TWI491599B - Compounds and coloring compositions - Google Patents

Description

Compound and coloring composition

The present invention relates to a compound useful as a dye and a colored composition comprising the same.

In a color filter for a display device used in a liquid crystal display panel, an electroluminescence panel, a plasma display panel, or the like, a dye is always used as a colorant. As such a dye, for example, a dibenzopyran compound such as C.I. Basic Red 1 is known (Patent Document 1).

Patent Document 1: Japanese Patent Laid-Open No. 2001-106712

When a dye having a high color shifting property is used as a coloring agent for a color filter for a display device, the dye moves to a resin film containing no coloring agent such as a color filter or a protective layer of another color, thereby causing a display device. The display characteristics are reduced. Here, the term "transferability" means that the dye contained in the target material adheres to other materials or is absorbed by air or water vapor as a medium, but the above-mentioned dibenzopyran compound may not be sufficiently satisfied. The situation of dyeing.

That is, the present invention provides the following [1] to [6].

[1] A compound represented by formula (I),

[In the formula (I), L represents a divalent saturated hydrocarbon group having a carbon number of 1 to 20, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and -CH ₂ - contained in the saturated hydrocarbon group may also be Substituting -CO- or -O-; R ¹ and R ² each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or a carbon number which may have a substituent a thiol group of 2 to 18; R ³ to R ¹⁰ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, or a carbon number which may have a substituent of 6 to 10 The monovalent aromatic hydrocarbon group, -CH ₂ - contained in the aliphatic hydrocarbon group may be substituted by -O-; and R ¹¹ to R ¹⁴ each independently represent a hydrogen atom or a methyl group.

X ^1- and X ^2- represent an inorganic anion or an organic anion].

[2] The compound of [1], wherein the L-based carbon number is 5 to 15 alkanediyl, and the -CH ₂ - contained in the alkanediyl group may be substituted by -O-.

[3] A dye containing a compound such as [1] or [2] as a main component.

[4] A coloring composition comprising: at least one selected from the group consisting of a resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and a coloring agent containing the dye of [3].

[5] A color filter formed using the coloring composition of [4].

[6] A display device comprising the color filter of [5].

The compound of the present invention is a compound represented by the formula (I) (hereinafter sometimes referred to as "compound (I)").

[In the formula (I), L represents a divalent saturated hydrocarbon group having a carbon number of 1 to 20, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and -CH ₂ - contained in the saturated hydrocarbon group may also be Substituted by -CO- or -O-.

R ¹ and R ² each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or a fluorenyl group having 2 to 18 carbon atoms which may have a substituent.

R ³ to R ¹⁰ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. The -CH ₂ - contained in the aliphatic hydrocarbon group may also be substituted by -O-.

R ¹¹ to R ¹⁴ each independently represent a hydrogen atom or a methyl group.

X ^1- and X ^2- represent an inorganic anion or an organic anion].

L represents a divalent linear saturated hydrocarbon group having a carbon number of 1 to 20, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted by a halogen atom, and -CH ₂ - contained in the saturated hydrocarbon group may also be subjected to -CO- Or -O- substituted.

The saturated hydrocarbon group may be an alkanediyl group having 1 to 20 carbon atoms, a cycloalkanediyl group having 3 to 20 carbon atoms, and any of the groups having a carbon number of 4 to 20 in combination.

Examples of the alkanediyl group include a methylene group, an ethylidene group, a propylenediyl group, a propylenediyl group, a butyldiyl group, a pentanediyl group, a hexyldiyl group, a hexyldiyl group, a octyldiyl group, a fluorenyl group, and a decyl group. Tetralinediyl and eicosanediyl and the like.

As the -CH ₂ -O-substituted alkanediyl group, -(CH ₂ ) ₃ -O-(CH ₂ ) ₃ -, -(CH ₂ ) ₃ -O-(CH ₂ ) ₄ -O -(CH ₂ ) ₃ - and -(CH ₂ ) ₃ -O-(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -O-(CH ₂ ) ₃ -.

Examples of the cycloalkanediyl group include a cyclopentadienyl group, a cyclohexanediyl group, and a cyclooctyldiyl group.

Examples of the group in which the alkanediyl group and the cycloalkanediyl group are combined include the groups shown below.

As L, it is preferred that -CH ₂ - may also be substituted with -O-, and the alkyl group having 5 to 15 carbon atoms, and preferably -CH ₂ - may be substituted by -O- 5 to 15 the linear alkyl group, more preferably is CH ₂ - may be substituted -O- carbon atoms of straight-chain alkanediyl group of 6 to 10. Preferred examples of the group include -(CH ₂ ) ₆ -, -(CH ₂ ) ₁₀ -, -(CH ₂ ) ₃ -O-(CH ₂ ) ₃ -, -(CH ₂ ) ₃ -O- (CH ₂ ) ₄ -O-(CH ₂ ) ₃ - or -(CH ₂ ) ₃ -O-(CH ₂ ) ₂ -O-(CH ₂ ) ₂ -O-(CH ₂ ) ₃ -.

