JP5861418B2 - Compound - Google Patents

Description

  The present invention relates to compounds useful as dyes.

The dye is used for color display using reflected light or transmitted light in fields such as a liquid crystal display device and an ink jet. As such a dye, for example, a compound represented by the following formula is known (Synthesis Example 3 of Patent Document 1).

JP 2010-32999 A

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

（式（１）中、
Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、−Ｒ^１３又は炭素数６〜１０の芳香族炭化水素基を表す。該炭素数６〜１０の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^１３、−ＯＨ、−ＯＲ^１３、−ＳＯ_３ ⁻、−ＳＯ_３Ｎａ、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^１３、−ＳＯ_３Ｈ、−ＳＯ_３Ｒ^１３又は−ＳＯ_２ＮＲ^９Ｒ^１０で置換されていてもよい。
Ｒ^３〜Ｒ^５は、それぞれ独立に、−ＳＯ_２ＮＲ^１１Ｒ^１２を表す。
Ｒ^６〜Ｒ^８は、それぞれ独立に、ハロゲン原子、−Ｒ^１３、−ＯＨ、−ＯＲ^１３、−ＳＯ_３ ⁻、−ＳＯ_３Ｎａ、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^１３、−ＳＯ_３Ｈ、−ＳＯ_３Ｒ^１３を表す。
Ｒ^９〜Ｒ^１１は、それぞれ独立に、水素原子又は炭素数１〜１０の飽和炭化水素基を表す。該炭素数１〜１０の飽和炭化水素基に含まれる水素原子は、−ＯＨ、−ＯＲ^１３、ハロゲン原子又は炭素数３〜１０の飽和環状エーテル基で置換されていてもよい。
Ｒ^１２は、炭素数１〜１０の飽和炭化水素基を表し、該炭素数１〜１０の飽和炭化水素基に含まれる水素原子は、−ＯＲ^１４で置換されている。
Ｒ^１３は、炭素数１〜１０の飽和炭化水素基を表す。該炭素数１〜１０の飽和炭化水素基に含まれる水素原子は、−ＯＨ、ハロゲン原子又は炭素数３〜１０の飽和環状エーテル基で置換されていてもよい。
Ｒ^１４は、炭素数１〜１０の飽和炭化水素基を表し、該炭素数１〜１０の飽和炭化水素基に含まれる水素原子は、炭素数３〜１０の飽和環状エーテル基で置換されている。
ｍ、ｎ、ｐ、ｑ、ｓ及びｔは、それぞれ独立に０〜５の整数を表す。
但し、ｍ＋ｑは５以下であり、ｎ＋ｓは５以下であり、ｐ＋ｔは５以下であり、ｍ＋ｎ＋ｐは１以上である。
ｍが２以上である場合、複数のＲ^３は、同一であっても異なっていてもよい。
ｎが２以上である場合、複数のＲ^４は、同一であっても異なっていてもよい。
ｐが２以上である場合、複数のＲ^５は、同一であっても異なっていてもよい。
ｑが２以上である場合、複数のＲ^６は、同一であっても異なっていてもよい。
ｓが２以上である場合、複数のＲ^７は、同一であっても異なっていてもよい。
ｔが２以上である場合、複数のＲ^８は、同一であっても異なっていてもよい。
Ｘは、ハロゲン原子を表す。ａは、０又は１を表す。） The present invention includes the inventions described in [1] to [8] below.
[1] A compound represented by formula (1).

