TWI538961B - Dye with salt - Google Patents

Description

Dye salt

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

In a display device such as a liquid crystal panel, an electroluminescence panel, or a plasma display panel, a color filter is used, and a material of the color filter is known to have a dye-containing colored photosensitive resin composition. A material of the dye constituting the colored photosensitive resin composition is known as a triphenylmethane compound (0-1) as described in Example 1 of Patent Document 1. (known technology)

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 5-229993

The molar absorption coefficient exhibited by the aforementioned triphenylmethane compound is not necessarily very satisfactory.

The inventors of the present invention have been working hard on the above-mentioned problems, and as a result, have found that according to the present invention, The salt composed of the cation (A) of the skeleton and the anion (B) having a triphenylmethane skeleton has a good molar absorption coefficient.

The invention includes the following invention.

[1] a salt which has The skeleton cation (A) and the anion (B) having a triphenylmethane skeleton are composed.

[2] The salt of [1], wherein the The cation (A) of the skeleton is a cation represented by the formula (1).

In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted. 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 . 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 from 0 to 5. When m is an integer of 2 or more, most 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 a 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 heterocyclic ring bonded to each other to form a 3 to 10 membered ring containing a nitrogen atom. The hydrogen atom contained in the saturated hydrocarbon group may also be substituted with -OH or a halogen atom. The -CH ₂ - contained in the saturated aliphatic hydrocarbon group may also be replaced by -O-, -CO-, -NH- or -NR ⁸ -. ]

[3] The salt according to [2], wherein R ⁶ and R ⁷ are each a hydrogen atom.

[4] of [1] to [3] salt of any one, which has the anion (B) represented triphenylmethane skeleton of the train to the formula (2) and having two -SO ₃ ^- anion.

[In the formula (2), R ⁵³ to R ⁵⁶ , R ⁶⁰ and R ⁶¹ each independently represent a hydrogen atom, and may have an alkyl group having 1 to 8 carbon atoms selected from the group of the following group P1 or may be An aromatic hydrocarbon group having 6 to 10 carbon atoms selected from the group selected from the group P2 below. 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 formulae (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 bonded limb.) Group P1: -SO ₃ ^- , -SO ₃ H and an aromatic hydrocarbon group having 6 to 10 carbon atoms (the aromatic hydrocarbon group may also have a group selected from the group P2) Group P2: -SO ₃ ^- , -SO ₃ H and alkoxy group having a carbon number of 1 to 8].

[5] A dye according to any one of [1] to [4] as an active ingredient.

[6] A coloring composition comprising the dye of [5].

The salt of the present invention has The cation (A) of the skeleton and the anion (B) having a triphenylmethane skeleton have a good Mohr absorption coefficient.

The salt of the present invention is derived from The cation (A) of the skeleton (hereinafter sometimes referred to as "cation (A)") and the salt derived from the anion (B) of the triphenylmethane compound (hereinafter sometimes referred to as "anion (B)").

Cationic (A) can be used a variety of coloring agents (especially dyes) of the cationic type of the skeleton, for example: a benzene ring-bonded amine group (-NR ₂ ), such that the amine group becomes =N ⁺ R ₂ and the conjugated compound is extended. The skeleton preferably has one or more aromatic hydrocarbon group bonds. Such a cation (A), particularly a cation represented by the above formula (1) is preferred. By combining the cation (A) with the anion (B), the molar absorption coefficient can be increased.

In the above formula (1), R ¹ to R ⁴ represent a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, for example, a phenyl group, a tolylmethyl group, a xylyl group, Base, propylphenyl and butylphenyl groups.

In the above formula (1), R ¹ to R ⁴ represent a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably having a group selected from the group consisting of -SO ₃ H and -SO ₂ NR ⁹ R ¹⁰ . At least one of them is preferably used as a substituent, and more preferably -SO ₂ NR ⁹ R ¹⁰ . When R ¹ to R ^{4 are} these groups, the colored composition (colored photosensitive resin composition) of the compound (1) is contained, and a foreign matter is small, and a coating film or pattern excellent in heat resistance can be formed.