R ¹ and R ² each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or a fluorenyl group having 2 to 18 carbon atoms which may have a substituent.

The monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be any of a linear chain, a branched chain or a cyclic group. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number is preferably from 6 to 10, more preferably from 1 to 4.

Examples of the above monovalent aliphatic hydrocarbon group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a second butyl group, a third butyl group, and a methyl butyl group (for example). 1,1,3,3-tetramethylbutyl or the like), methylhexyl (1,5-dimethylhexyl, etc.), ethylhexyl (2-ethylhexyl, etc.), cyclopentyl, cyclohexyl, Methylcyclohexyl (2-methylcyclohexyl, etc.) and cyclohexylalkyl.

The hydrogen atom contained in the above monovalent aliphatic hydrocarbon group may be substituted with an alkoxy group having 1 to 8 carbon atoms or a carboxyl group. Examples of the monovalent aliphatic hydrocarbon group substituted with an alkoxy group having 1 to 8 carbon atoms include a propoxypropyl group (3-(isopropoxy)propyl group, etc.) and an alkoxypropyl group (3- (2-ethylhexyloxy)propyl, etc.). Examples of the C _1-16 aliphatic hydrocarbon group substituted by a carboxyl group include a 2-carboxyethyl group, a 3-carboxyethylpropyl group, and a 4-carboxybutyl group.

The hydrogen atom contained in the fluorenyl group having 2 to 18 carbon atoms may be substituted by an alkoxy group having 1 to 8 carbon atoms. The carbon number of the fluorenyl group having a carbon number of 2 to 18 which may have a substituent includes the number of carbon atoms of the substituent, and the number is preferably 6 to 10. Examples of the mercapto group which may have a substituent include an ethyl fluorenyl group, a benzamidine group, a methoxybenzylidene group (p-methoxybenzylidene group, etc.).

R ¹ and R ^{2 are} preferably a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms or a mercapto group having 2 to 5 carbon atoms. Preferred examples of the group include a hydrogen atom, an ethenyl group and a propyl group, and more preferably a hydrogen atom.

R ³ to R ¹⁰ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may be substituted, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted. The carbon number of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms does not include the carbon number of the substituent, and the number is 1 to 8, preferably 1 to 4. The carbon number of the monovalent aromatic hydrocarbon group having a carbon number of 6 to 10 does not include the carbon number of the substituent, and the number is 6 to 10, preferably 6 to 8.

The monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms may be any of a linear chain, a branched chain or a cyclic group. Examples of the aliphatic hydrocarbon group include those having 1 to 8 carbon atoms in the group represented by the monovalent aliphatic hydrocarbon group of R ¹ and R ² .

The -CH ₂ - contained in the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms may also be substituted by -O-. The hydrogen atom contained in the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms may be substituted with a halogen atom such as a fluorine atom.

R ³ to R ^{10 are} preferably a hydrogen atom, and -CH ₂ - may be an -O-substituted alkyl group having 1 to 6 carbon atoms. Preferred examples thereof include a hydrogen atom, a methyl group, an ethyl group, -(CH ₂ ) ₂ CH(CH ₃ ) ₂ , -(CH ₂ ) ₂ -O-CH ₃ , or -(CH ₂ ) ₃ - O-CH _{3 is more} preferably a hydrogen atom or an ethyl group.

R ¹¹ to R ¹⁴ each independently represent a hydrogen atom or a methyl group, and preferably a methyl group.

X ^- represents an inorganic anion or an organic anion. Examples of the inorganic anion or organic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorous acid ion, p-toluene ion, CH ₃ -COO ⁻ , and Ph-COO. ^- , CH ₃ -SO ₃ ^- , CF ₃ -SO ₃ ^-, etc., preferably include chloride ion, perchloric acid ion, CH ₃ -COO ^- , p-toluene ion, CF ₃ -SO ₃ ^- . In particular, since organic ions are useful in the case of being contained in a resin-curable compound, and are also non-metal salts, they are also useful in the field of emphasizing insulation.

The compound (I) includes a compound represented by the formula (I-1) to the formula (I-18). L in the table indicates that the bond bond on the right side is a bond to the nitrogen atom of -NR ¹ -.

The compound (I) is preferably R ³ and R ⁷ , R ⁴ and R ⁸ , R ⁵ and R ⁹ , R ⁶ and R ¹⁰ , R ¹¹ and R ¹³ , R ¹² and R ¹⁴ , X ¹ and X ² respectively. The compound of the same group, that is, the compound represented by the formula (I-0), more preferably a compound wherein R ¹ and R ² are the same. In the case of these compounds, the compound (I) can be easily produced.

