JP5831135B2 - Compound - Google Patents

Description

  The present invention relates to compounds useful as dyes.

For example, dyes are used for color display using reflected light or transmitted light in fields such as fiber materials, liquid crystal display devices, and inkjets. As such a dye, for example, a compound represented by the following formula is known (Patent Document 1 Example 1).

JP 2011-16921 A

  The above known compounds have not always been sufficiently satisfactory in solubility in organic solvents.

［式（Ｉ）中、
Ｒ^１及びＲ^２は、互いに独立に、水素原子、水酸基又はスルホ基を表す。
Ｒ^３は、水素原子、ハロゲン原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、ニトロ基、シアノ基又は水酸基を表す。
Ｒ^４は、水素原子又は＊−ＣＯ−Ｌ−Ｘ−Ｒ^５で示される基を表す。
Ｌは、炭素数１〜８のアルカンジイル基を表す。
Ｘは、−ＣＯ−Ｏ−を表す。
Ｒ^５は、水素原子、メチル基又はエチル基を表す。
＊は、窒素原子との結合手を表す。］
で表される化合物。
［２］Ｒ^１が、水酸基である［１］記載の化合物。
［３］Ｒ^３が、水素原子である［１］又は［２］記載の化合物。
［４］Ｒ^４が、水素原子である［１］〜［３］のいずれか記載の化合物。
［５］Ｒ^４が＊−ＣＯ−Ｌ−Ｘ−Ｒ^５で示される基であり、Ｒ^５が水素原子である［１］〜［３］のいずれか記載の化合物。
［６］［１］〜［５］のいずれか記載の化合物を有効成分とする染料。
［７］［６］記載の染料を含む着色組成物。 The present invention includes the inventions described in [1] to [6] below.
[1] Formula (I)

[In the formula (I),
R ¹ and R ² each independently represent a hydrogen atom, a hydroxyl group or a sulfo group.
R ³ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group, a cyano group, or a hydroxyl group.
R ⁴ represents a hydrogen atom or a group represented by * —CO—L—X—R ⁵ .
L represents an alkanediyl group having 1 to 8 carbon atoms.
X represents -CO-O-.
R ⁵ represents a hydrogen atom, a methyl group or an ethyl group.
* Represents a bond with a nitrogen atom. ]
A compound represented by
[2] The compound according to [1], wherein R ¹ is a hydroxyl group.
[3] The compound according to [1] or [2], wherein R ³ is a hydrogen atom.
[4] The compound according to any one of [1] to [3], wherein R ⁴ is a hydrogen atom.
[5] The compound according to any one of [1] to [3], wherein R ⁴ is a group represented by * —CO—L—X—R ⁵ , and R ⁵ is a hydrogen atom.
[6] A dye comprising the compound according to any one of [1] to [5] as an active ingredient.
[7] A coloring composition containing the dye according to [6].

  The compound of the present invention is excellent in solubility in an organic solvent.

［式（Ｉ）中、
Ｒ^１及びＲ^２は、互いに独立に、水素原子、水酸基又はスルホ基を表す。
Ｒ^３は、水素原子、ハロゲン原子、炭素数１〜８のアルキル基、炭素数１〜８のアルコキシ基、ニトロ基、シアノ基又は水酸基を表す。
Ｒ^４は、水素原子又は＊−ＣＯ−Ｌ−Ｘ−Ｒ^５で示される基を表す。
Ｌは、炭素数１〜８のアルカンジイル基を表す。
Ｘは、−ＣＯ−Ｏ−を表す。
Ｒ^５は、水素原子、メチル基又はエチル基を表す。
＊は、窒素原子との結合手を表す。］ The compound of the present invention is a compound represented by formula (I) (hereinafter sometimes referred to as compound (I)). The compounds of the present invention include tautomers and salts thereof. Examples of such salts include alkali metal salts such as lithium salts, potassium salts, and sodium salts.