In the above formula (1), R ⁸ to R ¹⁰ represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group or pentyl group. , an isobutyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a decyl group, a decyl group, a dodecyl group, a hexadecyl group, a hexyl group, and the like, an alkyl group having 1 to 20 carbon atoms; a cycloalkyl group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group or a tricyclodecyl group;

R ⁹ and R ¹⁰ is a suitable number of different combinations of preferred carbon, for example, a saturated hydrocarbon group having from 1 or less carbon atoms (including hydrogen atoms) of the decision ¹⁰ wherein one of R ⁹ and R, and the carbon number of 2 or more, more A linear or branched alkyl group of 2 to 10 (e.g., a C _1-2 alkyl C _4-8 alkyl group such as ethylhexyl) is preferred.

In the above formula (1), R ⁶ and R ⁷ represent an alkyl group having 1 to 6 carbon atoms, and for example, those having 1 to 6 carbon atoms in the above-exemplified alkyl group.

m is preferably an integer from 1 to 4, an integer from 1 to 2 is better, and 1 is particularly preferred.

The cation (A) is preferably a cation represented by any one of the formulae (1-1) to (1-11) and the formula (1-21) to the formula (1-25). Further, in the following formula, Ra represents a 2-ethylhexyl group, and EtOH represents a hydroxyethyl group. Such cations can, for example, by having a -SO ₃ ^-, -SO ₃ H in the dye or dye intermediate chloride titration, and the obtained dye having the -SO ₂ Cl or pigments having intermediate with 2-ethyl It is synthesized by reacting an amine such as a hexylamino group.

Anion (B) may be used having an anionic triphenylmethane skeleton of the various colorants (particularly dye), for example, benzene rings in the knot of triphenylmethane at least one amine group (-NR _2), and a compound in which at least one of the amine groups becomes =N ⁺ R ₂ and extends a conjugated system, and the triphenylmethane skeleton, the amine group (-NR ₂ ), and the conjugated amine group (=N ⁺ R ₂ ) of the compound One or more of them are bonded to more anionic groups (-COO ^- , -SO ₃ ^-, etc., especially -SO ₃ ^- ) than the conjugated amine group. Such an anion (B) is preferably an anion (B) represented by the above formula (2).

In the above formula (2), an alkyl group having 1 to 8 carbon atoms, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, t-butyl, pentyl , isoamyl, neopentyl, third amyl and the like.

An alkyl group having 1 to 8 carbon atoms selected from the group of the above group P1, for example: -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, etc.; -CH ₂ Ph group, -C ₂ H ₄ Ph group, C ₃ H ₆ Ph group, etc. The aforementioned Ph group has a -SO ₃ ^- substitution as a P 2 group.

In the above formula (2), the aromatic hydrocarbon group having 6 to 10 carbon atoms may, for example, be a phenyl group, a tolylmethyl group or a xylyl group. Base, cumyl, benzyl, phenethyl, α-methylbenzyl, benzhydryl, benzylidene, styryl, cinnamyl, cinnamyl, naphthyl and the like.

In the present specification, the aromatic hydrocarbon group having 6 to 10 carbon atoms is defined as including a lower alkyl group (methyl group, ethyl group, propyl group, butyl group, etc.).

The above aromatic hydrocarbon group having 6 to 10 carbon atoms selected from the group of the group P2, for example: Wait. Also, * in the formula indicates a keyed limb.

In the above formula (2), an alkoxy group having 1 to 8 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a second butoxy group, Third butoxy group, pentyloxy group and the like.