In the formula (I-0), L, R ¹ to R ⁶ , R ¹¹ , R ¹² and X ^{1 have} the same meanings as described above. ]

The compound (I) can be produced by subjecting a compound represented by the formula (I-A) and a compound represented by the formula (I-A') to a solvent.

In the formula (IA) and the formula (I-A'), R ³ to R ¹⁴ , X ¹ and X ^{2 have} the same meanings as described above. Y ¹ and Y ² represent a hydroxyl group, -OR ²⁰ or a halogen atom. R ²⁰ represents an aliphatic hydrocarbon group having 1 to 8 carbon atoms. ]

And the compound represented by formula (I-B)

In the formula (IB), L, R ¹ and R ² represent the same meanings as described above. ]

The reaction was carried out at 0 to 250 °C.

Examples of the compound represented by the formula (IB) include ethylenediamine, butylenediamine, hexamethylenediamine, cyclohexanediamine, 1,12-diaminododecane, and 4,4-methylenebis ( 2-methylcyclohexylamine), isophorone diamine, 1,4-butanediol bis(3-aminopropyl)ether, diethylene glycol bis(3-aminopropyl)ether, and the like.

The compound represented by the formula (I-B) may be used singly or in combination of two or more. With respect to the total amount of the compound represented by the formula (IA) and the compound represented by the formula (I-A'), the compound represented by the formula (IB) is preferably used in an amount of 0.5 to 3 mol. ear.

In the case where Y ¹ and Y ² are a hydroxyl group, it is preferred to use the hydrochloride of the compound represented by the formula (IB).

Further, in the case where Y ¹ and Y ² are a hydroxyl group, it is preferred to use a known condensing agent. Examples of the condensing agent include (PhO) ₃ P, (PhO)PCl ₂ , PhPOCl ₂ , (C ₃ H ₇ ) ₃ P(O)O, POCl ₃ , SOCl ₂ -Et ₃ N, and Ph ₃ PC ₂ Cl. ₆ or the like is more preferably used in combination with pyridine in a alkylguanamine solvent. The amount of the condensing agent to be used is preferably from 2 to 10 mols, based on the total amount of the compound represented by the formula (IA) and the compound represented by the formula (I-A'). The pyridine is preferably used in an amount of from 20 to 80 mols per mol of the compound represented by the formula (IA) and the compound represented by the formula (I-A').

In the case where Y ¹ and Y ² are -OR ^20, it is preferred to add a known alkali catalyst. Examples of the base catalyst include sodium ethoxide and sodium hydride. The amount of the base catalyst to be used is preferably 0.01 to 2 moles based on the total amount of the compound represented by the formula (IA) and the compound represented by the formula (I-A').

The above reaction is carried out in a solvent. As the solvent, for example, water; ethers such as 1,4-dioxane (especially cyclic ethers); chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, and the like are preferable. Halogenated hydrocarbons such as dichloroethylene, trichloroethylene, perchloroethylene, dichloropropane, chloropentane, 1,2-dibromoethane; ketones such as acetone, methyl isobutyl ketone and cyclohexanone; benzene Carbonaceous aromatics such as toluene and xylene; N,N-dimethylformamide, N,N-dibutylformamide, N,N-dimethylacetamide, N-methylpyrrolidone Equivalent alkyl amides and the like. The solvent may be used singly or in combination of two or more. The solvent is preferably used in an amount of from 1 to 20 parts by mass, more preferably 2 parts by mass based on 1 part by mass of the total of the compound represented by the formula (IA) and the compound represented by the formula (I-A'). ~10 parts by mass.

The above reaction is preferably carried out under a nitrogen atmosphere or an argon atmosphere. It can also be carried out in air which is dried by using calcium chloride or the like.

The reaction temperature is preferably 0 to 250 ° C, more preferably 10 to 200 ° C. The reaction time is preferably from 1 to 25 hours, more preferably from 3 to 15 hours.

The order of addition of the compound represented by the formula (IA), the compound represented by the formula (I-A'), the compound represented by the formula (IB) and the solvent is not particularly limited, and it is preferred to include the formula (IA). The compound represented by the formula (IB) is added (dropwise) to the solution of the compound represented by the formula (I-A') and the solvent. In the case of using a condensing agent, it is preferred to add (drop) a solution containing a compound represented by the formula (IA), a compound represented by the formula (I-A'), a condensing agent, and a solvent. Compound represented by IB). In the case of using an alkali catalyst, it is preferred to add (drop) to a solution containing a compound represented by the formula (IA), a compound represented by the formula (I-A'), a base catalyst, and a solvent. a compound represented by the formula (IB).

