KR101826806B1 - Dyes and colored compositions - Google Patents

Abstract

A coloring composition comprising a dye and a solvent of any kind, and further comprising, if necessary, at least one selected from the group consisting of a resin, a polymerizable compound and a polymerization initiator.

Description

[0001] DYES AND COLORED COMPOSITIONS [0002]

The present invention relates to a coloring composition comprising a dye and a dye and a solvent.

Dyes are used as coloring agents for color filters included in display devices such as liquid crystal display panels, electroluminescence, and plasma display panels. Examples of such a dye include compounds represented by formula (III-2), C.I. Solvent Yellow 162 (Patent Document 1), and Valifast Yellow 1151 (Patent Document 2) are known.

[Patent Document 1] JP-A-2006-124634

[Patent Document 2] JP-A-2003-207887

When the solution prepared by dissolving the above-mentioned dye in an organic solvent has been stored for a long period of time, precipitation of dye or the like may occur, and storage stability may not always be sufficient.

The present invention provides the following [1] to [7].

[1] A dye comprising two or more compounds represented by formula (I).

Z ¹ , Z ² and L ¹ each independently represents a divalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent, and -CH ₂ - included in the aliphatic hydrocarbon group is -CO- Or -O-.

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

A ¹ and A ² each independently represent a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent.

B ¹ and B ² each independently represent a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent, ₂ - may be substituted with -CO-.]

[2] The dye according to [1], wherein B ¹ and B ² each independently represents a group represented by formula (II).

[In the formula (II), R ⁴ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent.

R ⁵ represents a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent.]

[3] A mixture obtained by reacting two or more compounds represented by formula (I) with one or more compounds represented by formula (I-A) and two or more compounds represented by formula (I-B ' Or [2].

In the formulas (I-A) and (I-B '), R ¹ , A ¹ , B ¹ , Z ¹ and L ¹ have the same meanings as defined above.

X ¹ and X ² each independently represent a halogen atom.

[4] A coloring composition comprising the dye and the solvent according to any one of [1] to [3].

[5] The coloring composition according to [4], further comprising at least one selected from the group consisting of a resin, a polymerizable compound and a polymerization initiator.

[6] A color filter formed using the coloring composition according to [4] or [5].

[7] A display device comprising the color filter according to [6].

The dye of the present invention contains two or more compounds represented by formula (I) (hereinafter sometimes referred to as " compound (I) ").

Z ¹ , Z ² and L ¹ each independently represents a divalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent, and -CH ₂ - included in the aliphatic hydrocarbon group is -CO- Or -O-.

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

A ¹ and A ² each independently represent a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent.

B ¹ and B ² each independently represent a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent, ₂ - may be substituted with -CO-.]

The number of carbon atoms of the substituent does not include the number of carbon atoms of the divalent aliphatic hydrocarbon group of ¹ to 16 carbon atoms which represents Z ¹ , Z ² and L ¹ , and the number thereof is preferably 2 to 10, more preferably 2 to 8.

Examples of the divalent aliphatic hydrocarbon having 1 to 16 carbon atoms include a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a pentanediyl group, a hexanediyl group, a heptanediyl group, an octanediyl group, a decanediyl group, a tetradecanediyl group, An alkanediyl group having 1 to 16 carbon atoms such as a decanediyl group; _{-CH 2 = CH 2 -, -CH} 2 -C (= CH 2) -, - , and the like having a carbon number of 1 to 16 eggs canned group such as _{- (CH 2) 2 -C (} = CH 2).

-CH ₂ - contained in the divalent aliphatic hydrocarbon having 1 to 16 carbon atoms may be substituted with -CO- or -O-, and the hydrogen atom contained in the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted with a halogen And may be substituted with an atom.

Z ¹ and Z ² as -CH ₂ - is -O- is the one having 1 to 8 carbon atoms alkanediyl group optionally substituted and preferably a, -CH ₂ - of 5 to 7 carbon atoms which optionally is substituted with -O- More preferably, it is alkandiyl. Examples of preferred groups _{- (CH 2) 3 -,} - (CH 2) 2 -O- (CH 2) 2 -, - (CH 2) 2 -O- (CH 2) 2 -O- (CH 2) 2 - and -CH ₂ -CH (CH ₃₎ - it can be given.

As L ¹ , it is preferably an alkanediyl group having 1 to 8 carbon atoms which may include -C (= CH ₂ ) -, more preferably an unsubstituted alkanediyl group having 1 to 8 carbon atoms, and an unsubstituted C4 To eight alkanediyl groups. Preferable groups include - (CH ₂ ) ₂ -, - (CH ₂ ) ₄ - or -CH ₂ -C (= CH ₂ ) -.

The monovalent saturated hydrocarbon group having 1 to 16 carbon atoms representing R ¹ and R ² may be any of linear, branched or cyclic. The number of carbon atoms of the substituent does not include the number of carbon atoms of the saturated hydrocarbon group, and the number thereof is 1 to 16, preferably 1 to 10, more preferably 1 to 4.

Examples of the monovalent saturated hydrocarbon group having 1 to 16 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- , 3,3-tetramethylbutyl group and the like), methylhexyl group (1,5-dimethylhexyl group and the like), ethylhexyl group (2-ethylhexyl group and the like), cyclopentyl group, cyclohexyl group, methylcyclohexyl (2-methylcyclohexyl group and the like), and cyclohexylalkyl group.

The hydrogen atom contained in the saturated hydrocarbon group may be substituted with an alkoxy group or a carboxy group having 1 to 8 carbon atoms. Examples of the aliphatic hydrocarbon group substituted with an alkoxy group having 1 to 8 carbon atoms include propoxypropyl group (such as 3-isopropoxypropyl group) and alkoxypropyl group (such as 3- (2-ethylhexyloxy) propyl group) . Examples of the saturated hydrocarbon group substituted with a carboxy group include a 2-carboxyethyl group, a 3-carboxypropyl group, and a 4-carboxybutyl group.

The hydrogen atom contained in the acyl group having ² to 18 carbon atoms representing R ¹ and R ² may be substituted with a carboxyl group or an alkoxy group having 1 to 8 carbon atoms. The number of carbon atoms of the acyl group is counted including the number of carbon atoms of the substituent, and the number thereof is preferably 2 to 18, more preferably 6 to 10. Examples of the acyl group which may have a substituent include an acetyl group, a benzoyl group, a methoxybenzoyl group (p-methoxybenzoyl group and the like) and the like.

As R ¹ and R ² , a hydrogen atom, an alkyl group having 1 to 4 carbon atoms and an acyl group having 2 to 5 carbon atoms are preferable, and a hydrogen atom, a methyl group and an acetyl group are more preferable.

Examples of the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent represented by A ¹ and A ² include a phenylene group and a naphthalenediyl group, and preferably a phenylene group. The carbon number of the aromatic hydrocarbon group does not include the carbon number of the substituent.

Examples of the substituent which may contain the aromatic hydrocarbon group include a halogeno group, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group, a sulfo group, a sulfamoyl group and an N-substituted sulfamoyl group .

Examples of the halogeno group include a fluoro group, a chloro group, a bromo group and an iodo group, and a fluoro group, a chloro group and a bromo group are preferable.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl. More preferably an alkyl group, a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable.

Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert- Preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group and an ethoxy group, and methoxy is particularly preferable.

The N-substituted sulfamoyl group includes -SO ₂ NHR ⁶ group or -SO ₂ NR ⁶ R ⁷ group. R ⁶ and R ⁷ each independently represent a saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent or an acyl group having 2 to 16 carbon atoms which may have a substituent. Examples of the saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent and the acyl group having 2 to 16 carbon atoms which may have a substituent include the same groups as described above.