(In the formula (1),
R ¹ and R ² each independently represents a hydrogen atom, —R ^13, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms is a halogen atom, —R ¹³ , —OH, —OR ¹³ , —SO ₃ ^— , —SO ₃ Na, —CO ₂ H, —CO ₂ R _{^13, -SO} 3 _H, optionally substituted by -SO ^{3 R 13} or _-SO 2 ^NR 9 ^{R 10.}
R ^{3 to} R ⁵ each independently represent —SO ₂ NR ¹¹ R ¹² .
R ^{6 to} R ⁸ are each independently a halogen atom, —R ¹³ , —OH, —OR ¹³ , —SO ₃ ^— , —SO ₃ Na, —CO ₂ H, —CO ₂ R ¹³ , —SO ₃ H represents a _-SO 3 ^{R 13.}
R ^{9 to} R ¹¹ each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with —OH, —OR ¹³ , a halogen atom, or a saturated cyclic ether group having 3 to 10 carbon atoms.
R ¹² represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms is substituted with —OR ¹⁴ .
R ¹³ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with —OH, a halogen atom, or a saturated cyclic ether group having 3 to 10 carbon atoms.
R ¹⁴ represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms is substituted with a saturated cyclic ether group having 3 to 10 carbon atoms. .
m, n, p, q, s and t each independently represent an integer of 0 to 5.
However, m + q is 5 or less, n + s is 5 or less, p + t is 5 or less, and m + n + p is 1 or more.
When m is 2 or more, the plurality of R ³ may be the same or different.
When n is 2 or more, the plurality of R ⁴ may be the same or different.
When p is 2 or more, the plurality of R ⁵ may be the same or different.
When q is 2 or more, the plurality of R ⁶ may be the same or different.
When s is 2 or more, the plurality of R ⁷ may be the same or different.
When t is 2 or more, the plurality of R ⁸ may be the same or different.
X represents a halogen atom. a represents 0 or 1. )

（式中、＊は結合手を表す。） [2] The compound according to [1], wherein R ¹ and R ² are both hydrogen atoms.
[3] The compound according to [1] or [2], wherein R ¹² is a group selected from the following groups.

(In the formula, * represents a bond.)

[4] A dye comprising the compound according to any one of [1] to [3] as an active ingredient.
[5] A coloring composition containing the dye according to [4].
[6] A coating film formed using the colored composition according to [5].
[7] A color filter formed using the colored composition according to [5].
[8] The color filter according to [7], which is formed by a photolithography method.

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

（式（１）中、
Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、−Ｒ^１３又は炭素数６〜１０の芳香族炭化水素基を表す。該炭素数６〜１０の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^１３、−ＯＨ、−ＯＲ^１３、−ＳＯ_３ ⁻、−ＳＯ_３Ｎａ、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^１３、−ＳＯ_３Ｈ、−ＳＯ_３Ｒ^１３又は−ＳＯ_２ＮＲ^９Ｒ^１０で置換されていてもよい。
Ｒ^３〜Ｒ^５は、それぞれ独立に、−ＳＯ_２ＮＲ^１１Ｒ^１２を表す。
Ｒ^６〜Ｒ^８は、それぞれ独立に、ハロゲン原子、−Ｒ^１３、−ＯＨ、−ＯＲ^１３、−ＳＯ_３ ⁻、−ＳＯ_３Ｎａ、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^１３、−ＳＯ_３Ｈ、−ＳＯ_３Ｒ^１３を表す。
Ｒ^９〜Ｒ^１１は、それぞれ独立に、水素原子又は炭素数１〜１０の飽和炭化水素基を表す。該炭素数１〜１０の飽和炭化水素基に含まれる水素原子は、−ＯＨ、−ＯＲ^１３、ハロゲン原子又は炭素数３〜１０の飽和環状エーテル基で置換されていてもよい。
Ｒ^１２は、炭素数１〜１０の飽和炭化水素基を表し、該炭素数１〜１０の飽和炭化水素基に含まれる水素原子は、−ＯＲ^１４で置換されている。
Ｒ^１３は、炭素数１〜１０の飽和炭化水素基を表す。該炭素数１〜１０の飽和炭化水素基に含まれる水素原子は、−ＯＨ、ハロゲン原子又は炭素数３〜１０の飽和環状エーテル基で置換されていてもよい。
Ｒ^１４は、炭素数１〜１０の飽和炭化水素基を表し、該炭素数１〜１０の飽和炭化水素基に含まれる水素原子は、炭素数３〜１０の飽和環状エーテル基で置換されている。
ｍ、ｎ、ｐ、ｑ、ｓ及びｔは、それぞれ独立に０〜５の整数を表す。
但し、ｍ＋ｑは５以下であり、ｎ＋ｓは５以下であり、ｐ＋ｔは５以下であり、ｍ＋ｎ＋ｐは１以上である。
ｍが２以上である場合、複数のＲ^３は、同一であっても異なっていてもよい。
ｎが２以上である場合、複数のＲ^４は、同一であっても異なっていてもよい。
ｐが２以上である場合、複数のＲ^５は、同一であっても異なっていてもよい。
ｑが２以上である場合、複数のＲ^６は、同一であっても異なっていてもよい。
ｓが２以上である場合、複数のＲ^７は、同一であっても異なっていてもよい。
ｔが２以上である場合、複数のＲ^８は、同一であっても異なっていてもよい。
Ｘは、ハロゲン原子を表す。ａは、０又は１を表す。） The compound of the present invention is a compound represented by formula (1) (hereinafter sometimes referred to as compound (1)). The compounds of the present invention include tautomers and salts thereof.