The method of obtaining the compound (I) as the target compound from the reaction mixture obtained in the above manner is not particularly limited, and various known methods (such as acid precipitation or salting out) can be employed. The crystals collected by filtration are usually washed with water or the like and then dried. Further, it may be further purified by a known method such as recrystallization as needed.

Since the compound of the present invention exhibits high solubility, low transferability, and high spectroscopic concentration, it can be used as a dye in a fiber material, a liquid crystal display device or the like which performs color display by reflected light or transmitted light. Further, the compound of the present invention has a maximum absorption in a wavelength band of 500 to 600 nm when measuring an absorption spectrum, and thus can be used as a red or violet dye.

The dye of the present invention is a dye containing a compound of the present invention as a main component, and is a dye containing 50% by mass or more of the compound of the present invention.

The dye of the present invention may be the compound (I) alone, and it is preferred to mix two or more kinds of the dye of the compound (I). Among them, a dye obtained by mixing two or more kinds of compounds (I) different in L is more preferable. By combining these compounds, the solubility in a solvent is excellent. As a preferable combination of the compound (I), for example, a compound represented by the formula (I-1) and a compound represented by the formula (I-2).

A dye obtained by mixing two or more kinds of the compound (I) can be obtained by separately producing each compound (I) and then mixing them, or by preparing a mixture at the time of production. The latter can be produced, for example, by using two or more compounds represented by the formula (IB) in the reaction of the compound represented by the formula (IA) and the compound represented by the formula (I-A') and the formula (IB). Obtained as a mixture.

The coloring composition of the present invention is selected from the group consisting of a resin (hereinafter sometimes referred to as "resin (B)"), a photopolymerizable compound (hereinafter sometimes referred to as "photopolymerizable compound (C)"), and photopolymerization initiation. At least one of a group consisting of a reagent (hereinafter sometimes referred to as "photopolymerization initiator (D)") and a solvent (hereinafter sometimes referred to as "solvent (E)"), and a dye containing the dye of the present invention A coloring agent (hereinafter sometimes referred to as "coloring agent (A)").

The colorant (A) may further contain a dye (A-2) different from the dye of the present invention.

As the dye different from the dye of the present invention, it can be exemplified by the Colour Index (published by The Society of Dyers and Colourists), and classified into a solvent (Solvent), an acid (Acid), a basic (Basic), and a reaction ( Reactive), direct, disperse, or reduced (Vat) compounds. More specifically, the dyes of the following dye index (C.I.) number are mentioned, but it is not limited to these.

C.I. Solvent yellow 25, 79, 81, 82, 83, 89;

C.I. Acid yellow 7, 23, 25, 42, 65, 76;

C.I. Reaction yellow 2, 76, 116;

C.I. Direct yellow 4, 28, 44, 86, 132;

C.I. Disperse yellow 54, 56;

C.I. Solvent Orange 41, 54, 56, 99;

C.I. Acidic oranges 56, 74, 95, 108, 149, 162;

C.I. Reaction 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 Blue 35, 37, 38, 44, 59, 64, 67, 70;

C.I. Acid blue 40, 45, 78, 80, 83, 90, 100, 171, 185;

C.I. Basic blue 65, 140;

C.I. Reaction Blue 15, 38;

C.I. Disperse blue 143;

C.I. Direct Blue 86, 87;

C.I. Solvent Green 1, 5;

C.I. Acidic green 3, 5, 9, 25, 28;

C.I. Alkaline green 1;

C.I. Restore green 1;

C.I. Acid black 58, 60, 107;

C.I. Solvent black 27 and the like.

The pigment (A-2) is exemplified by an organic pigment or an inorganic pigment which is usually used in a pigment dispersion resist. Examples of the inorganic pigment include a metal compound such as a metal oxide or a metal salt, and specific examples thereof include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. Composite metal oxide. Further, specific examples of the organic pigment and the inorganic pigment include a compound classified as a pigment in a Colour Index (published by The Society of Dyers and Colourists). More specifically, the following dye index (C.I.) number of pigments may be mentioned, but it is not limited thereto.

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 oranges 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 Blue 15 (15:3, 15:4, 15:6, etc.), 21, 28, 60, 64 and 76;

C.I. Pigment Green 7, 10, 15, 25, 36 and 47;

C.I. Pigment Brown 28;

C.I. Pigment black 1 and 7, etc.

The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, even more preferably from 10 to 50% by mass, based on the solid content of the coloring composition. . Here, the solid content component means a total of components other than the solvent in the coloring composition.

In the case where the colorant (A) further contains a dye or pigment (A-2) different from the dye of the present invention, the content of the dye of the present invention in the colorant (A) is preferably from 3 to 80% by mass. More preferably, it is 3 to 70% by mass, and more preferably 3 to 50% by mass.

The content of the pigment (A-2) in the colorant (A) is 20 to 97% by mass, preferably 30 to 97% by mass, more preferably 50 to 97% by mass.