Examples of the monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which represent B ¹ and B ² include a phenyl group and a naphthyl group. The carbon number of the aromatic hydrocarbon group does not include the carbon number of the substituent.

Examples of the monovalent heterocyclic group having 3 to 14 carbon atoms which may have a substituent represented by B ¹ and B ² include groups represented by the following formulas.

[R represents a hydrogen atom or an organic group]

As such an organic group, there may be mentioned, for example, a group of the same type as R ⁴ described below.

The hydrogen atom contained in the monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms and the monovalent heterocyclic group having 3 to 14 carbon atoms is substituted with a hydroxyl group, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, a cyano group, an amino group or an N-substituted amino group . The hydrogen atom contained in the above aromatic hydrocarbon group may be substituted with an oxo group. -CH ₂ - included in the heterocyclic group may be substituted with -CO-.

Examples of the N-substituted amino group include -NHR ⁸ group and -SO ₂ NR ⁸ R ⁹ group. R ⁸ and R ⁹ each independently represent a monovalent C 1-16 aliphatic hydrocarbon group which may have a substituent or a monovalent C 1-14 heterocyclic group which may have a substituent. Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent and the monovalent carbon-3 to 14-membered monovalent heterocyclic group which may have a substituent include the same groups as the groups introduced as the above-mentioned heterocyclic group.

B ¹ and B ² are preferably groups represented by formula (II).

[In the formula (II), R ⁴ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent.

R ⁵ represents a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent.]

The pyridone ring of the group represented by the formula (II) may be a keto group or an enol form.

Examples of the monovalent saturated hydrocarbon group having 1 to 16 carbon atoms representing R ⁴ and R ⁵ include the same groups as described above.

Examples of R ⁴ include a methyl butyl group (1,1,3,3-tetramethyl butyl group, etc.), a methylhexyl group (1,5-dimethylhexyl group and the like), an ethylhexyl group (2-ethylhexyl group and the like) A branched chain saturated hydrocarbon group such as hexyl group (2-methylcyclohexyl group and the like), alkoxypropyl group [3- (2-ethylhexyloxy) propyl group and the like] is preferable.

R ⁵ is preferably a methyl group.

Examples of the compound (I) include compounds represented by the formulas (I-1) to (I-18). In the formula, A ¹ , A ² , Z ^1, and Z ² represent the bonding hands on the right hand side closer to L ¹ .

It is more preferable that B ¹ and B ² are groups having the same skeleton, and furthermore, it is more preferable that A ¹ and A ² , R ¹ and R ² , Z ¹ and Z ² have the same skeleton. Such a group facilitates the preparation of the compound (I).

As the two or more compounds (I) contained in the dyes of the present invention, at least one kind selected from the group consisting of A ¹ , A ² , R ¹ , R ² , Z ¹ , Z ² and L ¹ in formula (I) or more preferably a mixture consisting of at least compound of two kinds of mutually different structures, and, Z ^1, Z ^2, and a mixture is more than one type of compound selected from the group consisting of L ¹ is made of two or more kinds of compounds different from each other structural More preferably a mixture of two or more compounds having a structure in which only L ¹ is different from each other.

Among these, a mixture of a compound represented by the formula (I-6) and a compound represented by the formula (I-7) is preferable. The ratio of the content of the compound represented by the formula (I-6) to the content of the compound represented by the formula (I-7) is preferably from 10:90 to 89:11, and more preferably from 30:70 to 70:30. When the ratio of the content is within the above range, the solubility in an organic solvent is excellent.

The compound (I) can be produced by reacting the compound represented by the formula (I-A) and the compound represented by the formula (I-A ') with the compound represented by the formula (I-B) at 0 to 150 캜 in a solvent.

Z ¹ , Z ² , Z ³ , R ¹ , R ² , A ¹ , A ² , B ¹ and B ^{2 in} formula (I-A), formula (I-A ' Have the same meanings as above.

R ³¹ and R ³² each independently represent -OR ³³ or a halogen atom. And R ³³ represents a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms.

R ³¹ and R ³² are preferably a halogen atom, and more preferably a chlorine atom.

Examples of the compound represented by the formula (I-B) include dimethyl malonate, isobutyl succinate, dimethyl adipate and diethyl suverate, malonic acid chloride, succinic acid chloride, adipic acid chloride, suberic acid chloride and sebacic acid chloride. .

The amount of the compound represented by the formula (I-B) is preferably 0.5 to 3 moles, more preferably 0.5 to 3 moles per 1 mole of the total amount of the compound represented by the formula (I-A) 1 mole is more preferred. When water is contained in the solvent, the amount of the compound represented by the formula (I-B) is preferably in the range of 1 mole to 1 mole of the total amount of the compound represented by the formula (I-A) More preferably 0.6 to 3 moles.

When R ³¹ and R ³² of the compound represented by the formula (I-B) are -OR ³³ , it is preferable to add a known acid catalyst. Examples of the acid catalyst include sulfuric acid and para-toluenesulfonic acid. The amount of the acid catalyst to be used is preferably 0.01 to 2 moles per 1 mole of the total amount of the compound represented by the formula (I-A) and the compound represented by the formula (I-A ').

The reaction between the compound represented by the formula (I-A) and the compound represented by the formula (I-A ') and the compound represented by the formula (I-B) is carried out in a solvent. As the solvent, for example, water; Ethers such as 1,4-dioxane (particularly, cyclic ethers); Halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, trichlorethylene, perchlorethylene, dichloropropane, amyl chloride and 1,2-dibromoethane; Ketones such as acetone, methyl isobutyl ketone, and cyclohexanone; Carbon-based aromatic compounds such as benzene, toluene and xylene; And alkylamides such as N, N-dimethylformamide, N, N-dibutylformamide, N, N-dimethylacetamide and N-methylpyrrolidone are preferable, and two or more kinds of solvents may be used in combination . The amount of the solvent to be used is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass, relative to 1 part by mass of the total amount of the compound represented by formula (I-A) and the compound represented by formula (I-A ' to be.

The reaction of the compound represented by the formula (I-A) and the compound represented by the formula (I-A ') with the compound represented by the formula (I-B) may be carried out in air dried with calcium chloride or the like, Or under an argon atmosphere.

The reaction temperature is preferably from 0 to 150 캜, more preferably from 10 to 130 캜. The reaction time is preferably 1 to 25 hours, more preferably 3 to 15 hours.

The order of addition of the compound represented by the formula (I-A), the compound represented by the formula (I-A '), the compound represented by the formula (I-B) and the solvent is not particularly limited, , The compound represented by the formula (I-A ') and the solvent is preferably added (added dropwise) to the solution represented by the formula (I-B). When an acid catalyst is used, the compound represented by the formula (I-B) is added to a solution of the compound represented by the formula (I-A), the compound represented by the formula (I-A ' ).

The method for obtaining the desired compound (I) from the reaction mixture obtained as above is not particularly limited, but various known methods may be employed. For example, the reaction mixture is extracted with an organic solvent and purified, the compound (I) is eluted into the organic phase by mixing the reaction mixture with the organic solvent and water, and the solvent on the organic phase separated by the separating rod is removed by evaporation, Compound (I) can be obtained. The extraction temperature is preferably 10 to 50 占 폚, more preferably 20 to 30 占 폚. The precipitation is preferably carried out at the above temperature for 0.5 to 4 hours. The compound (I) after the precipitation is washed with an alkaline aqueous solution, an acidic aqueous solution or the like, and then dried. Further, it may be further purified by a known technique such as recrystallization, if necessary.