(In the formula (1),
R ¹ and R ² each independently represents a hydrogen atom, —R ^13, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms is a halogen atom, —R ¹³ , —OH, —OR ¹³ , —SO ₃ ^— , —SO ₃ Na, —CO ₂ H, —CO ₂ R _{^13, -SO} 3 _H, optionally substituted by -SO ^{3 R 13} or _-SO 2 ^NR 9 ^{R 10.}
R ^{3 to} R ⁵ each independently represent —SO ₂ NR ¹¹ R ¹² .
R ^{6 to} R ⁸ are each independently a halogen atom, —R ¹³ , —OH, —OR ¹³ , —SO ₃ ^— , —SO ₃ Na, —CO ₂ H, —CO ₂ R ¹³ , —SO ₃ H represents a _-SO 3 ^{R 13.}
R ^{9 to} R ¹¹ each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with —OH, —OR ¹³ , a halogen atom, or a saturated cyclic ether group having 3 to 10 carbon atoms.
R ¹² represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms is substituted with —OR ¹⁴ .
R ¹³ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with —OH, a halogen atom, or a saturated cyclic ether group having 3 to 10 carbon atoms.
R ¹⁴ represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms is substituted with a saturated cyclic ether group having 3 to 10 carbon atoms. .
m, n, p, q, s and t each independently represent an integer of 0 to 5.
However, m + q is 5 or less, n + s is 5 or less, p + t is 5 or less, and m + n + p is 1 or more.
When m is 2 or more, the plurality of R ³ may be the same or different.
When n is 2 or more, the plurality of R ⁴ may be the same or different.
When p is 2 or more, the plurality of R ⁵ may be the same or different.
When q is 2 or more, the plurality of R ⁶ may be the same or different.
When s is 2 or more, the plurality of R ⁷ may be the same or different.
When t is 2 or more, the plurality of R ⁸ may be the same or different.
X represents a halogen atom. a represents 0 or 1. )

  Examples of the halogen atom represented by X in Formula (1) include fluorine, chlorine, and bromine.

Examples of the saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ^{9 to} R ¹⁴ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl Octyl, 2-ethylhexyl, cyclooctyl, nonyl, decanyl, tricyclodecanyl and the like.

Examples of the group in which the hydrogen atom contained in the saturated hydrocarbon group is substituted with a saturated cyclic ether group having 3 to 10 carbon atoms include groups represented by the following formulas.

Examples of the group in which the hydrogen atom contained in the saturated hydrocarbon group is substituted with —OH or a halogen atom include groups represented by the following formulae.