In the formula (2), at least one of a combination of R ⁵³ and R ⁵⁴ , a combination of R ⁵⁵ and R ⁵⁶ , and a combination of R ⁶⁰ and R ⁶¹ (for example, one group, more preferably two groups, more preferably Among them, one of them is an aromatic hydrocarbon group having 6 to 10 carbon atoms as an alkyl group having 1 to 8 carbon atoms of P1 (for example, -CH ₂ Ph group, -C ₂ H ₄ Ph group, and C) Any of ₃ H ₆ Ph groups and the like (except that the aforementioned Ph group has a -2 ₃ ^- substituted as a P 2 group) and an aromatic hydrocarbon group having a P 2 group having 6 to 10 carbon atoms, the other of which is hydrogen An atom or an unsubstituted alkyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms). The remaining groups are preferably both unsubstituted carbon groups having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms). Z is preferably Z1, and R ⁵⁷ , R ⁵⁹ and R ^{62 are} preferably the same or different, and are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (especially a methyl group).

The anion (B) is preferably an anion represented by any one of the formulae (2-1) to (2-5), for example.

A salt composed of a cation (A) and an anion (B), for example, the following salts.

The salt of the present invention can be produced by reacting a cation (A) with an 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.

The solvent is not particularly limited, and a guanamine solvent is preferred. The guanamine solvent is specifically, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or the like. Among them, N,N-dimethylformamide is preferred.

At this time, it is preferred to react the salt containing an anion (B) with the salt containing the cation (A) at a molar ratio of 1:1 to 1:4. The anion (B), when represented by the molar ratio (anion (B) / cation (A)), is preferably 1/10 or more, 1/7. The above is even better. Further, when the anion (B) is represented by the molar ratio (anion (B) / cation (A)), it is preferably 10/1 or less, more preferably 2/1 or less.

The method for obtaining the target compound salt from the reaction mixture is not particularly limited, and can be obtained by subjecting the target compound salt precipitated in the reaction mixture to solid-liquid treatment such as filtration. Also, other well-known methods can be employed. For example, the reaction mixture may be mixed with an inorganic salt (for example, salt, etc.) and water, and the precipitated crystals may be collected by filtration. The inorganic salt may be previously prepared as an aqueous solution of an inorganic salt, and then the reaction mixture is added to the aqueous solution.

The temperature at the time of adding the reaction mixture is preferably 10 ° C or more and 50 ° C or less, more preferably 10 ° C or more and 40 ° C or less, and still more preferably 10 ° C or more and 25 ° C or less. Further, after the reaction mixture is added to the aqueous solution of the inorganic salt, it is preferably stirred at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water or the like, and then dried. Further, it may be further purified by a known method such as recrystallization, as needed.

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

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

Further, the dye of the present invention preferably contains a salt of the cation (A) and the anion (B): for example, 3% by mass or more and 100% by mass or less, preferably 50% by mass or more and 100% by mass or less, and more preferably 80% by mass or more. It is preferably 100% by mass or less.

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

The coloring agent (C) may further contain a pigment and/or a dye different from the dye of the present invention, in addition to the dye of the present invention.

A dye different from the dye of the present invention, such as the Colour Index (published by The Society of Dyers and Colourists), classified as Solvent, Acid, Basic, Reactive, Direct (Direct), Disperse, or Vat dyes. More specifically, the following color index (C.I.) numbered dyes may be mentioned, but are not limited thereto. CI Solvent Yellow 25, 79, 81, 82, 83, 89; CI Acid Yellow 7, 23, 25, 42, 65, 76; CI Reaction Yellow 2, 76, 116; CI Direct Yellow 4, 28, 44, 86, 132; CI disperse yellow 54, 76; CI solvent orange 41, 54, 56, 99; CI acid orange 56, 74, 95, 108, 149, 162; CI reaction orange 16; CI direct orange 26; CI solvent red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218; CI 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.

A pigment such as an organic pigment or an inorganic pigment which is usually used for a pigment dispersion resist.

An inorganic pigment such as a metal compound such as a metal oxide or a metal salt, specifically, an oxide or a composite of a metal such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc or bismuth. Metal oxide.