The resin (B) is not particularly limited, and any resin can be used. For example, the resin (B) contains a structural unit derived from (meth)acrylic acid. Here, (meth)acrylic acid means acrylic acid and/or methacrylic acid.

As the resin (B), specifically, preferred are: methacrylic acid/benzyl methacrylate copolymer, methacrylic acid/benzyl methacrylate/styrene copolymer, methacrylic acid/benzyl methacrylate /Isobornyl methacrylate copolymer, methacrylic acid / styrene / benzyl methacrylate / N-phenyl maleimide copolymer, methacrylic acid and selected from the formula (B-1-1) A copolymer of at least one of the compound represented by the compound represented by the formula (B-1-2) and the like.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 5,000 to 35,000, more preferably 6,000 to 30,000, and particularly preferably 7,000 to 28,000.

The acid value of the resin (B) is preferably from 50 to 150, more preferably from 60 to 135, and particularly preferably from 70 to 135.

The content of the resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, particularly preferably from 17 to 55% by mass, based on the solid content of the coloring composition.

The photopolymerizable compound (C) is not particularly limited as long as it is a compound which can be polymerized by an active radical, an acid or the like generated from the photopolymerization initiator (D) by irradiation with light. For example, a compound having a polymerizable carbon-carbon unsaturated bond or the like can be given.

The photopolymerizable compound (C) is preferably a photopolymerizable compound having three or more polymerizable groups. Examples of the photopolymerizable compound having three or more polymerizable groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethyl acrylate, dipentaerythritol hexaacrylate, and the like. Dipentaerythritol hexamethacrylate or the like. The photopolymerizable compound (C) may be used singly or in combination of two or more.

The content of the photopolymerizable compound (C) is preferably from 5 to 65% by mass, and more preferably from 10 to 60% by mass, based on the solid content of the coloring composition.

Examples of the photopolymerization initiator (D) include a living radical generator, an acid generator, and the like. The living radical generating agent is a compound which generates an active radical by irradiating light. Examples of the living radical generating agent include an acetophenone compound, a benzoin compound, a benzophenone compound, a thioxanthone compound, and the like. Compounds, hydrazine compounds, and the like.

Examples of the acetophenone compound include diethoxyacetophenone and 2-N-morpholinyl-1-(4-methylsulfanylphenyl)-2-methylpropan-1-one. , 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin dimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy) Phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one As the oligomer or the like, 2-morpholinyl-1-(4-methylsulfanylphenyl)-2-methylpropan-1-one or the like is preferably exemplified.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl ortho-benzoylbenzoate, 4-phenylbenzophenone, and 4-benzylidene-4'-methyldiphenyl. Thioether, 3,3',4,4'-tetrakis(t-butylperoxycarboxy)benzophenone, 2,4,6-trimethylbenzophenone, and the like.

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

As the above three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5 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.

Examples of the ruthenium compound include an O-fluorenyl fluorene-based compound, and specific examples thereof include N-benzimidyloxy-1-(4-phenylsulfanylphenyl)butane-1. -keto-2-imine, N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-acetoxy-1 -[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-B -6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolylmethoxy)benzylidenyl}-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 also be used. ,5,5'-tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylhydrazine, diphenylethylenedione, 9,10-phenanthrenequinone , camphorquinone, methyl phenylglyoxylate, titanium titanate compound, and the like.

An acid generator is a compound which generates an acid by irradiating light.

Examples of the acid generator include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethenoxyphenyldimethylate.鋶p-toluenesulfonate, 4-acetoxyphenyl-methyl-benzyl hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl An anthracene salt such as p-toluenesulfonate or diphenylphosphonium hexafluoroantimonate or a nitrobenzyl tosylate or a benzoin tosylate.

Further, among the above-mentioned compounds which are active radical generating agents, there are also compounds which generate an acid simultaneously with the generation of active radicals, for example, three A photopolymerization initiator can also be used as the acid generator.

The content of the photopolymerization initiator (D) is preferably from 0.1 to 30% by mass, and more preferably from 1 to 20% by mass, based on the total amount of the resin (B) and the photopolymerizable compound (C). When the content of the photopolymerization initiator is within the above range, the sensitivity is increased and the exposure time is shortened, thereby improving productivity.

Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones other than the above, alcohols, esters, and guanamines.

Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and 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, two Ethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether Acid ester, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, anisole, phenethyl ether, methyl anisole, and the like.

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

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

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

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, and butyric acid. Ethyl ester, butyl butyrate, alkyl ester, methyl lactate, ethyl lactate, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxy acetic acid Methyl ester, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Methyl 2-methoxy-2-methylpropanoate, 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.

Examples of the above guanamines include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

As the solvent (E), preferred are propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate.