Examples of the group in which the hydrogen atom contained in the saturated hydrocarbon group represented by R ^{9 to} R ¹¹ is substituted with —OR ¹³ include methoxypropyl, ethoxypropyl, hexyloxypropyl, 2-ethylhexyloxypropyl, methoxyhexyl. , Ethoxypropyl and the like.

（式中、＊は結合手を表す。） R ¹² is preferably a group selected from the following groups.

(In the formula, * represents a bond.)

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ¹ and R ² include phenyl and naphthyl.

（式中、＊は結合手を表す。） Examples of —SO ₃ R ¹³ include methanesulfonyl, ethanesulfonyl, hexanesulfonyl, decanesulfonyl, and the like. Moreover, group represented by a following formula is also mentioned.

(In the formula, * represents a bond.)

（式中、＊は結合手を表す。） —CO ₂ R ¹³ includes methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, isobutyloxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl, Hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, cyclooctyloxycarbonyl, nonyloxycarbonyl, decanyloxycarbonyl, tricyclodecanyloxycarbonyl, methoxypropyl Oxycarbonyl, ethoxypropyloxycarbonyl, f Siloxy propyl oxycarbonyl, 2-ethylhexyloxy propyloxy, methoxy hexyloxycarbonyl and the like. Moreover, group represented by a following formula is also mentioned.

(In the formula, * represents a bond.)

The -SO ₂ NR ⁹ R ^10, sulfamoyl, methanesulfonyl sulfamoyl, ethane sulfamoyl, propane sulfamoyl, isopropane sulfamoyl, butane sulfamoyl, isobutane sulfamoyl, pen wardrobe sulfamoyl, isopentanol chest Alpha Moyl, neopentanesulfamoyl, cyclopentanesulfamoyl, hexanesulfamoyl, cyclohexanesulfamoyl, heptanesulfamoyl, cycloheptanesulfamoyl, octanessulfamoyl, 2-ethylhexanesulfamoyl, 1, 5-Dimethylhexanesulfamoyl, cyclooctanesulfamoyl, nonanesulfamoyl, decanesulfamoyl, tricyclodecanesulfamoyl, methoxypropanesulfamoyl, ethoxypropanes Famoyl, propoxypropane sulfamoyl, isopropoxypropane sulfamoyl, hexyloxypropane sulfamoyl, 2-ethylhexyloxypropane sulfamoyl, methoxyhexanesulfamoyl, 3-phenyl-1-methylpropanesulfamoyl, etc. Is mentioned. Moreover, group represented by a following formula is also mentioned.

In the above formula, X ¹ represents a halogen atom. Examples of the halogen atom for X ¹ include a fluorine atom, a chlorine atom, and a bromine atom.

R ¹ and R ² are preferably both hydrogen atoms.

Examples of —SO ₂ NR ¹¹ R ¹² include a group represented by the following formula.

R ^{3 to} R ⁵ are preferably groups selected from the following groups.

Specific examples of compound (1) are shown below.

Compound (1) is, for example, a dye or dye intermediate having —SO ₃ H is chlorinated by a conventional method, and the obtained dye or dye intermediate having —SO ₂ Cl is represented by R ¹¹ R ¹² —NH. It can be produced by reacting with an amine.

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.

  As a method for forming a color filter pattern using the colored composition of the present invention, for example, the colored composition of the present invention is applied to a substrate or another resin layer (for example, another formed on the substrate in advance). A coating composition is formed by removing volatile components such as a solvent to form a coating film, exposing the coating film through a photomask, and developing the film (that is, a photolithographic method) And a method using an inkjet apparatus that does not require a photolithographic method. Photolithographic methods are preferred.

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.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “%” and “parts” are by weight and parts by weight unless otherwise specified.

