].

  The salt of the cation (A) having a xanthene skeleton and the anion (B) having a triphenylmethane skeleton according to the present invention has a good molar extinction coefficient.

  The salt of the present invention comprises a cation (A) derived from a xanthene skeleton (hereinafter sometimes referred to as “cation (A)”) and an anion (B) derived from a triphenylmethane compound (hereinafter referred to as “anion (B)”). In some cases).

  As the cation (A), a cation represented by the above formula (1) (hereinafter sometimes referred to as “cation (1)”) is preferable.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ^{1 to} R ⁴ in the above formula (1) include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and A butylphenyl group etc. are mentioned.

The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ^{1 to} R ⁴ in the above formula (1) is a group consisting of —SO ₃ H and —SO ₂ NR ⁹ R ¹⁰ as a substituent. It is preferable to have at least one selected from the group consisting of —SO ₂ NR ⁹ R ¹⁰ . When R ^{1 to} R ⁴ are these groups, the colored photosensitive resin composition containing the compound (1) can form a coating film or a pattern with less generation of foreign matters and excellent heat resistance.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^{8 to} R ¹⁰ in the above formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and pentyl. Group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group and other alkyl groups having 1 to 20 carbon atoms; cyclopropyl group , A cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group and the like, and a cycloalkyl group having 3 to 20 carbon atoms;

The alkyl group having 1 to 6 carbon atoms represented by R ⁶ and R ⁷ in the formula (1), of the alkyl groups listed above, include those having 1 to 6 carbon atoms.

  The cation (1) is preferably a cation represented by any one of the formulas (1-1) to (1-12). In the following formula, Ra represents a 2-ethylhexyl group.

  The anion (B) is preferably an anion represented by the above formula (2) (hereinafter sometimes referred to as “anion (2)”).

  Examples of the alkyl group having 1 to 8 carbon atoms in the above formula (2) include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group and isopentyl group. , Neopentyl group, tert-pentyl group and the like.

As the alkyl group having 1 to 8 carbon atoms having a group selected from the group P1,
^{_{-C 2 H 4 SO 3 -,}} -C 2 H 4 SO 3 H, -C 3 H 6 SO 3 -, -C 3 H 6 SO 3 H, -C 4 H 8 SO 3 -, -C 4 H 8 SO ₃ H and the like.

  Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms in the above formula (2) include phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, benzyl group, phenethyl group, α-methylbenzyl group, benzhydryl group, Examples include a benzylidene group, a styryl group, a cinnamyl group, a cinnamylidene group, and a naphthyl group.

等が挙げられる。 As the aromatic hydrocarbon group having 6 to 10 carbon atoms having a group selected from the group P2,

Etc.

  Examples of the alkoxy group having 1 to 8 carbon atoms in the above formula (2) include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and a pentyloxy group. Is mentioned.

The anion (2) is preferably an anion represented by any one of the formulas (2-1) to (2-5).

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

  The salt according to the present invention can be produced by reacting the cation (A) and the anion (B) in a solvent. Specifically, the salt containing the anion (B) and the salt containing the cation (A) may be subjected to a salt exchange reaction in a solvent. In that case, it is preferable to react the salt containing an anion (B) and the salt containing a cation (A) at a molar ratio of 1: 1 to 1: 4.

  The method for obtaining the target compound salt from the reaction mixture is not particularly limited, and the target compound salt precipitated in the reaction mixture can be obtained, for example, by solid-liquid treatment such as filtration. In addition, various other known methods can be employed. For example, the reaction mixture can be mixed with an inorganic salt (eg, sodium chloride) and water, and the precipitated crystals can be collected by filtration. The inorganic salt can be prepared by preparing an aqueous solution of an inorganic salt in advance and then adding the reaction mixture to the aqueous solution. The temperature at which the reaction mixture is added is preferably 10 ° C. or higher and 50 ° C. or lower, more preferably 10 ° C. or higher and 40 ° C. or lower, and further preferably 10 ° C. or higher and 25 ° C. or lower. Moreover, after adding a reaction mixture to the aqueous solution of an inorganic salt, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  The salt of the present invention thus obtained is useful as a dye. In particular, since the salt of the present invention has a high spectral density, it is useful as a dye used for color filters, fiber materials, and the like of display devices such as liquid crystal display devices that perform color display using reflected light or transmitted light.

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

  The colored composition of the present invention preferably contains the dye of the present invention as a colorant (hereinafter sometimes referred to as “colorant (C)”) and further contains a resin (D). More preferably, the colored composition of the present invention further contains a polymerizable compound (E), a polymerization initiator (D), and a solvent (G).