Further, as an organic pigment and an inorganic pigment, specifically, for example, a compound classified as a pigment in a Colour Index (published by The Society of Dyers and Colourists). More specifically, for example, the following color index (C.I.) numbered pigments are not limited thereto. CI 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 Pigment; orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 and 71; CI Pigment Red 9, 97, 105, 122, 123, 144 Red pigments such as 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255 and 264; CI Pigment Violet 14, 19, 23, 29, 32, 33, 36, Purple pigments such as 37 and 38; C.I. Pigment green 7, 7, 15, 25, 36, 47 and 58 and other green pigments.

The content of the colorant (C) is preferably from 5 to 60% by mass, more preferably from 7 to 40% by mass, even more preferably from 10 to 20% by mass, based on the solid content of the coloring composition. Here, the solid content means the total of the components which do not contain a solvent in a coloring composition.

The content of the dye of the present invention contained in the colorant (C) is preferably from 3 to 100% by mass, more preferably from 50 to 100% by mass, even more preferably from 80 to 100% by mass.

The dyes and pigments different from the dye of the present invention may be used singly or in combination of two or more kinds thereof together 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 a resin containing a structural unit derived from (meth)acrylic acid is more preferable. Here, (meth)acrylic acid represents acrylic acid and/or methacrylic acid.

Resin (D) specifically, for example, methacrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/styrene copolymer, methacrylic acid/benzyl methacrylate/methacrylic acid Isodecyl ester copolymer, methacrylic acid/styrene/benzyl methacrylate/N-phenylmaleimide copolymer, methacrylic acid/styrene/glycidyl methacrylate copolymer, and the like.

Among them, a methacrylic acid/benzyl methacrylate copolymer is preferred.

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

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

The content of the resin (D) is preferably 7 to 65% by mass, and more preferably 13 to 60% by mass based on the solid content of the coloring composition. In the coloring composition, the content of the resin (D) is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, based on 1 part by mass of the coloring agent (C). It is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.

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

The polymerizable compound (E) is preferably a photopolymerizable compound having three or more polymerizable groups. A photopolymerizable compound having three or more polymerizable groups, for example, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, hexamethyl group Dipentaerythritol acrylate or the like. The polymerizable compound (E) may be used singly or in combination of two or more.

The polymerizable compound (E) is preferably dipentaerythritol hexaacrylate.

The content of the polymerizable compound (E) is preferably from 5 to 65% by mass, more preferably from 10 to 60% by mass, based on the solid content of the coloring composition. In addition, the content of the polymerizable compound (E) in the coloring composition is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and still more preferably 1 part by mass based on 1 part by mass of the coloring agent (C). The above is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 2 parts by mass or less. Among them, 1.5 parts by mass is preferred.

The polymerization initiator (F), for example, an active radical generator, an acid generator, or the like. The living radical generator generates active radicals due to heat or light. The aforementioned living radical generating agent, such as an alkyl phenone compound, a thioxanthone compound, three Compounds, hydrazine compounds, and the like.

The aforementioned alkyl phenone compound, for example: 2-methyl-2- Olostino-1-(4-methylsulfanylphenyl)propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl Ketone, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, and the like.

The aforementioned thioxanthone compound, for example: 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro -4-propoxythioxanthone and the like.

The aforementioned three a compound such as 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.

The above hydrazine compound, for example, an O-mercapto fluorene-based compound, and specific examples thereof, for example, N-benzylideneoxy-1-(4-phenylsulfanylphenyl)butan-1-one-2- Imine, N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-acetoxy-1-[9-ethyl -6-(2-methylbenzhydryl)-9H- Oxazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2) , 4-dioxalanylmethoxy)benzhydryl}-9H-indazol-3-yl]ethane-1-imine, and the like.

Further, as the living radical generating agent, for example, 2,4,6-trimethylbenzimidyldiphenylphosphine oxide or 2,2'-bis(o-chlorophenyl)-4,4' may be used. 5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylhydrazine, benzyl, 9,10-phenanthrenequinone, camphorquinone, benzene Methyl glyoxylate, titanium titanate compound, and the like.