[In the formula (I),
R ¹ and R ² each independently represent a hydrogen atom, a hydroxyl group or a sulfo group.
R ³ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group, a cyano group, or a hydroxyl group.
R ⁴ represents a hydrogen atom or a group represented by * —CO—L—X—R ⁵ .
L represents an alkanediyl group having 1 to 8 carbon atoms.
X represents -CO-O-.
R ⁵ represents a hydrogen atom, a methyl group or an ethyl group.
* Represents a bond with a nitrogen atom. ]

［式（ＩＩ）中、Ｒ^１〜Ｒ^４は、それぞれ上記と同じ意味を表す。］ Of the compounds (I), the compound represented by the formula (II) is preferable from the viewpoint of obtaining raw materials.

[In formula (II), R ^{1 to} R ⁴ each represent the same meaning as described above. ]

R ¹ and R ^2, independently of each other, hydrogen atom, a hydroxyl group or a sulfo group, preferably R ¹ is a hydroxyl group, and more preferably R ² R ¹ is a hydroxyl group is a sulfo group.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ³ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and n-pentyl group. N-hexyl group, n-heptyl group, n-octyl group, 1-methylbutyl group, 1,1,3,3-tetramethylbutyl group, 1,5-dimethylhexyl group, 2-ethylhexyl group and the like. .

  Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and the like. .

  Examples of the halogen atom include a chlorine atom and a bromine atom.

R ³ is preferably a hydrogen atom.

R ⁵ is a hydrogen atom, a methyl group or an ethyl group, and is preferably a hydrogen atom.

  Examples of the alkanediyl group having 1 to 8 carbon atoms represented by L include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, and a butane-1,4-diyl group. Group, butane-1,3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group and the like. .

The orientation of the -CO-O- bond in X may be either. That is, it may be * -CO-O- or * -O-CO-. Here, * represents a bond with L.
Of these, X is preferably * —CO—O— because the compound of the present invention is easy to produce.

（式（Ｉ−Ａ）中、Ｒ^１、Ｒ^２及びＲ^４は、それぞれ上記と同じ意味を表す。＊は、窒素原子との結合手を表す。）
で表される基としては、例えば、それぞれ式（ｅ−１）〜式（ｅ−７）、式（ｅ−１１）〜式（ｅ−１４）、式（ｅ−２１）〜式（ｅ−２４）、式（ｅ−３１）〜式（ｅ−３４）及び式（ｅ−４１）〜式（ｅ−４４）で表される基が挙げられる。これらの基のうち、耐光性の観点から式（ｅ−１）で表される基又は式（ｅ−１１）で表される基が好ましい。

In formula (I),

(In the formula (IA), R ¹ , R ² and R ⁴ each have the same meaning as above. * Represents a bond with a nitrogen atom.)
Examples of the group represented by formula (e-1) to formula (e-7), formula (e-11) to formula (e-14), and formula (e-21) to formula (e- 24), groups represented by formula (e-31) to formula (e-34) and formula (e-41) to formula (e-44). Among these groups, the group represented by the formula (e-1) or the group represented by the formula (e-11) is preferable from the viewpoint of light resistance.

［式（Ｉ−Ｂ）中、Ｒ^３は、上記と同じ意味を表す。＊は、窒素原子との結合手を表す。］
で表される基としては、例えば、それぞれ式（ｆ−１）〜式（ｆ−１２）で表される基が挙げられる。 In formula (I),

[In formula (IB), R ³ represents the same meaning as described above. * Represents a bond with a nitrogen atom. ]
As group represented by, group represented by a formula (f-1)-a formula (f-12), respectively is mentioned, for example.

Examples of compound (I) include compound (I-1) to compound (I-110). In Tables 1 to 3, column G represents the numbers of the groups represented as examples of the group represented by formula (IB) above, and column D represents the formula (IA) above. Represents the number of the formula of the group shown as an example of the group.

  Especially, since the solubility to an organic solvent is especially high, a compound (I-1) or a compound (I-55) is preferable.