In addition to the dye of the present invention, the colorant (C) may further contain a pigment and / or a dye different from the dye of the present invention.
As dyes different from the dyes of the present invention, the Color Index (published by The Society of Dyers and Colorists), Solvent, Acid, Basic, reactive, direct And dyes classified as (Direct), Disperse, or Vat. More specifically, dyes having the following color index (CI) numbers can be mentioned, but the dye is not limited thereto.
C. I. Solvent Yellow 25, 79, 81, 82, 83, 89;
C. I. Acid Yellow 7, 23, 25, 42, 65, 76;
C. I. Reactive Yellow 2, 76, 116;
C. I. Direct yellow 4, 28, 44, 86, 132;
C. I. Disperse Yellow 54,76;
C. I. Solvent orange 41, 54, 56, 99;
C. I. Acid Orange 56, 74, 95, 108, 149, 162;
C. I. Reactive Orange 16;
C. I. Direct orange 26;
C. I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;
C. I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;
C. I. Acid Violet 102;
C. I. Solvent Green 1,5;
C. I. Acid Green 3, 5, 9, 25, 28;
C. I. Basic Green 1;
C. I. Bat Green 1 etc.

Examples of the pigment include organic pigments and inorganic pigments usually used for pigment dispersion resists. Examples of inorganic pigments include metal compounds such as metal oxides and metal complex salts. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony and other metal compounds. Oxides or mixed metal oxides may be mentioned. Specific examples of organic pigments and inorganic pigments include compounds classified as Pigment under the Color Index (published by The Society of Dyers and Colorists). More specifically, pigments having the following color index (CI) numbers can be mentioned, but the invention is not limited to these.
C. I. Pigment yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173 and 180;
C. I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264;
C. I. Pigment violet 14, 19, 23, 29, 32, 33, 36, 37 and 38;
C. I. Pigment Green 7, 10, 15, 25, 36, 47 and 58 etc.

The content of the colorant (C) is preferably 5 to 60% by mass with respect to the solid content in the colored composition. Here, solid content means the sum total of the component except a solvent in a coloring composition.
The content of the dye of the present invention contained in the colorant (C) is preferably 3 to 100% by mass.
Dyes and pigments different from the dye of the present invention may be used alone or in combination of two or more with the dye of the present invention.

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

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

The weight average molecular weight in terms of polystyrene of the resin (D) is preferably from 5,000 to 35,000, more preferably from 6,000 to 30,000.
The acid value of the resin (D) is preferably 50 to 150, and more preferably 60 to 135.
Content of resin (D) becomes like this. Preferably it is 7-65 mass% with respect to solid content of a coloring composition, More preferably, it is 13-60 mass%.

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

The polymerizable compound (E) is preferably a photopolymerizable compound having 3 or more polymerizable groups. Examples of the photopolymerizable compound having 3 or more polymerizable groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate and the like. Is mentioned. The photopolymerizable compound (E) may be used alone or in combination of two or more.
It is preferable that content of polymeric compound (E) is 5-65 mass% with respect to solid content of a coloring composition, More preferably, it is 10-60 mass%.

  As said polymerization initiator (F), an active radical generator, an acid generator, etc. are mentioned. Active radical generators generate active radicals by the action of heat or light. Examples of the active radical generator include alkylphenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.

  Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, Examples include benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, and the like.

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

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4 -Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl)- 6- [2- (5-Methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (Trichloromethyl 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the oxime compound include O-acyloxime compounds, and specific examples thereof include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N -Benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] Ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H -Carbazol-3-yl] ethane-1-imine and the like.

  Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1, 2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like may be used.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl, Onium salts such as methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.
The polymerization initiators (F) may be used alone or in combination of two or more.

  The content of the polymerization initiator (F) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 with respect to 100 parts by mass of the total amount of the resin (D) and the polymerizable compound (E). Part by mass. When the content of the polymerization initiator is within the above range, it is preferable because the sensitivity is increased, the exposure time is shortened, and the productivity is improved.

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

  Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. , Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like.

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

  Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, and cyclopentanone. And cyclohexanone.

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

  Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, and lactic acid. Ethyl, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methylpropionic acid Chill, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ -Butyrolactone etc. are mentioned.

Examples of the amides include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.
These solvents may be used alone or in combination of two or more.

  Content of the solvent (G) in a coloring composition becomes like this. Preferably it is 70-95 mass% with respect to a coloring composition, More preferably, it is 75-90 mass%.

  The coloring composition of the present invention may be added as necessary, such as surfactants, fillers, other polymer compounds, adhesion promoters, antioxidants, ultraviolet absorbers, light stabilizers, chain transfer agents, etc. An agent may be included.

Next, the present invention will be described more specifically with reference to examples.
In Examples and Comparative Examples, “%” and “part” representing content or use amount are based on mass unless otherwise specified.

  In the following examples, the structure of the compound was confirmed by elemental analysis (VARIO-EL; (Elemental Co., Ltd.)) and mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).

[Example 1]
A solution (s1) was prepared by dissolving 8.5 parts of Acid Blue 90 in 20 ml of N, N-dimethylformamide. Separately, a compound represented by the following formula (d-1) was obtained according to the production method described in Synthesis Example 3 of JP2010-32999A.