The aforementioned acid generator, for example, 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-ethenyloxyphenyldimethylhydrazine Tosylate, 4-ethyloxyphenyl ‧ methyl ‧ benzyl hexafluoroantimonate, triphenyl sulfonium p-toluene sulfonate, triphenyl sulfonium hexafluoroantimonate, diphenyl hydrazine An onium salt such as p-toluenesulfonate or diphenylphosphonium hexafluoroantimonate; or a nitrobenzyl tosylate or a benzoin tosylate. The polymerization initiator (F) may be used singly or in combination of two or more. The polymerization initiator (F) is preferably an alkylphenone compound. Among them, benzyldimethylketal is preferred.

The content of the polymerization initiator (F) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total of the resin (D) and the polymerizable compound (E).

When the content of the polymerization initiator is in the above range, the sensitivity is high, the exposure time is shortened, and the productivity is improved, which is preferable.

The solvent (G) is, for example, an ether, an aromatic hydrocarbon, a ketone, an alcohol, an ester or a guanamine.

The above ethers, for example: tetrahydrofuran, tetrahydropyran, 1,4-two Alkane, 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 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.

The aforementioned aromatic hydrocarbons, for example, benzene, toluene, xylene, Wait.

The aforementioned ketones, for example: acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-pentyl Ketone, cyclopentanone, cyclohexanone, and the like.

The aforementioned alcohols are, for example, methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin or the like.

The aforementioned esters are, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Butyl butyrate, methyl lactate, ethyl lactate, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetic acid Ester, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 2-methoxypropionic acid Ester, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2- Methyl methacrylate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, Ethyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, γ-butyrolactone, and the like.

The aforementioned guanamines are, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or the like.

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

The solvent (G) is preferably a guanamine. Among them, N,N-dimethylformamide is preferred.

The content of the solvent (G) in the coloring composition is preferably from 70 to 95% by mass, more preferably from 75 to 90% by mass, based on the coloring composition. In addition, the content of the solvent (G) in the coloring composition is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and still more preferably 30 parts by mass or more based on 1 part by mass of the coloring agent (C). It is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, and still more preferably 50 parts by mass or less.

The colored composition of the present invention may contain various additives such as a surfactant, a filler, another polymer compound, an adhesion promoter, an antioxidant, an ultraviolet absorber, a photostabilizer, and a chain transfer agent, as needed.

[Examples]

Next, the present invention will be more specifically described by way of examples.

In the examples and comparative examples, the % and parts of the representative content and the amount used are based on the mass basis unless otherwise specified.

In the following examples, the structures of the compounds were confirmed by elemental analysis (VARIO-EL; (manufactured by Elementar)) and mass analysis (LC; Model 1200 manufactured by Agilent, MASS; LC/MSD type manufactured by Agilent).

[Example 1]

A solution (s1) obtained by dissolving 8.5 parts of Acid Blue 90 in 20 ml of N,N-dimethylformamide was prepared.

Further, a compound represented by the following formula (d-1) is obtained according to the method described in Synthesis Example 3 of JP-A-2010-32999. That is, the dye represented by the following formula (d-0) is chlorinated according to the method, and the obtained pigment intermediate having SO ₂ Cl is reacted with an amine to obtain a compound represented by the formula (d-1).

Identification of compounds represented by formula (d-1)

(mass analysis) ionization mode = ESI-: m/z = 824.0 [M]-

A solution (t1) obtained by dissolving 8.2 parts of the compound represented by the formula (d-1) in 20 ml of N,N-dimethylformamide was prepared.

The solution of (s1) was added dropwise at 25 ° C for 1 hour in (t1), followed by stirring for 2 hours. Thereafter, 100 ml of ion-exchanged water was added, and the mixture was further stirred for 1 hour. Thereafter, the mixture was suction filtered, and washed with 100 ml of ion-exchanged water to obtain 3.0 parts of the salt represented by the formula (I-1).