滴下終了後、２０℃以下に維持しながら同温度で３時間維持して反応させ、その後も攪拌下２０℃以下に維持しながら、Ｎ−ブチルエタノールアミン２４．９部及びトリエチルアミン５４．１部の混合液を滴下して加えた。その後、同温度で５時間攪拌して反応させた。次いで得られた反応混合物をロータリーエバポレーターで溶媒留去した後、メタノールを少量加えて激しく攪拌した。この混合物を、３０％酢酸水溶液９００部の中に攪拌しながら加えて、結晶を析出させた。析出した結晶を濾別し、イオン交換水でよく洗浄し、６０℃で減圧乾燥して、混合物Ａ１（化合物Ａ１−１〜化合物Ａ１−８の混合物）４６．５部を得た。

Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 50.0 parts of a dye represented by the formula A0 (manufactured by Chugai Kasei), 360 parts of chloroform and 24.5 parts of N, N-dimethylformamide, and stirred at 20 ° C. While maintaining the following, 29.9 parts of thionyl chloride was added dropwise.

After completion of the dropwise addition, the reaction was continued for 3 hours at the same temperature while maintaining the temperature at 20 ° C. or lower, and thereafter, 24.9 parts of N-butylethanolamine and 54.1 parts of triethylamine were maintained at 20 ° C. or lower with stirring. The mixture was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to 900 parts of a 30% aqueous acetic acid solution with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion exchange water, and dried under reduced pressure at 60 ° C. to obtain 46.5 parts of a mixture A1 (mixture of compound A1-1 to compound A1-8).

Example 1
A flask equipped with a condenser and a stirrer was charged with 1500 parts of a 50% aqueous sodium hydroxide solution and 50.0 parts of tetrabutylammonium hydrogen sulfate, while maintaining the temperature at 20 ° C. or lower with stirring, 1500 parts of tetrahydrofuran, synthesis example 2.0 parts of the mixture A1 (mixture of compound A1-1 to compound A1-8) obtained in 1 and 21.3 parts of 3- (chloromethyl) -3-methyloxetane were added. After the addition, the temperature was raised to 20 ° C., the same temperature was maintained for 12 hours, and the reaction was carried out with vigorous stirring. Next, 2000 parts of saturated saline was added to the resulting reaction solution for washing. The organic solvent layer separated using the separatory funnel was further washed with 2000 parts of ion-exchanged water. About the organic-solvent layer isolate | separated using the separating funnel, distillation was implemented using the rotary evaporator. To the obtained viscous solution, 15 parts of tetrahydrofuran was added and stirred vigorously. This mixture was added to 750 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration and washed thoroughly with ion exchange water. The obtained product was dried under reduced pressure at 60 ° C. to obtain 1.5 parts of dye A2 (mixed dye of dye A2-1 to dye A2-8).

Dissolve 0.35 g of dye A2 (mixed dye of dye A2-1 to dye A2-8) in ethyl lactate to a volume of 250 cm ³ , of which 2 cm ³ is diluted with ion-exchanged water to a volume of 100 cm ³ ( The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.3 (arbitrary unit) at λmax = 526 nm.

Example 2
In a flask equipped with a condenser and a stirrer, at room temperature, 1.00 part of dye A1 (mixed dye of dye A1-1 to dye A1-8), 0.01 part of benzyltriethylammonium chloride, N-methylpyrrolidone 10 Department was put in. The solution was heated to 60 ° C. while stirring to obtain a homogeneous solution, 0.25 part of epichlorohydrin was added, and the mixture was stirred at the same temperature for 5 minutes. Next, 0.11 part of pulverized sodium hydroxide powder was added to the reaction solution, and the reaction was further performed by stirring for 12 hours at the same temperature. The mixture was added to 900 parts of a 30% aqueous acetic acid solution with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion exchange water, and dried under reduced pressure at 60 ° C. to obtain 0.96 parts of Dye A3 (mixed dye of Dye A3-1 to Dye A3-8).

The absorption spectrum of the dye A3 was measured in the same manner as the dye A2 of Example 1.
Absorption spectrum: Absorbance 2.4 (arbitrary unit) was exhibited at λmax = 527 nm.