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

The content of the solvent (E) in the coloring composition is preferably 70 to 95% by mass, and more preferably 75 to 90% by mass based on the coloring composition.

The coloring composition of the present invention may further comprise a surfactant (G). Examples of the surfactant (G) include a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom.

Examples of the polyfluorene-based surfactant include a surfactant having a decane bond. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Polyether Modified Emu Oil SH8400 (trade name: Dow Corning Toray Limited Co., Ltd.) Manufactured by the company), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials) Japan contract company manufacturing) and so on.

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain. Specific examples include Fluorad (trade name) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (trade name) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac R30 (limited in DIC shares) Manufactured by the company, Eftop (trade name) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (trade name) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass Co., Ltd. Manufacturing), E5844 (manufactured by Daikin Precision Chemical Research Co., Ltd.), etc.

Examples of the polyfluorene-based surfactant having the above fluorine atom include a surfactant having a decane bond and a fluorocarbon chain. Specific examples include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, Megafac F443 (manufactured by DIC Corporation), and the like.

The content of the surfactant (G) is preferably 0.00001 to 0.2% by mass, and more preferably 0.001 to 0.1% by mass based on the coloring composition. When the content of the surfactant (G) is within the above range, flatness tends to be good, and it is preferred.

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

As a method of forming a color filter or a pattern thereof using the coloring composition of the present invention, for example, a method of applying the coloring composition of the present invention to a substrate or another resin layer (for example, other previously formed on a substrate) may be mentioned. In the coloring composition layer or the like, a method of removing and drying a volatile component such as a solvent to form a colored layer, and developing the colored layer through a photomask, and developing the inkjet device without using a photolithography method.

The film thickness of the coating film in this case is not particularly limited, and may be appropriately adjusted depending on the material to be used, the use, and the like, and is preferably 0.1 to 30 μm, more preferably 1 to 20 μm, and even more preferably 1~6 μm.

Examples of the coating method of the coloring composition include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Further, a dip coater, a bar coater, a spin coater, a slit & spin coater, or a knife coater (sometimes referred to as a squeeze coater or a curtain spray) may be used. Coating by a coater such as a coater or a non-rotating coater.

As for the removal or drying of the solvent, for example, natural drying, air drying, and reduced-pressure drying can be mentioned. The specific drying temperature is preferably from 10 to 120 ° C, more preferably from 25 to 100 ° C.

The drying time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes. In the case of drying under reduced pressure, it is preferably carried out at a temperature of from 50 to 150 Pa at a temperature ranging from 20 to 25 °C.

The dried coating film is exposed through a photomask for forming a target pattern. The shape of the pattern on the mask at this time is not particularly limited, and a pattern shape corresponding to the intended use can be used.

As the light source for exposure, a light source which generates light of a wavelength of 250 to 450 nm is preferable. Specific examples thereof include a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, etc., and may be cut off using a filter that cuts off a specific band, or selectively extracted by using a band pass filter that extracts a specific band, and performs exposure.

In order to be able to uniformly illuminate the entire exposed surface with parallel rays or to precisely position the mask with the substrate, it is preferred to use a mask aligner, a stepper or the like.

After the exposure, development can be carried out by bringing a specific portion, for example, an unexposed portion, into contact with the developer to obtain a pattern. The developing solution may, for example, be an aqueous solution of a basic compound (potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide or the like) which may contain a surfactant.

The development method may be any of a liquid coating method, a dipping method, a spray method, and the like. Further, the substrate can be tilted at an arbitrary angle during development. It is preferred to carry out water washing after development.

Further, post-baking treatment may be performed as needed. The post-baking treatment is preferably in the range of, for example, 150 to 230 ° C for 10 to 240 minutes.

The coloring composition of the present invention can be suitably used to form a color filter or a colored pattern. According to the coloring composition of the present invention, a coloring pattern and a color filter excellent in color density, brightness, contrast, sensitivity, resolution, heat resistance, and the like can be obtained. Further, the color filters or colored patterns may be used as part of components such as an optical film, an array substrate, and a color filter substrate. Further, at least one type selected from the group consisting of the optical film, the array substrate, and the color filter substrate can be used in a display device such as a liquid crystal display device or an organic EL (Electroluminescence) device. Medium; solid-state imaging device and the like in a machine related to coloring images.

Since the compound of the present invention has low transferability, a color filter for a display device having excellent display characteristics can be produced from a coloring composition containing a dye containing a compound of the present invention as a main component.

Example

Hereinafter, the present invention will be more specifically described by way of examples. In addition, "%" and "part" in the examples and comparative examples are mass% and mass parts unless otherwise specified.