As the alkaline aqueous solution, a known alkaline substance dissolved in water may be used. The pH range of the hydrogen ion concentration of the alkaline aqueous solution is preferably 8 to 12, more preferably 9 to 11. The alkaline substance is not particularly limited, and examples thereof include sodium carbonate, potassium carbonate, sodium acetate, sodium hydroxide, potassium hydroxide, cesium hydroxide, ammonia and the like.

As the acidic aqueous solution, a known acidic substance dissolved in water may be used. The range of the hydrogen ion concentration of the acidic aqueous solution is preferably pH = 0 to 6, more preferably 1 to 5. The acidic substance is not particularly limited, and examples thereof include ammonium chloride, oxalic acid, acetic acid, hydrochloric acid and sulfuric acid.

The dye of the present invention is preferably a mixture obtained by reacting at least one compound represented by formula (I-A) with at least two compounds represented by formula (I-B) Is more preferably a mixture obtained by mixing two or more compounds represented by the formula (I-B ') and stirring.

In the formulas (I-A) and (I-B '), R ¹ , A ¹ , B ¹ , Z ¹ and L ¹ have the same meanings as defined above.

X ¹ and X ² each independently represent a halogen atom.

Examples of the compound represented by the formula (I-B ') include malonic acid chloride, succinic acid chloride, adipic acid chloride, suberic acid chloride and sebacic acid chloride.

Examples of combinations of compounds represented by the formula (I-B ') which are used in combination of two or more types include malonic acid chloride and adipic acid chloride, succinic acid chloride and adipic acid chloride, succinic acid chloride and suberic acid chloride, succinic acid chloride and sebacic acid chloride, Chlorinated hydrocarbons such as chlorobenzene, chlorobenzene, chlorobenzene, chlorobenzene, chlorobenzene, and the like.

The total amount of the compounds represented by the formula (I-B ') of two or more is preferably 0.5 to 3 moles, more preferably 0.5 to 1 mole, per 1 mole of the total amount of the compounds represented by formula (I-A) Do. When water is contained in the solvent, the total amount of the compounds represented by the formula (I-B ') of two or more is 0.6 to 3 moles per one mole of the total amount of the compounds represented by formula (I-A) .

The reaction of one or more compounds represented by the formula (I-A) with two or more compounds represented by the formula (I-B ') is carried out in a solvent. As the solvent, the same ones as mentioned above can be mentioned. The amount of the solvent to be used is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass, based on 1 part by mass of the total amount of the compounds represented by formula (I-A).

The reaction of one or more compounds represented by the formula (I-A) with two or more compounds represented by the formula (I-B ') may be carried out in the air dried with calcium chloride or the like, but in a nitrogen atmosphere or an argon atmosphere .

The reaction temperature is preferably from 0 to 150 캜, more preferably from 10 to 130 캜. The reaction time is preferably 1 to 25 hours, more preferably 3 to 15 hours.

The order of addition of one or more compounds represented by the formula (I-A), two or more compounds represented by the formula (I-B ') and the solvent is not particularly limited, but may be one or more compounds represented by the formula (I- It is preferable to add (drop) two or more compounds represented by the formula (I-B ') to a solution made of a solvent.

The method for obtaining the dye of the present invention from the reaction mixture thus obtained is not particularly limited, but any known method may be employed. For example, the dye of the present invention is extracted and purified by an organic solvent, the dye of the present invention is dissolved in an organic phase by mixing the reaction mixture with an organic solvent and water, and the organic phase on the organic phase collected by a separating rod or the like is evaporated Thus, the purified dye of the present invention can be obtained. When eluted in the organic phase, the temperature is preferably 10 to 50 占 폚, more preferably 20 to 30 占 폚, and preferably about 0.5 to 4 hours. After the precipitation, the purified dye of the present invention is washed with an alkaline aqueous solution, an acidic aqueous solution or the like, and then dried. Further, it may be further purified by a known technique such as recrystallization, if necessary.

As the alkaline aqueous solution, a known alkaline substance dissolved in water may be used. The range of the hydrogen ion concentration of the alkaline aqueous solution is preferably pH = 8 to 12, more preferably 9 to 11. The alkaline substance is not particularly limited, and examples thereof include sodium carbonate, potassium carbonate, sodium acetate, sodium hydroxide, potassium hydroxide, cesium hydroxide, ammonia and the like.

As the acidic aqueous solution, a known acidic substance dissolved in water may be used. The range of the concentration of hydrogen ions in the acidic aqueous solution is preferably pH = 0 to 6, more preferably 1 to 5. The acidic substance is not particularly limited, and examples thereof include ammonium chloride, oxalic acid, acetic acid, hydrochloric acid and sulfuric acid.

Compound (I) can be produced by subjecting a compound represented by formula (I-C) to a coupling reaction with a compound represented by formula (I-D) and a compound represented by formula (I-D '). The compound (I) can be obtained by reacting the compound represented by the formula (I-C) with the compound represented by the formula (I-D) and the compound represented by the formula (I-D ' Can be manufactured.

In the formulas (I-C) and (I-D), Z ¹ , Z ² , L ¹ , R ¹ , R ² , A ¹ , A ² , B ¹ and B ² have the same meanings as defined above.

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, hypochlorite ion, CH ₂ -COO ^- , Ph-COO ^- chloride ion, bromide ion, CH ₃ -COO ^- may be mentioned.

Since the dye of the present invention exhibits high solubility and high spectral density, it can be used for a fiber material or a liquid crystal display device which displays a color by using reflected light or transmitted light. Further, since the dye of the present invention has maximum absorption in the wavelength range of 400 to 450 nm when measuring the absorption spectrum, it is preferably used as a yellow dye.

(B), a polymerizable compound (C), a colorant (A), and a solvent (E), wherein the coloring composition of the present invention comprises a colorant containing the dye of the present invention And a polymerization initiator (D).

The colorant (A) may contain, in addition to the two or more compounds (I), a dye different from the compound (I) and / or the pigment (A-2).

The dyes which are different from the compound (I) include Solvent, Acid, Basic, Reactive, Direct in the Color Index [published by The Society of Dyers and Colourists] , Disperse or Vat, and the like. More specifically, the dyes of the following color index (CI) numbers are exemplified, but are 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. Dispulse 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 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. Reactive Blue 15, 38;

C.I. Dispulse Blue 143;

C.I. Direct Blue 86, 87;

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;

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

C.I. Solvent Black 27 and so on.

Examples of the pigment (A-2) include organic pigments and inorganic pigments commonly used in pigment-dispersed resists. Specific examples of the inorganic pigments include metallic compounds such as metal oxides and metal complex salts. Specific examples thereof include metal oxides or complex metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, . Specific examples of the organic pigments and inorganic pigments include those classified in the Color Index (Pigment) by The Society of Dyers and Colourists. More specifically, the pigment of the color index (C.I.) number may be exemplified as follows, but 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 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 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 and others.

The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, and still more preferably from 10 to 50% by mass, based on the solid content in the coloring composition. Here, the solid content refers to the sum of components excluding the solvent in the coloring composition.

When the colorant (A) further comprises a dye and / or pigment (A-2) different from the compound (I), the content of the total of two or more selected from the group consisting of the compound (I) By mass, preferably 3 to 70% by mass, and more preferably 3 to 50% by mass.

The content of the pigment (A-2) is preferably 20-97 mass%, more preferably 30-97 mass%, and even more preferably 50-97 mass% with respect to the colorant (A).