A method for producing compound (I) will be described.
The azo compound can be produced by diazo coupling of a diazonium salt and a naphthylamine compound (see JP 2011-16921 A).

［式（ａ１）及び式（ａ２）中、Ｒ^３は、上記と同じ意味を表す。Ａ^１は、無機アニオン又は有機アニオンを表す。］ The diazonium salt represented by the formula (a2) can be obtained, for example, by diazotizing the amine represented by the formula (a1) with nitrous acid, nitrite or nitrite.

[In Formula (a1) and Formula (a2), R ³ represents the same meaning as described above. A ¹ represents an inorganic anion or an organic anion. ]

Examples of the inorganic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, and the like. Examples of the organic anion, for ^{_{example, CH 3 COO -, C 6}} H 5 COO - , and the like. Preferably chloride, _bromide, CH 3 COO ^- is.

［式（ｂ１）中、Ｒ^１及びＲ^２は、それぞれ上記と同じ意味を表す。］ R ⁴ is a hydrogen atom by diazo coupling a diazonium salt represented by the formula (a2) and a compound represented by the formula (b1) (hereinafter sometimes referred to as “compound (b1)”). Compound (I) can be produced. The reaction temperature is preferably -5 ° C to 60 ° C, more preferably 0 ° C to 30 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours. This reaction is preferably carried out in the presence of an aqueous solvent. As the aqueous solvent, water is more preferable.

[In formula (b1), R ¹ and R ² each represent the same meaning as described above. ]

Next, a method for producing compound (I) in which R ⁴ is a group represented by * —CO—L—X—R ⁵ will be described.

［式（ｂ２）及び式（ｂ３）中、Ｒ^１、Ｒ^２、Ｒ^５、Ｌ及びＸは、それぞれ上記と同じ意味を表す。Ｚは塩素原子又は臭素原子を表す。］ By reacting the compound (b1) with a compound represented by the formula (b2) (hereinafter sometimes referred to as “compound (b2)”), a compound represented by the formula (b3) (hereinafter referred to as “compound (b3)”). Can be obtained). The reaction temperature is preferably 0 ° C to 80 ° C, more preferably 10 ° C to 50 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours. This reaction is preferably carried out in the presence of an aqueous solvent. As the aqueous solvent, water is more preferable.

[In formula (b2) and formula (b3), R ¹ , R ² , R ⁵ , L and X each have the same meaning as described above. Z represents a chlorine atom or a bromine atom. ]

［式（ｂ４）中、Ｌは上記と同じ意味を表す。］ When -X-R ⁵ is -COOH, a compound represented by the formula (b4) (hereinafter sometimes referred to as "compound (b4)") can be used instead of the compound (b2).

[In formula (b4), L represents the same meaning as described above. ]

  The amount of compound (b2) or compound (b4) to be used is preferably 1 mol or more and 1.5 mol or less, more preferably 1 mol, per 1 mol of compound (b1), from the viewpoint of reaction selectivity. The amount is 1.2 mol or less.

  In the reaction, an acidic catalyst can be used in order to make the reaction proceed smoothly. Examples of the acidic catalyst include mineral acids such as sulfuric acid and hydrochloric acid.

  Although the usage-amount of these catalysts is arbitrary, Preferably it is 0.01 mol or more and 4 mol or less with respect to 1 mol of compounds (b1), More preferably, it is 0.8-2 mol.

R ⁴ is a group represented by * —CO—L—X—R ⁵ by diazo coupling a diazonium salt represented by the formula (a2) and a compound represented by the formula (b3). Compound (I) can be produced. The reaction temperature is preferably -5 ° C to 60 ° C, more preferably 0 ° C to 30 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours. This reaction is preferably carried out in the presence of an aqueous solvent. As the aqueous solvent, water is more preferable.