Example 1

The following reaction was carried out under a nitrogen atmosphere. After adding 20.0 parts of N-methylpyrrolidone to 15.0 parts of C.I. basic red in a four-necked flask equipped with a reflux tube, the mixture was stirred for 30 minutes to prepare a reaction solution. The reaction solution was stirred while stirring at room temperature, and 1.05 part of 1,12-diaminododecane was added dropwise. After the completion of the dropwise addition, the reaction vessel was kept at 140 degrees while stirring for 3 hours. Further, 0.53 parts of 1,12-diaminododecane was added to the reaction solution, and the mixture was stirred while maintaining the reaction vessel at 140 degrees for 3 hours. Further, 0.53 parts of 1,12-diaminododecane was added to the reaction solution, and the mixture was stirred while maintaining the reaction vessel at 140 degrees for 3 hours. The reaction solution cooled to room temperature was poured into 0.2 liter of 10% hydrochloric acid water to obtain a red suspension. The red solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 1.3 parts of the compound represented by the formula (I-1) (yield 23%).

The structure of the compound (I-2) is determined by mass spectrometry. The mass spectrometer was JMS-700 (manufactured by JEOL Ltd.).

Mass spectrometry: ionization mode = FD +: m / z = 1065

0.35 g of the compound (I-2) was dissolved in ethyl lactate to have a volume of 250 cm ³ , and 2 cm ³ of the solution was diluted with ion-exchanged water to have a volume of 100 cm ³ (concentration: 0.028 g/L). The absorption spectrum was measured using an ultraviolet-visible near-infrared spectrophotometer (V-650; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 1.6 (arbitrary unit) at λmax = 529 nm.

Example 2

The following reaction was carried out under a nitrogen atmosphere. After adding 20.0 parts of N-methylpyrrolidone to 15.0 parts of C.I. basic red in a four-necked flask equipped with a reflux tube, the mixture was stirred for 30 minutes to prepare a reaction solution. The reaction solution was stirred while stirring at room temperature, and 1.07 parts of 1,4-butanediol bis(3-aminopropyl)ether was added dropwise. After the completion of the dropwise addition, the reaction vessel was kept at 140 degrees while stirring for 3 hours. Further, 0.54 parts of 1,4-butanediol bis(3-aminopropyl)ether was added to the reaction solution, and the mixture was stirred while maintaining the reaction vessel at 140 degrees for 3 hours. Further, 0.54 parts of 1,4-butanediol bis(3-aminopropyl)ether was added to the reaction solution, and the mixture was stirred while maintaining the reaction vessel at 140 degrees for 3 hours. The reaction solution cooled to room temperature was poured into 0.2 liter of 10% hydrochloric acid water to obtain a red suspension. The red solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 1.6 parts of the compound represented by the formula (I-3) (yield 29%).

The structure of the compound (I-3) is determined by mass spectrometry. The mass spectrometer was JMS-700 (manufactured by JEOL Ltd.).

Mass spectrometry: ionization mode = FD +: m / z = 1068

0.35 g of the compound (I-2) was dissolved in ethyl lactate to have a volume of 250 cm ³ , and 2 cm ³ of the solution was diluted with ion-exchanged water to have a volume of 100 cm ³ (concentration: 0.028 g/L). The absorption spectrum was measured using an ultraviolet visible near-infrared spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.0 (arbitrary unit) at λmax = 530 nm.

Resin Synthesis Example 1

Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was introduced at 0.02 L/min to form a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 3-methoxybutyl B were added. 100 parts by mass of the acid ester was heated to 70 ° C while stirring. Then, 98 parts by mass of methacrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate (expressed in a molar ratio of 50:50 (B-1-1)) 394 parts by mass of the compound and the compound represented by the formula (B-1-2) were dissolved in 140 parts by mass of 3-methoxy-1-butanol to prepare a solution, and the solution was dropped in 4 hours using a drip pump. Add to 70 ° C to the flask. On the other hand, using another drip pump, 240 parts by mass of 3-methoxybutyl acetate was dissolved with a polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile). 27 parts by mass of the solution was added dropwise to the flask over 4 hours. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin B1) having a solid content of 44.3 mass%. The obtained resin B1 had a weight average molecular weight Mw of 7,500, a molecular weight distribution of 1.7, and an acid value of 111 mgKOH/g.

The components used in the following examples may be omitted as described below.

(I-2) Colorant: The azo compound synthesized in Example 1

(I-3) Colorant: the azo compound synthesized in Example 2

(II-1) Colorant: Alkaline Red 1

(B-1) Resin: Resin B1 solution

(B-2) Resin: 33.8% of methacrylic acid/benzyl methacrylate (Morby: 30/70) copolymer (manufactured by Tajika Chemical Industry Co., Ltd., average molecular weight 10700, acid value 70 mgKOH/g) Propylene glycol monomethyl ether acetate solution

(C-1) Polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)

(D-1) Photopolymerization initiator: N-benzylideneoxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (Irgacure OXE01; BASF Japan Made by the company)

(G-1) Surfactant: Polyether modified eucalyptus oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.)