The coloring composition of the present invention preferably contains the resin (B). The resin (B) is not particularly limited, but it is preferably an alkali-soluble resin, and the alkali-soluble resin contains a constituent unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

Examples of the resin (B) include copolymers of [K1] to [K4].

[K1] A monomer (a) having a cyclic ether having 2 to 4 carbon atoms (hereinafter also referred to as "(a)") and a monomer (b) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride ) Or more (hereinafter sometimes referred to as " (b) ").

(C) (hereinafter sometimes referred to as "(c)") which is copolymerizable with [K2] (a) and (b) ≪ / RTI >

[K3] Copolymer of (b) and (c).

[K4] Resin obtained by reacting (a) a copolymer of (b) and (c).

As the resin (B), a resin containing a structural unit derived from (a) is preferable. By including the structural unit derived from (a) in the resin (B), it is possible to further enhance the reliability of the obtained color pattern in terms of heat resistance, chemical resistance and the like.

(a) may be, for example, a cyclic ether having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of oxiran ring, oxetane ring and tetrahydrofuran ring (oxolane ring) Refers to a polymerizable compound having a polymerizable group other than an ether. (a) is preferably a cyclic ether having 2 to 4 carbon atoms and a monomer having an ethylenic carbon-carbon double bond, more preferably a cyclic ether having 2 to 4 carbon atoms and a monomer having a (meth) acryloyloxy group Do.

Further, in the present specification, the term "(meth) acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning.

(a1) having an oxiranyl group (hereinafter may be referred to as "(a1)"), a monomer (a2) having an oxetanyl group (hereinafter referred to as " , And a monomer (a3) having a tetrahydrofuryl group [hereinafter sometimes referred to as "(a3)").

The monomer (a1) having an oxiranyl group refers to a polymerizable compound having a polymerizable group other than an oxiranyl group and an oxiranyl group. (a1) may be a monomer (a1-1) having a structure obtained by epoxidizing an alkene (hereinafter sometimes referred to as "(a1-1)"), a monomer having a structure obtained by epoxidizing a cycloalkene a1-2) (hereinafter sometimes referred to as " (a1-2) ").

(a1) is preferably a monomer having an oxiranyl group and an ethylenic carbon-carbon double bond, more preferably a monomer having an oxiranyl group and a (meth) acryloyloxy group.

(meth) acrylate,? -methyl glycidyl (meth) acrylate,? -ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl Vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl- Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- ) Styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5- , 3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) have.

(a1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Selenoxide 2000; (Manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate [for example, CYRAMER A400; (Manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate [for example, Cyclomer M100; (Manufactured by Daicel Chemical Industries, Ltd.), a compound represented by the formula (B1-1) and a compound represented by the formula (B1-2).

[In the formulas (B1-1) and (B1-2), R ^a and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group .

X ^a and X ^b independently represent a single bond, -R ^c -, -R ^c -O-, -R ^c -S- or -R ^c -NH-.

R ^c represents an alkanediyl group having 1 to 6 carbon atoms.

* Stands for a binding hand with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.

Examples of the hydroxyalkyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy- , A 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group and a 4-hydroxybutyl group.

Examples of R ¹ and R ² include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a pentanediyl group, and a hexanediyl group.

X ¹ and X ² are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- (* represents a bond with O), * -CH ₂ CH ₂ -O- group , More preferably a single bond, * -CH ₂ CH ₂ -O- group.

Examples of the compound represented by the formula (B1-1) include a compound represented by the formula (B1-1-1) to (B1-1-15), preferably a compound represented by the formula (B1-1-1) (B1-1-3), (B1-1-5), (B1-1-7), (B1-1-9), (B1-1-11) ), More preferably a compound represented by formula (B1-1-1), formula (B1-1-7), formula (B1-1-9) or formula (B1-1-15) Compounds.

Examples of the compound represented by the formula (B1-2) include compounds represented by the formulas (B1-2-1) to (B1-2-15), preferably the compounds represented by the formulas (B1-2-1), B1-2-3), the formula (B1-2-5), the formula (B1-2-7), the formula (B1-2-9), the formula (B1-2-11) ), More preferably a compound represented by formula (B1-2-1), formula (B1-2-7), formula (B1-2-9) or formula (B1-2-15) Compounds.

The compound represented by formula (B1-1) and the compound represented by formula (B1-2) may be used alone. They may be mixed at an arbitrary ratio. In the case of mixing, the mixing ratio thereof is preferably from 5:95 to 95: 5, more preferably from 10:90 to 90:10 as the formula (B1-1): (B1-2) Preferably 20:80 to 80:20.

The monomer (a2) having an oxetanyl group refers to a polymerizable compound having a polymerizable group other than an oxetanyl group and an oxetanyl group. (a2) is preferably a monomer having an oxetanyl group and an ethylenic carbon-carbon double bond, more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. (a2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3- 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

The monomer (a3) having a tetrahydrofuryl group refers to a polymerizable compound having a polymerizable group other than a tetrahydrofuryl group and a tetrahydrofuryl group. (a3) is preferably a monomer having a tetrahydrofuryl group and an ethylenic carbon-carbon double bond, more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group.

Specific examples of the monomer (a3) include tetrahydrofurfuryl acrylate (for example, Viscot V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

(a1) is preferable in that the reliability of heat resistance, chemical resistance, etc. of the obtained color pattern can be further enhanced. Furthermore, (a1-2) is more preferable in view of excellent storage stability of the coloring composition.

(b) include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as hydrophthalic acid and 1,4, -cyclohexanedicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- 5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy- [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, Unsaturated dicarboxylic acid anhydrides such as dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-eno anhydride (hymic acid anhydride);

(Meth) acryloyloxyalkyl] unsaturated monocarboxylic acid mono [(meth) acryloyloxyethyl] phthalic acid mono [2- (meth) acryloyloxyethyl] Esters;

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule such as? - (hydroxymethyl) acrylic acid.

Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.

(meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- (Meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (Meth) acrylate, dicyclopentanyl (meth) acrylate, and tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (Meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, aryl (meth) acrylate, propargyl (Meth) acrylate , Benzyl (meth) (meth) acrylic acid esters such as acrylate;

Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

2,1-hept-2-ene, 5-methylbicyclo [2.2.1] 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] 2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1 ] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] 2,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy- Methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2 1] hepto-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] 2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-bis (tert-butoxycarb Cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene, and the like;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as 6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

But are not limited to, styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Of these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable in view of copolymerization reactivity and heat resistance.

In the resin [K1], the ratio of the structural units derived from each of the resins [K1] is preferably within the following range among the total structural units constituting the resin [K1].

a structural unit derived from (a); 60 to 98 mol% (more preferably 65 to 95 mol%),

a structural unit derived from (b); 2 to 40 mol% (more preferably 5 to 35 mol%)

When the ratio of the structural units of the resin [K1] is within the above range, the storage stability, developability and solvent resistance of the cured pattern tend to be good.

Resin [K1] can be prepared by, for example, the method described in "Experimental Method of Polymer Synthesis" (Takatsuki Otsu, 1st Edition, Chemical Issuer Co., Ltd., 1st Printing, March 1, 1972) Can be prepared by referring to the reference documents listed in the literature.

Concretely, there is exemplified a method in which a prescribed amount of (a) and (b), a polymerization initiator and a solvent are mixed in a reaction vessel, and oxygen is replaced by nitrogen, thereby stirring, heating and maintaining the temperature under deoxygenation. The polymerization initiator, solvent and the like to be used herein are not particularly limited, but any of those conventionally used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides (benzoyl peroxide and the like) And as the solvent, any one may be used as long as each monomer is dissolved. As the solvent of the photosensitive resin composition, a solvent described later or the like may be used.