Comparative Example 1
Dye B1 (mixed dye of dye B1-1 to dye B1-8) was obtained by the method described in Synthesis Example 3 of Patent Document 1.

<Evaluation of solubility in solvent>
The solubility of the dyes obtained in Example 1, Example 2 and Comparative Example 1 in the solvent was determined as follows.

In a 50 mL sample tube, each dye is mixed with each solvent shown in Table 1 so that the mixing ratio is 5% (W / V), 10% (W / V), and 15% (W / V), After sealing, the mixture was shaken with an ultrasonic shaker at 40 ° C. for 10 minutes. Then, after standing at room temperature for 30 minutes, the mixture was filtered to check for insoluble matters.
1% (W / V) adjusted mixed solution with insoluble matter is less than 1% solubility (x), 1% (W / V) adjusted mixed solution is free of insoluble matter and 5% (W / V) The mixed solution with the insoluble matter in the adjusted mixed solution has a solubility of less than 1 to 5% (Δ), and the mixed solution adjusted with 5% (W / V) has no insoluble matter and 10% (W / V) ) The adjusted mixed solution with insoluble matter is less than 5-10% solubility (◯), and the 10% (W / V) adjusted mixed solution without insoluble matter is taken as 10% solubility or higher ( ◎). The results are shown in Table 1.

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

Claims (8)

The compound represented by Formula (1).

(In the formula (1),
R ¹ and R ² each independently represents a hydrogen atom, —R ^13, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms is a halogen atom, —R ¹³ , —OH, —OR ¹³ , —SO ₃ ^— , —SO ₃ Na, —CO ₂ H, —CO ₂ R _{^13, -SO} 3 _H, optionally substituted by -SO ^{3 R 13} or _-SO 2 ^NR 9 ^{R 10.}
R ^{3 to} R ⁵ each independently represent —SO ₂ NR ¹¹ R ¹² .
R ^{6 to} R ⁸ are each independently a halogen atom, —R ¹³ , —OH, —OR ¹³ , —SO ₃ ^— , —SO ₃ Na, —CO ₂ H, —CO ₂ R ¹³ , —SO ₃ H represents a _-SO 3 ^{R 13.}
R ^{9 to} R ¹¹ each independently represent a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with —OH, —OR ¹³ , a halogen atom, or a saturated cyclic ether group having 3 to 10 carbon atoms.
R ¹² represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms is substituted with —OR ¹⁴ .
R ¹³ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with —OH, a halogen atom, or a saturated cyclic ether group having 3 to 10 carbon atoms.
R ¹⁴ represents a saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms is substituted with a saturated cyclic ether group having 3 to 10 carbon atoms. .
m, n, p, q, s and t each independently represent an integer of 0 to 5.
However, m + q is 5 or less, n + s is 5 or less, p + t is 5 or less, and m + n + p is 1 or more.
When m is 2 or more, the plurality of R ³ may be the same or different.
When n is 2 or more, the plurality of R ⁴ may be the same or different.
When p is 2 or more, the plurality of R ⁵ may be the same or different.
When q is 2 or more, the plurality of R ⁶ may be the same or different.
When s is 2 or more, the plurality of R ⁷ may be the same or different.
When t is 2 or more, the plurality of R ⁸ may be the same or different.
X represents a halogen atom. a represents 0 or 1. ) The compound according to claim 1, wherein R ¹ and R ² are both hydrogen atoms. The compound according to claim 1 or 2, wherein R ¹² is a group selected from the following groups.

(In the formula, * represents a bond.)   The dye which uses the compound in any one of Claims 1-3 as an active ingredient.   A coloring composition comprising the dye according to claim 4.   The coating film formed using the coloring composition of Claim 5.   A color filter formed using the colored composition according to claim 5.   The color filter according to claim 7, which is formed by a photolithography method.