Identification of compound represented by formula (d-1) (mass spectrometry) ionization mode = ESI−: m / z = 824.0 [M] ⁻

  A solution (t1) was prepared by dissolving 8.2 parts of the compound represented by the formula (d-1) in 20 ml of N, N-dimethylformamide. At 25 ° C., the solution of (s1) was added dropwise to (t1) over 1 hour, and then stirred for 2 hours. Thereafter, 100 ml of ion exchange water was added, and the mixture was further stirred for 1 hour. Then, suction filtration was performed and the product was washed with 100 ml of ion exchange water to obtain 3.0 parts of the salt represented by the formula (I-1).

Identification of the compound represented by formula (I-1);
(Elemental analysis) C: 66.3, H: 6.2, N: 6.4, S: 8.2

<Measurement of absorbance>
0.35 g of each compound was dissolved in ethyl lactate to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with ethyl lactate to 100 cm ³ to prepare a solution having a concentration of 0.028 g / L. About this solution, the maximum absorption wavelength (λmax) and the molar extinction coefficient were measured using an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). The results are shown in Table 1.

[Example 2]
[Preparation of colored photosensitive resin composition]
(A) Colorant: Compound (I-1): Compound synthesized in Example 1 20 parts (B-1) Resin: Methacrylic acid / benzyl methacrylate copolymer (molar ratio; 30/70; weight average molecular weight 10700, Acid value 70 mg KOH / g) 70 parts (C-1) polymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.) 30 parts (D-1) photopolymerization initiator: benzyldimethyl ketal (Irgacure (registered trademark)) 651; manufactured by Ciba Japan Co., Ltd.) 15 parts (E-1) Solvent: 680 parts of dimethylformamide are mixed to obtain a colored resin composition.

[Production of color filters]
On the glass, the colored resin composition obtained above is applied by a spin coating method to volatilize volatile components. After cooling, light irradiation is performed using a quartz glass photomask having a pattern and an exposure machine. After light irradiation, development is performed with an aqueous potassium hydroxide solution, and the color filter is obtained by heating to 200 ° C. in an oven.

  As a result of Table 1, it can be seen that the compound of the present invention exhibits a high spectral concentration because of its high absorbance. In addition, the colored resin composition containing the compound has excellent color performance and can produce a high-quality color filter.

The salt of the present invention is useful as a dye. Since it has a high molar extinction coefficient and shows solubility in organic solvents, it is particularly useful as a dye for use in color filters of display devices such as liquid crystal display devices.
In addition, the colored composition containing the salt of the present invention has various colored images such as a display device (for example, a known liquid crystal display device or an organic EL device) having a color filter as a part of its constituent parts, a solid-state imaging device, or the like. It can be used in a known manner for devices related to the above.

Claims (6)

  A salt comprising a cation (A) having a xanthene skeleton and an anion (B) having a triphenylmethane skeleton. The salt according to claim 1, wherein the cation (A) having a xanthene skeleton is a cation represented by the formula (1).

[In Formula (1), R ^{1 to} R ⁴ each independently represents a hydrogen atom, —R ⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and is included in the aromatic hydrocarbon group. The hydrogen atom to be substituted is a halogen atom, —R ⁸ , —OH, —OR ⁸ , —SO ₃ H, —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ R ⁸ or —SO ₂ NR ⁹ R ¹⁰ . May be.
R ⁵ represents —OH, —SO ₃ H, —CO ₂ H, —CO ₂ R ⁸ , —SO ₃ R ^8, or —SO ₂ NR ⁹ R ¹⁰ .
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁵ are the same or different.
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a 3- to 10-membered heterocyclic ring containing a nitrogen atom bonded to each other. Form. The hydrogen atom contained in the saturated hydrocarbon group may be substituted with —OH or a halogen atom, and —CH ₂ — contained in the saturated aliphatic hydrocarbon group is —O—, —CO—, — NH— or —NR ⁸ — may be substituted. ] The salt according to claim 2, wherein both R ⁶ and R ⁷ are hydrogen atoms. Anions having a triphenylmethane skeleton (B) is represented by the formula (2), and, -SO ₃ ^- salt of any one of claims 1 to 3, a two having anions.

[In the formula (2), R ^{53 to} R ⁵⁶ , R ⁶⁰ and R ⁶¹ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a group selected from the following group P1 or The C6-C10 aromatic hydrocarbon group which may have group chosen from the following group P2. R ⁵⁷ and R ⁵⁹ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, —SO ₃ ^— or —SO ₃ H.
Z represents a group represented by the following formula (Z1) or (Z2).

(In the formulas (Z1) and (Z2), R ⁶² and R ⁶³ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and * represents a bond. Represents.)
Group P1: —SO ₃ ^— , —SO ₃ H, and an aromatic hydrocarbon group having 6 to 10 carbon atoms (the aromatic hydrocarbon group may have a group selected from Group P2)
Group P2: —SO ₃ ^— , —SO ₃ H and an alkoxy group having 1 to 8 carbon atoms]   The dye which uses the salt as described in any one of Claims 1-4 as an active ingredient.   A coloring composition comprising the dye according to claim 5.