The solution obtained after the reaction may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) extracted by a method such as re-precipitation may be used. Particularly, the solvent after the reaction can be used as it is by using the solvent (D) described later as a solvent in the polymerization, and the production process can be simplified.

In the resin [K2], the proportion of the structural units derived from each of the resins [K2] is preferably in the following range among the total structural units constituting the resin [K2].

a structural unit derived from (a); 2 to 95 mol% (more preferably 5 to 80 mol%)

a structural unit derived from (b); 2 to 40 mol% (more preferably 5 to 35 mol%)

a structural unit derived from (c); 1 to 65 mol% (more preferably 1 to 60 mol%)

When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability, developability, solvent resistance of the cured pattern, heat resistance and mechanical strength tend to be good.

The resin [K2] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

Concretely, there is a method in which a prescribed amount of (a), (b) and (c), a polymerization initiator and a solvent are mixed in a reaction vessel and oxygen is replaced by nitrogen to stir, have. The solution obtained after the reaction may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) extracted by re-precipitation or the like may be used.

In the resin [K3], the proportion of the structural units derived from each of the resins [K3] is preferably in the following range among the total structural units constituting the resin [K3].

(b) 2 to 40 mol%, more preferably 5 to 35 mol%

(c) 60 to 98 mol%, more preferably 65 to 95 mol%

The resin [K3] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

The resin [K4] can be obtained by obtaining a copolymer of (b) and (c) and adding a carboxyl group having (c) to a cyclic ether having 2 to 4 carbon atoms having (a). First, a copolymer of (b) and (c) is prepared in the same manner as described for the production of [K1]. In this case, it is preferable that the proportion of the structural units derived from each of the total structural units constituting the copolymer of (b) and (c) falls within the following range.

(b) 5 to 50 mol%, more preferably 10 to 45 mol%

(c) 50 to 95 mol%, more preferably 55 to 90 mol%

Subsequently, a cyclic ether having 2 to 4 carbon atoms having (a) is reacted with a part of the carboxyl group and / or the carboxylic anhydride contained in the structural unit derived from (c) in the copolymer.

(a), a reaction catalyst of a carboxyl group and a cyclic ether (for example, tris (dimethylaminomethyl) thiophene) in the presence of a catalyst, Phenol and the like) in an amount of 0.001 to 5 mass% based on the total amount of the components (a) to (c) and 0.001 to 5 parts by mass relative to the total amount of the polymerization inhibitor (such as hydroquinone) The resin [K4] can be obtained by putting the mass% in a flask, for example, at 60 to 130 DEG C for 1 to 10 hours. The reaction conditions such as the compounding method, the reaction temperature and the time can be suitably adjusted in consideration of the production equipment or the amount of heat generated by polymerization. In addition, the mixing method and the reaction temperature can be appropriately adjusted in consideration of the production equipment or the amount of heat generated by polymerization in the same manner as the polymerization conditions.

The amount of (a) in this case is preferably 5 to 80 mol%, more preferably 10 to 75 mol%, and still more preferably 15 to 70 mol% based on (b). Within this range, the balance between storage stability, developability, solvent resistance, heat resistance, mechanical strength and sensitivity tends to be improved.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxy tricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) Resin [K1] such as coalescence; (Meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxy tricyclo [5.2] .1.0 ^2.6] decyl acrylate / (meth) resins such as acrylic acid / N- cyclohexyl maleimide copolymer, 3-methyl-3- (meth) acryloyloxyethyl-methyl oxetane / (meth) acrylic acid / styrene copolymer [K2]; Resins [K3] such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; A resin obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate / (meth) acrylic acid copolymer, a resin obtained by adding glycidyl (meth) acrylate to tricyclodecyl (meth) acrylate / styrene / ) Resin such as a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) . Among them, the resin [K1] and the resin [K2] are preferable, the resin [K1] is more preferable, and the 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate / (meth) desirable.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 5,000 to 35,000, more preferably 6,000 to 30,000, and still more preferably 7,000 to 28,000. When the molecular weight is in the above range, the hardness of the coating film is improved and the residual film ratio is also increased, the solubility of the unexposed portion in the developing solution is good, and the resolution tends to be improved.

The acid value of the resin (B) is preferably 50 to 150, more preferably 60 to 135, still more preferably 70 to 135. Here, the acid value is a value measured as an amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass, based on the solid content of the coloring composition. When the content of the resin (B) is in the above range, a pattern can be formed, and the resolution and the residual film ratio tend to be improved.

The coloring composition of the present invention preferably contains a polymerizable compound (C). The polymerizable compound (C) is not particularly limited as long as it is a compound capable of polymerizing with an active radical or an acid generated from the polymerization initiator (D) by irradiation with light, and includes a compound having a polymerizable carbon-carbon unsaturated bond .

The polymerizable compound (C) is preferably a compound having three or more polymerizable groups, and more preferably a compound having three or more (meth) acryloyloxy groups. As the polymerizable compound (C), for example, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate , Dipentaerythritol hexamethacrylate, and the like. These polymerizable compounds (C) may be used alone or in combination of two or more.

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

The coloring composition of the present invention preferably contains a polymerization initiator (D). The polymerization initiator (D) is a compound capable of initiating polymerization of the polymerizable compound (C) that generates active radicals, acids, etc. by the action of light or heat. The polymerization initiator (D) is preferably a compound which generates a radical by ultraviolet rays. Examples of the active radical generator include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, and oxime compounds.

Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- 2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl Ketones and oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, 1- (4-methylsulfanylphenyl) propane-1-one.

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

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'- -Butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

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

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis Azine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4- dimethoxyphenyl) ethenyl] 5-triazine and the like.

Specific examples of the oxime compounds include O-acyloxime compounds such as N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N 2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl] ethan-1-imine, N-acetoxy-1- [9-ethyl-6- { } -9H-carbazol-3-yl] ethan-1-imine.

Examples of the different active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'- Benzyl, 9,10-phenanthrenequinone, camphaquinone, methyl phenylglyoxylate, titanocene compounds, and the like can be given. have.

As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate , 4-acetoxyphenyl-methylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, Diphenyliodonium hexafluoroantimonate and diphenyl iodonium hexafluoroantimonate; and nitrobenzyl tosylates, benzoin tosylates and the like.

Among the above-mentioned compounds as active radical generating agents, there are also compounds which generate an acid at the same time as an active radical. For example, a triazine compound is also used as an acid generator.

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

The coloring composition of the present invention may further contain a polymerization initiator (F). The polymerization initiator (F) is generally used in combination with the polymerization initiator (D) and is a compound or photosensitizer used for promoting polymerization of a polymerizable compound initiated by polymerization initiator.

Examples of the polymerization initiator (F) include an amine compound, an alkoxyanthracene compound, and a thioxanthone compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2- N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively, Michler's ketone), 4,4'-bis (diethylamino) benzo Phenanone, 4,4'-bis (ethylmethylamino) benzophenone, and the like, among which 4,4'-bis (diethylamino) benzophenone is preferable. For example, a commercially available product such as a trade name " EAB-F " (manufactured by Hodogaya Chemical Co., Ltd.) may be used as a polymerization initiator.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

The thioxanthone compound is also used as a polymerization initiator (F). Specifically, the thioxanthone compound may be the same as described above.

When the polymerization initiator (F) is used, the amount thereof to be used is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol, per 1 mol of the polymerization initiator (D).