(E-1) Solvent: propylene glycol monomethyl ether

(E-2) Solvent: propylene glycol monomethyl ether acetate

(E-3) Solvent: N,N-dimethylformamide

Example 3 [Preparation of coloring composition]

(I-2) 0.30 parts by mass

(B-1) 1.67 parts by mass

(C-1) 0.74 parts by mass

(D-1) 0.22 parts by mass

(G-1) 0.001 parts by mass

(E-1) 6.23 parts by mass

(E-2) 0.84 parts by mass

Mixing to obtain a coloring composition.

[Preparation of Resin Composition]

(B-2) 40.2 parts by mass

(C-1) 5.8 parts by mass

(D-1) 0.58 parts by mass

(G-1) 0.01 parts by mass

(E-1) 46.6 parts by mass

(E-2) 6.8 parts by mass

The resin composition was obtained by mixing.

[Formation of Colored Coating Film]

The coloring composition obtained above was applied onto glass (#1737; Corning) by a spin coating method, and the volatile component was volatilized at 100 ° C for 3 minutes. After cooling, an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used to irradiate light at an exposure amount of 150 mJ/cm ² (365 nm basis) in an atmosphere to form a coating film of the colored composition ( The film thickness is 2.2 μm).

[Formation of Resin Coating Film]

The coloring composition obtained above was applied onto glass (#1737; Corning) by a spin coating method, and the volatile component was volatilized at 100 ° C for 3 minutes. After cooling, an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used, and light irradiation was performed under an atmospheric environment at an exposure amount of 150 mJ/cm ² (365 nm). The film was heated at 220 ° C for 2 hours in an oven to form a coating film of a resin composition (film thickness: 2.2 μm).

[Transplantation evaluation]

The coating film of the coloring composition and the coating film of the resin composition were opposed to each other at a space of 70 μm, and heated at 230 ° C for 120 minutes, using a colorimeter (OSP-SP-200; OLYMPUS Co., Ltd. Manufacture) The color difference (ΔEab*) before and after heating of the coating film of the resin composition was measured. The coating film obtained was subjected to the above evaluation of the transferability, and as a result, the color difference (ΔEab*) of the resin composition was 2.2.

Example 4 [Transplantation evaluation]

The same procedure as in Example 3 was carried out except that the (I-2) colorant: the azo compound synthesized in Example 1 was changed to the (I-3) colorant: the azo compound synthesized in Example 2, in the same manner as in Example 3. The coating film of the coloring composition and the coating film of the resin composition were prepared, and the transfer property was evaluated. As a result, the color difference (ΔEab*) of the resin composition was 1.8.

Comparative example 2 [Preparation of coloring composition]

(II-1) 0.30 parts by mass

(B-1) 1.67 parts by mass

(C-1) 0.74 parts by mass

(D-1) 0.22 parts by mass

(G-1) 0.001 parts by mass

(E-2) 0.84 parts by mass

(E-3) 6.23 parts by mass

Mixing to obtain a coloring composition.

[Formation and Evaluation of Coating Film]

In the same manner as in Example 4, the coating film of the coloring composition and the coating film of the resin composition were prepared, and the transfer property was evaluated. As a result, the color difference (ΔEab*) of the resin composition was 57.2.

From the above results, it was found that the compound of the example had a very low transferability as compared with the compound of the comparative example.

[Industrial availability]

Since the compound of the present invention has low transferability, a color filter for a display device having excellent display characteristics can be produced by using a coloring composition containing a dye containing a compound of the present invention as a main component.

Claims (6)

a compound represented by formula (I): [In the formula (I), L represents a divalent saturated hydrocarbon group having a carbon number of 1 to 20, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and -CH ₂ - contained in the saturated hydrocarbon group may also be - CO- or -O-substituted; R ¹ and R ² each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having a carbon number of 1 to 16 which may have a substituent, or a carbon number which may have a substituent of 2~ a mercapto group of 18; R ³ to R ¹⁰ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, or a carbon number which may have a substituent of 6 to 10 a valent aromatic hydrocarbon group, -CH ₂ - contained in the aliphatic hydrocarbon group may also be substituted with -O-; R ¹¹ to R ¹⁴ each independently represent a hydrogen atom or a methyl group; and X ¹ and X ²⁻ represent an inorganic anion or Organic anion]. The compound of claim 1, wherein the L-based carbon number is 5 to 15 alkanediyl, and the -CH ₂ - contained in the alkanediyl group may be substituted by -O-. A dye comprising a compound as claimed in claim 1 or 2 as a main component. A coloring composition comprising: at least one selected from the group consisting of a resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and a coloring agent containing the dye of claim 3. A color filter formed using the colored composition of claim 4. A display device comprising the color filter of claim 5.