Identification of the salt 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 of the compound represented by the formula (I-1), Acid Blue 90 (Comparative Example 1), and the compound represented by the formula (d-1) (Comparative Example 2) was dissolved in ethyl lactate. a volume of 250cm ^3, wherein 2cm ³ and diluted with ethyl lactate to 100cm ^3, prepared at a concentration 0.028g / L of solution. For the solution, a maximum absorption wavelength (λ max) and a molar absorption coefficient were measured using an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz colorimetric tube, optical path length; 1 cm). The results are shown in Table 1.

[Embodiment 2] [Preparation of coloring composition]

The following ingredients were mixed to prepare a coloring composition.

[Production of color filter]

The coloring composition obtained above was applied by spin coating on glass, and the volatile component was volatilized. After cooling, a patterned quartz glass reticle and an exposure machine were used to illuminate. After illuminating, it was developed with an aqueous solution of potassium hydroxide and heated in an oven to 200 ° C to obtain a color filter.

As is clear from the results of Table 1, the salt of the present invention exhibits a high spectroscopic concentration due to a high molar absorption coefficient. Further, the colored resin composition containing the compound has excellent color properties and can produce a high-quality color filter.

[Industry Utilization]

The salts of the invention are useful as dyes. Since the molar absorption coefficient is high and the solubility is exhibited for an organic solvent, it is particularly useful as a dye used for a color filter of a display device such as a liquid crystal display device.

In addition, the coloring composition containing the salt of the present invention can be used in a known manner in a display device in which a color filter is used as a part thereof (for example, a known liquid crystal display device, an organic EL device, etc.), and a solid-state imaging device. A variety of devices related to coloring images.

Claims (4)

a salt Skeleton of the cation (A) and an anion having a triphenylmethane skeleton of the (B) constituting the triphenylmethane anion having a skeleton of the (B) is represented by an expression (2) and having two -SO ₃ ^- anion of: [In the formula (2), R ⁵³ to R ⁵⁶ , R ⁶⁰ and R ⁶¹ each independently represent a hydrogen atom, and may have an alkyl group having 1 to 8 carbon atoms selected from the group of the following group P1 or may be An aromatic hydrocarbon group having 6 to 10 carbon atoms selected from the group consisting of 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 base represented by the following formula (Z1) or (Z2); (In the formulae (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 bonded limb) R ⁵³ And at least one of a combination of R ⁵⁴ , a combination of R ⁵⁵ and R ⁵⁶ , and a combination of R ⁶⁰ and R ⁶¹ , wherein one of the groups is an alkyl group having 1 to 8 carbon atoms having an aromatic hydrocarbon group having 6 to 10 carbon atoms; Any one of the aromatic hydrocarbon groups having 6 to 10 carbon atoms selected from the group of the group P2, and the other one of a hydrogen atom or an unsubstituted alkyl group having 1 to 8 carbon atoms, the group P1:- SO ₃ ^- , -SO ₃ H and an aromatic hydrocarbon group having 6 to 10 carbon atoms (the aromatic hydrocarbon group may also have a group selected from the group of P2) P2: -SO ₃ ^- , -SO ₃ H and carbon number 1 ~8 alkoxy], wherein the The cation of the skeleton (A) is a cation represented by the formula (1): In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁸ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted. 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 ; R ⁵ represents -SO ₃ H or -SO ₂ NR ⁹ R ¹⁰ ; m represents an integer of 0 to 5; when m is an integer of 2 or more, most of R ⁵ may be the same or different; and R ⁶ and R ⁷ are each independently, and represent a hydrogen atom or a carbon number. An alkyl group of 1 to 6; R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom; and 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 heterocyclic ring bonded to each other and forming a 3 to 10 membered ring containing a nitrogen atom; the hydrogen atom contained in the saturated hydrocarbon group may be substituted with -OH or a halogen atom, The -CH ₂ - contained in the saturated aliphatic hydrocarbon group may also be replaced by -O-, -CO-, -NH- or -NR ⁸ -]. The salt of claim 1, wherein R ⁶ and R ⁷ are each a hydrogen atom. A dye which is used as an active ingredient with a salt according to any one of claims 1 to 2. A coloring composition comprising a dye as in claim 3 of the scope of the patent application.