The coloring composition of the present invention comprises a solvent (E).

Examples of the solvent (E) include an ester solvent (a solvent having -COO-), an ether solvent other than an ester solvent (a solvent having -O- and no -COO-), an ether ester solvent (-COO- and -O- (A solvent having -CO- and having no -COO-), an alcohol solvent (a solvent having OH, and having no -COO-, -O- and -CO-), a ketone solvent Aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide, and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, Butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

Examples of the ether solvent include 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, propylene glycol Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1 , 4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, .

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, Ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, Methyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, propyleneglycol monomethyl ether acetate, Ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol mono Ether and the like can be mentioned acetate, diethylene glycol monobutyl ether acetate.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4- Cyclohexanone, isophorone, and the like.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.

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

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

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

Among the above solvents, an organic solvent having a boiling point of at least 120 캜 and not more than 180 캜 at 1 atm is preferable from the viewpoint of coatability and dryness of the coloring composition, and propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether are more preferable .

The content of the solvent (E) in the coloring composition is preferably 70 to 95 mass%, more preferably 75 to 90 mass%, with respect to the coloring composition.

The coloring composition of the present invention may further contain a surfactant (G). Examples of the surfactant (G) include at least one selected from the group consisting of a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom.

Examples of the silicone surfactant include surfactants having a siloxane bond. Specific examples of the silicone oil include silicone oils such as silicone oils such as Toren Silicone DC3PA, Toresilicon SH7PA, Toresilicon DC11PA, Toresilicon SH21PA, Toresilicon SH28PA, Toresilicon SH29PA, Toresilicon SH30PA and Polyether Modified Silicone Oil SH8400 (trade name: Torre- (Product of Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance, Performance), KP321, KP323, KP324, KP326, KP340 and KP341 Japan Joint Venture Company).

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, there may be mentioned Fluoride (trade name) FC430, Fluoride FC431 (manufactured by Sumitomo 3M Limited), Megapack (trade name) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, Megapack F183, Epson EF301, Epson EF303, Epson EF351 and Epson EF352 (manufactured by Mitsubishi Material Electronics Co., Ltd.), Chapron (trade name) S381, Chapron S382, (Manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Research Co., Ltd.), and the like.

Examples of the silicon-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorinated carbon chain. Specific examples thereof include Megapac (registered trademark) R08, Megapack BL20, Megapack F475, Megapack F477, and Megapack F443 (manufactured by DIC Corporation).

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

The content of the surfactant (G) is preferably 0.0001 mass% or more and 0.2 mass% or less, and more preferably 0.001 to 0.1 mass% with respect to the coloring composition. When the content of the surfactant (G) is in the above range, the flatness of the film coated with the coloring composition tends to be improved.

When the coloring composition of the present invention comprises only the dye and the solvent (E) of the present invention, it can be prepared by mixing and dissolving the dye of the present invention and the solvent (E). After mixing, it is preferable to remove the insoluble matter by filtration using a filter. The diameter of the filter is preferably 3 占 퐉 or less, and more preferably 0.1 to 2 占 퐉.

When the coloring composition of the present invention contains a component other than the dye and the solvent (E) of the present invention, the coloring composition consisting solely of the dye and the solvent (E) of the present invention prepared by the above- Component of the present invention. At the time of mixing, the solvent (E) may further be added. Components other than the dye of the present invention may be mixed after dissolving or dispersing in the solvent (E). The solvent (E) used to dissolve each of the above components may be the same or different as long as they are compatible. After mixing, it is preferable to remove the insoluble matter by filtration using a filter. The diameter of the filter is 10 μm or less, preferably 5 to 1 μm when the colorant (A) contains a pigment, and 3 μm or less, preferably 0.1 to 1 μm when the colorant (A) 2 mu m.

As a method for forming a color filter or a pattern thereof using the coloring composition of the present invention, for example, a method of forming the coloring composition of the present invention on a substrate or a separate resin layer (for example, a separate coloring composition layer , A method of removing a volatile component such as a solvent to form a colored layer and exposing the colored layer to light through a photomask, and a method using an ink jet machine that does not require a photolithography method .

The film thickness of the coating film in this case is not particularly limited, but it can be suitably adjusted in accordance with the materials used, the use, and the like, and is preferably from 0.1 to 30 탆, more preferably from 1 to 20 탆, still more preferably from 1 to 6 탆 to be.

The coating method of the coloring composition includes, for example, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method and a die coating method. In addition, a coater such as a deep coater, a bar coater, a spin coater, a slit & spin coater, a slit coater (also referred to as a die coater, a curtain flow coater, or a spinless coater) Or the like.

For example, natural drying, ventilation drying, and vacuum drying can be used to remove or dry the solvent. The specific drying temperature is preferably 10 to 120 占 폚, more preferably 25 to 100 占 폚. The drying time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. In the case of performing the reduced-pressure drying, it is preferably carried out at a temperature of 20 to 25 캜 under a pressure of 50 to 150 Pa.

The coated film after drying is exposed through a photomast to form a desired pattern. At this time, the pattern form on the photomask is not particularly limited, but a pattern form according to the intended use is used.

As a light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. Specific examples thereof include mercury lamps, light emitting diodes, metal halide lamps, and halogen lamps. It may be selectively extracted by using a band pass filter that cuts out a specific wavelength region using a cut filter or selects a specific wavelength region and exposes it.

It is preferable to use a mask aligner, a stepper, or the like in order to uniformly irradiate the entire surface of the exposure surface with a parallel light beam or to align the mask with the substrate accurately.

After exposure, a pattern can be obtained by dissolving and developing a predetermined portion, for example, an unexposed portion, which is brought into contact with a developing solution. Examples of the developing solution include aqueous solutions of alkaline compounds (potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide, etc.) which may contain a surfactant.

The developing method may be any one of a paddle method, a dipping method, a spray method, and the like. Further, the substrate may be inclined at an arbitrary angle in development. After development, it is preferable to wash with water.

Furthermore, post baking may be performed as necessary. The post-baking is preferably carried out at, for example, 150 to 230 캜 for 10 to 240 minutes.

According to the present invention, it becomes possible to provide a dye excellent in storage stability against a solution dissolved in an organic solvent.

The coloring composition containing the dye of the present invention can be suitably used for forming a color filter or a coloring pattern and can be used suitably for forming a coloring pattern excellent in color density, brightness, contrast, sensitivity, resolution, Can be obtained. Such a color filter or a colored pattern can be used as a part of constituent parts such as an optical film, an array substrate, and a color filter substrate. Furthermore, at least one selected from the group consisting of the optical film, the array substrate, and the color filter substrate may be a display device such as a liquid crystal display device or an organic EL device; A solid-state image sensor or the like.

Example

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

Example 1

After adding 200 parts of water to 10 parts of m-toluidine-4-sulfonic acid [compound represented by the formula (a-2)], the pH was adjusted to 7 to 8 with 30% aqueous sodium hydroxide solution under ice-cooling. The following operation was carried out under ice-cooling. 11.1 parts of sodium nitrite was added and stirred for 30 minutes. 39 parts of 35% hydrochloric acid was added in small portions to make a brown solution, which was then stirred for 2 hours. An aqueous solution prepared by dissolving 10.1 parts of amide sulfuric acid in 101 parts of water was added to the reaction solution and stirred to obtain a suspension containing the diazonium salt.

To a mixture of 14 parts of 1- (2-ethylhexyl) -3-cyano-4-methyl-6-hydroxypyrid-2-one [compound represented by the formula (c-2) After adding 25 parts of ralidon, the mixture was adjusted to pH 8 to 9 with 30% aqueous sodium hydroxide solution under ice-cooling.