  The method for obtaining the target compound (I) from the reaction mixture is not particularly limited, and various known techniques can be employed. For example, if necessary, the reaction mixture can be mixed with water in the presence of an acid (for example, acetic acid and the like), and the precipitated crystals can be collected by filtration. The acid is preferably prepared by preparing an aqueous solution of the acid 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 20 ° C. or higher and 50 ° C. or lower, and further preferably 20 ° C. or higher and 30 ° C. or lower. Moreover, after adding a reaction mixture to the aqueous solution of an acid, it is preferable to further stir at the said 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 compound of the present invention thus obtained is useful as a dye. In addition, since the compound of the present invention has high solubility in 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.

The dye of the present invention is a dye containing the compound of the present invention 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 (A)”) and further contains a resin (B). More preferably, the colored composition of the present invention further contains a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).

In addition to the dye of the present invention, the colorant (A) 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 Examples thereof include 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 (A) 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 (A) is preferably 3 to 100% by mass.
The 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 (B) is not particularly limited, and any resin may be used. The resin (B) 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 (B) 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 (B) is preferably 5,000 to 35,000, and more preferably 6,000 to 30,000.
The acid value of the resin (B) is preferably 50 to 150, and more preferably 60 to 135.
Content of resin (B) 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 (C) 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 (D). For example, the compound etc. which have a polymerizable ethylenically unsaturated bond are mentioned.

The polymerizable compound (C) 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 polymerizable compound (C) may be used alone or in combination of two or more.
It is preferable that content of a polymeric compound (C) is 5-65 mass% with respect to solid content of a coloring composition, More preferably, it is 10-60 mass%.

As said polymerization initiator (D), 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 (D) may be used alone or in combination of two or more.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). 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 (E) include ether solvents, aromatic hydrocarbon solvents, ketone solvents, alcohol solvents, ester solvents, amide solvents, and the like.

  Examples of the ether solvent 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, B 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 hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.
Examples of the ketone solvent 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 alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, and the like.

  Examples of the ester solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl ester, methyl lactate, and ethyl lactate. , Butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionic acid Ethyl, 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 amide solvent 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 (E) 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.

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

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

  In the following examples, the structure of the compound was confirmed by NMR (JMM-ECA-500; manufactured by JEOL Ltd.). For the maximum absorption wavelength (λmax), an aqueous solution with a compound concentration of 0.1 g / ml was prepared using an acetonitrile / water mixed solvent (volume ratio 1: 1), and an ultraviolet-visible spectrophotometer (V-650DS; JASCO Corporation) )) (Quartz cell, optical path length: 1 cm).

[Example 1]
After adding 80 parts of water to 16.2 parts of 4-aminophthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.4 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 19.7 parts of 35% aqueous sodium nitrite solution was added, and then 26.2 parts of 35% hydrochloric acid was added little by little to dissolve and stirred for 2 hours to obtain a suspension containing a diazonium salt.

Subsequently, 23.9 parts of 6-amino-4-hydroxy-2-naphthalenesulfonic acid was suspended in 100 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise thereto using a pump over 15 minutes. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. The suspension was stirred for 1 hour and then stirred for 1 hour. The red solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 40.5 parts of a compound represented by the formula (I-1). When the maximum absorption wavelength of this compound was measured, λmax was 545 nm.

The structure of this compound was confirmed by ¹ H-NMR.
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ): 2.42 (2H, s), 7.31 to 7.63 (3H, m), 7.75 (1H, s), 7.83 (1H, s ), 8.35 (1H, s), 8.99 (1H, s), 12.84 (2H, s), 16.33 (1H, s).

[Example 2]
After adding 100 parts of water to 23.9 parts of 6-amino-4-hydroxy-2-naphthalenesulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.4 of succinic anhydride is added, and at 30 ° C. for 3 hours. Stir. After completion of the reaction, the resulting crystals were filtered to obtain 33.5 parts of a compound represented by the formula (g-1).