The following operation was carried out under ice-cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and the suspension containing the diazonium salt was dropped by a pump over 2 hours while adjusting the pH to 8 to 9 with 30% sodium hydroxide aqueous solution. After completion of the dropwise addition, the mixture was further stirred for 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried under reduced pressure at 60 캜 to obtain 21.4 parts (yield: 87%) of a compound represented by the formula (d-3).

0.35 g of the compound (d-3) was dissolved in N, N-dimethylformamide to make a volume of 250 cm 3, and 2 cm 3 of the solution was diluted with water to make a volume of 100 cm 3 (concentration: 0.028 g / The absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound has a? _Max = 433 nm and an absorbance of 2.9 (arbitrary unit).

5.0 parts of the compound (d-3), 35 parts of acetonitrile and 1.6 parts of N, N-dimethylformamide were fed into a flask equipped with a stirrer, a cooling tube and a stirrer, and thionyl chloride 2.4 And then added dropwise. After completion of dropwise addition, the temperature was raised to 40 占 폚, reacted while maintaining the same temperature for 2 hours, and then cooled to 20 占 폚. The cooled reaction solution was poured into 150 parts of ice water while stirring, followed by stirring for 30 minutes. The precipitated yellow crystals were separated by filtration, washed well with tap water, and dried under reduced pressure at 60 DEG C for 2 hours. A flask equipped with a cooling tube and a stirrer was separately prepared, 2.0 parts of 1-amino-2-propanol and 20 parts of N-methylpyrrolidone were added thereto, and while the temperature was maintained at 20 ° C or lower while stirring, Over a period of time. After adding the yellow crystals, the liquid temperature was raised to room temperature, and then the reaction solution was stirred for 30 minutes. After 40 parts of methanol was added to the reaction solution and stirred, the mixture was stirred in a mixed solution of 29 parts of acetic acid and 300 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 3.9 parts (yield: 69%) of a compound represented by the formula (III-3).

0.35 g of the compound (III-3) was dissolved in ethyl lactate to make a volume of 250 cm 3, and 2 cm 3 of the solution was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / Quartz cell, optical path length: 1 cm) was used to measure the absorption spectrum. This compound has a? _Max = 431 nm and an absorbance of 2.3 (arbitrary unit).

The following reaction was carried out in a nitrogen atmosphere. After adding 150 parts of N-methylpyrrolidone to 49.9 parts of the compound (III-3), the reaction solution was adjusted by stirring for 30 minutes. Under stirring at room temperature, 6.8 parts of sebacic acid chloride was added dropwise while stirring the reaction solution. After completion of the dropwise addition, stirring was continued for another 8 hours. 7.8 parts of adipic acid chloride was added dropwise. After completion of the dropwise addition, stirring was continued for another 8 hours. After the reaction solution was poured into 300 parts of water, 80 parts of ethyl acetate was added and stirred for 30 minutes. The organic phase was collected by using a separating rod, and then washed with 500 parts of water, 3000 parts of 10% sodium carbonate aqueous solution, 1000 parts of 10% acetic acid aqueous solution and 1000 parts of ion-exchanged water. The separated organic phase was evaporated to remove the solvent to obtain 2.0 parts of a dye (a) which is a mixture of the compound represented by the formula (I-6) and the compound represented by the formula (I-7). Yield 85%.

0.35 g of the dye (a) was dissolved in ethyl lactate to make a volume of 250 cm 3, and 2 cm 3 of the solution was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / , Optical path length: 1 cm) was used to measure the absorption spectrum. This compound has a? _Max = 431 nm and an absorbance of 2.2 (arbitrary unit).

≪ Measurement of the content ratio in the mixture &

The content ratio of the compound represented by the formula (I-6) and the compound represented by the formula (I-7) in the dye (a) was measured by a calibration curve method using liquid chromatography (HPLC). The calibration curve method is a method of determining the unknown concentration from the concentration-absorbance relationship of a standard column of known concentration at the time of determining the substance concentration in the solution

HPLC apparatus Prominence (manufactured by Shimadzu Corporation)

Two liquid delivery units: LC-20AT

Autosampler: One SIL-20A

Column Oven: One CTO-20A

UV detector: 1 SPD-20A

Online degasser: 1 DGU-20A

Column Wakosil II 3C18HG (3 占 퐉, 3 mm? 150 mm)

Liquid phase A; 0.1% TBAB / water: acetonitrile (9: 1)

Solution B; 0.1% TBAB / water: acetonitrile (1: 9)

Gradient [solution B]

B initial concentration 25%

25% → (30 minutes) → 100% (20 minutes)

Detection wavelength 254 nm

Column temperature 40 ° C

Flow rate 0.5 mL / min

Injection amount 5 μL

TBAB: tetrabutylammonium bromide

The compound represented by the formula (I-6) and the compound represented by the formula (I-7) were each dissolved in acetonitrile to prepare a solution having the concentration shown in Table 22. The solution was subjected to liquid chromatography analysis under the above-mentioned conditions, and elution time and peak area were measured. The results are shown in Table 22.

From the concentration of the solution and the area of the measured peak, the calibration curve was obtained by the following equation.

Calibration curve of the compound represented by the formula (I-6): (peak area) = 72.2 x (concentration)

Calibration curve of the compound represented by the formula (I-7): (peak area) = 76.0 x (concentration)

13.9 mg of the dye (a) was dissolved in acetonitrile to make the volume 50 cm 3 (concentration: 0.278 g / L), and the liquid chromatography analysis was carried out under the above conditions to measure the elution time and the peak area. The compound represented by the formula (I-7) was eluted at an elution time of 35.9 minutes, and its peak area was 944436. At the elution time of 37.9 minutes, the compound represented by the formula (I-6) was eluted, and the peak area thereof was 1108707.

The content of each compound in the mixture (a) was determined using the above calibration curve, and as a result, the compound represented by the formula (I-6) / the compound represented by the formula (I-7) = 44.7 / 55.3.

Example 2

101 parts of the compound represented by the formula (I-6) and 101 parts of the compound represented by the formula (I-7) were mixed in an agate mortar to prepare a dye (b).

12.9 mg of the dye (b) was dissolved in acetonitrile to adjust the volume to a solution of 50 cm 3 (concentration: 0.258 g / L). The elution time and peak area were measured in the same manner as in Example 1. The compound represented by the formula (I-7) was eluted at an elution time of 37.6 minutes, and its peak area was 964928. At the elution time of 39.8 minutes, the compound represented by the formula (I-6) was eluted and its peak area was 902508. Using the above calibration curve, the content ratio of each compound in the mixture (B) was determined. As a result, the compound represented by the formula (I-6) / the compound represented by the formula (I-7) = 49.9 / 50.1.

Example 3

141 parts of the compound represented by the formula (I-6) and 60 parts of the compound represented by the formula (I-7) were mixed in an agate mortar to prepare the dye (III).

11.5 mg of the dye (c) was dissolved in acetonitrile to adjust the volume to a solution of 50 cm 3 (concentration: 0.230 g / L). The elution time and peak area were measured in the same manner as in Example 1. The compound represented by the formula (I-7) was eluted at an elution time of 37.6 minutes, and its peak area was 512173. At the elution time of 39.9 minutes, the compound represented by the formula (I-6) was eluted and its peak area was 1152000. Using the above calibration curve, the content ratio of each compound in the mixture (C) was determined. As a result, the compound represented by the formula (I-6) / the compound represented by the formula (I-7) = 70.3 / 49.9.

Example 4

180 parts of the compound represented by the formula (I-6) and 20 parts of the compound represented by the formula (I-7) were mixed in an agate mortar to prepare a dye (D).

10.9 mg of the dye (D) was dissolved in acetonitrile to adjust the volume to a solution of 50 cm 3 (concentration: 0.218 g / L). The elution time and peak area were measured in the same manner as in Example 1. The compound represented by the formula (I-7) was eluted at an elution time of 37.6 minutes, and its peak area was 173668. At the elution time of 39.8 minutes, the compound represented by the formula (I-6) was eluted and its peak area was 1336073. Using the above calibration curve, the content ratio of each compound in the mixture (D) was determined. As a result, the compound represented by the formula (I-6) / the compound represented by the formula (I-7) = 89.9 / 10.1.

Example 5

≪ Adjustment of coloring composition >

In the sample tube, 5 parts of the dye (a) and 95 parts of propylene glycol monomethyl ether acetate were mixed, tightly sealed, and then vibrated with an ultrasonic vibrator at 40 占 폚 for 10 minutes. Subsequently, the mixture was allowed to stand at room temperature for 30 minutes, and then filtered through a membrane filter (HLC-DISK 13, manufactured by Kanto Chemical Co.) having a diameter of 0.45 μm to obtain a colored composition. Insolubles and the like were visually confirmed on the filter at the time of filtration.

Synthesis Example 1

The following compound (III-2) was synthesized by the method described in Patent Document 1. 0.35 g of Compound (III-2) was dissolved in ethyl lactate to make a volume of 250 cm 3, and 2 cm 3 of the solution was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / Quartz cell, optical path length: 1 cm) was used to measure the absorption spectrum. This compound has a? _Max = 425 nm and an absorbance of 2.2 (arbitrary unit).

Examples 6 to 8 and Comparative Examples 1 to 3

A coloring composition was obtained in the same manner as in Example 5 except that the dye shown in Table 23 and a solvent were mixed.

In Table 23, PGMEA represents propylene glycol monomethyl ether acetate.

<Evaluation of Storage Stability>

The sample tube in which the coloring composition was sealed was kept at 5 캜 in an incubator (Sanyo Denki Kogyo: MIR-553).

With respect to the colored composition after storage, the presence or absence of the precipitate was visually confirmed. When no insoluble matter was confirmed after 10 days, no insoluble matter was found in the coloring composition after 10 days of storage, and when insoluble matter was confirmed in the coloring composition after 20 days of storage, the result was stored for 20 days When insoluble matter was not found in the coloring composition after 30 days of storage, it was rated as? When insoluble matter was identified in the coloring composition after 30 days of storage, and when the insoluble matter was not identified in the coloring composition after 30 days of storage, it was rated as?. The results are shown in Table 24.

Example 9

[Preparation of coloring composition]

(A) Colorant: dye (b) 0.30 parts by mass

(B) resin: methacrylic acid / benzyl methacrylate copolymer (molar ratio 30/70, average molecular weight: 10700, acid value: 70 mgKOH / g) [HN-123; Manufactured by Taoka Chemical Industry Co., Ltd.] 33.8% propylene glycol monomethyl ether acetate solution 1.67 parts by mass

(C) Polymerizable compound: dipentaerythritol hexaacrylate [KAYARAD DPHA; (Manufactured by Nippon Kayaku Co., Ltd.) 1.48 parts by mass

(D) Polymerization initiator: 0.22 parts by mass of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Irgacure OXE01 (produced by BASF Japan)

(G) Surfactant: polyether-modified silicone oil [Torensilicon SH8400; 1% propylene glycol monoethyl ether acetate solution (manufactured by Toray-Dow Corning Co., Ltd.)

0.10 parts by mass

(E) Solvent: Propylene glycol monomethyl ether acetate 6.23 parts by mass

To obtain a coloring composition.

<Evaluation of Storage Stability>

The sample tube filled with the coloring composition was stored at 5 占 폚 for 30 days in an incubator (Sanyo Denki; MIR-553).

[Production of color filter]

The colored composition after being stored on glass (# 1737; Corning) was applied by a spin coat method and baked at 100 ° C for 3 minutes to volatilize the volatile components. After the glass coated with the coloring composition was cooled to room temperature, an exposure machine (TME-150RSK; (Manufactured by Topcon Co., Ltd.) was irradiated with light at an exposure apparatus (based on 365 nm) at 150 mJ / cm 2 in the air atmosphere. Then, it was baked in an oven at 220 DEG C for 2 hours to prepare a color filter (film thickness 2.2 mu m).

[Foreign object evaluation]

The obtained color filter was observed at a magnification of 250 times using a surface shape measuring microscope (VF-7510; manufactured by KYENS), and the number of foreign objects in the form of a black spot or a white spot in the visual field was examined. In the case where the number of foreign matters is 20 or less, it is determined that the number of foreign matters derived from the deposition of the dye is small, and when the number of foreign matters is more than 20, the number is determined as x. The results are shown in Table 25.

Example 10

A colored composition was obtained in the same manner as in Example 9 except that the dye (a) was changed to the dye (b). Evaluation of storage stability was carried out in the same manner as in Example 9. The results are shown in Table 25.

From the results shown in Tables 24 and 25, it was confirmed that the coloring composition comprising the dye of the present invention and the organic solvent suppressed the generation of precipitates and improved the storage stability.

The dye of the present invention is a solution dissolved in an organic solvent and is excellent in storage stability. The coloring composition containing the dye of the present invention can be suitably used for forming a color filter or a coloring pattern and is excellent in coloring patterns having few foreign matters and excellent in color density, brightness, contrast, sensitivity, resolution, heat resistance, Can be obtained. Such a color filter or a colored pattern can be used as a part of constituent parts such as an optical film, an array substrate, and a color filter substrate. Furthermore, at least one selected from the group consisting of the optical film, the array substrate, and the color filter substrate may be a display device such as a liquid crystal display device or an organic EL device; Solid-state activation devices, and the like.

Claims (7)

A dye comprising two or more compounds represented by formula (I).

[In the formula (I), Z ¹ and Z ² each independently represent an alkanediyl group having 1 to 8 carbon atoms, and -CH ₂ - in the alkanediyl group may be substituted with -O-.
L ¹ represents an alkanediyl group having 1 to 8 carbon atoms which may contain -C (= CH ₂ ) -.
R ¹ and R ² each independently represent a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, or an acyl group having 2 to 5 carbon atoms.
A ¹ and A ² each independently represent a phenylene group which may have an alkyl group having 1 to 8 carbon atoms.
B ¹ and B ² each independently represent a group represented by formula (II).

[In the formula (II), R ⁴ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 16 carbon atoms, and the hydrogen atom in the saturated hydrocarbon group may be substituted with an alkoxy group or a carboxy group having 1 to 8 carbon atoms.
And R &lt; ⁵ &gt; represents a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms. delete The method according to claim 1,
Wherein the compound represented by the formula (I) is a mixture obtained by reacting at least one compound represented by the formula (I-A) with at least two compounds represented by the formula (I-B ').

In the formulas (I-A) and (I-B '), R ¹ , A ¹ , B ¹ , Z ¹ and L ¹ have the same meanings as defined above.
X ¹ and X ² each independently represent a halogen atom. A coloring composition comprising a dye and a solvent according to claim 1. 5. The method of claim 4,
Further, a coloring composition comprising at least one selected from the group consisting of a resin, a polymerizable compound and a polymerization initiator. A color filter formed using the coloring composition of claim 4. A display device comprising the color filter according to claim 6.