  After adding 80 parts of water to 16.2 parts of 4-aminophthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.4 parts of sodium hydroxide was added and dissolved. Under ice-cooling, 19.7 parts of 35% aqueous sodium nitrite solution was added, and then 26.2 parts of 35% hydrochloric acid was added little by little to dissolve and stirred for 2 hours to obtain a suspension containing a diazonium salt.

Next, 33.5 parts of the compound represented by the formula (g-1) was suspended in 100 parts of water, and the pH was adjusted to 9.0 using sodium hydroxide. The suspension containing the diazonium salt was added dropwise thereto using a pump over 15 minutes. After completion of dropping, the mixture was further stirred for 30 minutes to obtain a yellow suspension. The suspension was stirred for 1 hour and then stirred for 1 hour. The red solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 51.2 parts of a compound represented by the formula (I-55). When the maximum absorption wavelength of this compound was measured, λmax was 512 nm.

The structure of this compound was confirmed by ¹ H-NMR.
¹ H-NMR (500 MHz, δ value (ppm, TMS standard), DMSO-d ₆ ): 2.41 (2H, s), 2.63 (2H, s), 7.44 to 7.63 (3H, m), 7.75 (1H, s ), 7.83 (1H, s), 8.02 to 8.39 (3H, m), 8.69 (1H, s), 12.54 (2H, s), 15.83 (1H, s).

[Comparative Example 1]
According to the method described in Patent Document 1, a compound represented by the following formula (d-2) described in Example 1 was synthesized.

<Evaluation of solubility>
The solubility of each of the compounds obtained in Examples 1 and 2 and Comparative Example 1 in dimethylformamide (hereinafter abbreviated as DMF) and N-methylpyrrolidone (hereinafter abbreviated as NMP) was determined as follows.
In a 50 mL sample tube, the compound and the solvent were mixed in the following ratio, and then the sample tube was sealed and vibrated with an ultrasonic vibrator at 30 ° C. for 3 minutes. Then, after standing at room temperature for 30 minutes, suction filtration was performed, and the residue was visually observed. If no residue (that is, insoluble matter) could not be confirmed, the solubility was judged to be good and marked in Table 4, and if the residue could be confirmed, the solubility was judged to be poor. Marked with x.
0.5% compound 0.1 g, solvent 20 g
1% compound 0.1 g, solvent 10 g
3% Compound 0.3g, Solvent 10g
5% compound 0.1 g, solvent 2 g

Example 3
<Preparation of coloring composition>
(A) Colorant: Compound (I-1): Compound obtained 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 BASF Japan Ltd.) 15 parts (E-1) Solvent: 680 parts of dimethylformamide are mixed to obtain a colored composition.
Example 4
In Example 3, it replaced with the compound (I-1) obtained in Example 1 as a coloring agent, and it replaced with the compound (I-55) obtained in Example 2, and was carried out similarly to Example 3. A colored composition is obtained.

[Production of color filters]
On the glass, the colored composition obtained in Example 3 or 4 is applied by spin coating 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.

  According to the above results, it can be seen that the compound of the present invention exhibits high solubility in an organic solvent. In addition, if a colored composition containing the compound is used, it is possible to produce a high-quality color filter with less generation of foreign matters.

  The compound of the present invention is excellent in solubility in an organic solvent.

Claims (4)

Formula (I)

[In the formula (I),
R ¹ and R ² each independently represent a hydrogen atom, a hydroxyl group or a sulfo group.
R ³ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group, a cyano group, or a hydroxyl group.
R ⁴ represents a group represented by * —CO—L—X—R ⁵ .
L represents an alkanediyl group having 1 to 8 carbon atoms.
X represents -CO-O-.
R ⁵ represents a hydrogen atom.
* Represents a bond with a nitrogen atom. ]
A compound represented by The compound according to claim 1, wherein R ¹ is a hydroxyl group. The compound according to claim 1 or 2, wherein R ³ is a hydrogen atom. The dye which uses the compound in any one of Claims 1-3 as an active ingredient.