KR101725265B1 - Compound - Google Patents

Abstract

[식(I)에서, Z¹, Z² 및 Z³은, 각각 독립으로, 치환기를 가지고 있어도 되는 2가의 C_{1 -16} 지방족 탄화수소기를 나타내고, Z¹, Z² 및 Z³에 포함되는 -CH₂-는, -CO- 또는 -O-으로 치환되어 있어도 되고,
R¹ 및 R²는, 각각 독립으로, 수소원자, 치환기를 가지고 있어도 되는 1가의 C_1-16 지방족 탄화수소기 또는 치환기를 가지고 있어도 되는 C_{2 -18} 아실기를 나타내고,
A¹ 및 A²는, 각각 독립으로, 치환기를 가지고 있어도 되는 2가의 C_{6 -14} 방향족 탄화수소기를 나타내고,
B¹ 및 B²는, 각각 독립으로, 치환기를 가지고 있어도 되는 1가의 C_{6 -14} 방향족 탄화수소기 또는 치환기를 가지고 있어도 되는 C_{3 -14} 방향족 복소환기를 나타낸다.]A compound represented by formula (I).

In the formula (I), Z ^1, Z ² and Z ³ are, each independently, a divalent C _{1 -16} aliphatic hydrocarbon group which may have a substituent, -CH contained in Z ^1, Z ² and Z ³ ₂ - may be substituted with -CO- or -O-,
R ¹ and R ² each independently represent a hydrogen atom, a monovalent C _1-16 aliphatic hydrocarbon group which may have a substituent or a C _{2 -18} acyl group which may have a substituent,
A ¹ and A ² are, each independently, a divalent aromatic C _{6 -14} hydrocarbon group which may have a substituent,
B ¹ and B ² each independently represent a monovalent C _{6 -14} aromatic hydrocarbon group which may have a substituent or a C _{3 -14} aromatic heterocyclic group which may have a substituent.

Description

Compound {COMPOUND}

The present invention relates to a compound useful as a dye and a colored photosensitive resin composition containing the compound.

Dyes are used as colorants contained in color filters for display devices such as liquid crystal display panels, electroluminescence and plasma display panels. As a dye, for example, a compound represented by the formula (III-4) is described in Patent Document 1.

[Patent Document 1]

Japanese Patent Application Laid-Open No. 2006-124634

The compound represented by the formula (III-4) has a problem that the solubility in a solvent is not sufficient and the transferability is high. The dyes refer to dyes contained in any material adhered to or absorbed by other materials using air or water vapor as a medium.

Thus, the inventors of the present invention have studied to improve the solubility and migration property of a solvent, and have reached the present invention.

That is, the present invention provides the following [1] to [5].

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

In the formula (I), Z ^1, Z ² and Z ³ are, each independently, a divalent C _{1 -16} aliphatic hydrocarbon group which may have a substituent, -CH contained in Z ^1, Z ² and Z ³ ₂ - may be substituted with -CO- or -O-,

R ¹ and R ² each independently represent a hydrogen atom, a monovalent C _1-16 aliphatic hydrocarbon group which may have a substituent or a C _{2 -18} acyl group which may have a substituent,

A ¹ and A ² are, each independently, a divalent aromatic C _{6 -14} hydrocarbon group which may have a substituent,

B ¹ and B ² each independently represent a monovalent C _{6 -14} aromatic hydrocarbon group which may have a substituent or a C _{3 -14} aromatic heterocyclic group which may have a substituent.

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

In the formula (II), R ³ represents a monovalent C _{1 -16} aliphatic hydrocarbon group which may have a hydrogen atom or a substituent,

R ⁴ represents a monovalent C _{1 -16} aliphatic hydrocarbon group which may have a substituent.

[3] A colored photosensitive resin composition comprising a colorant, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent containing the compound according to [1] or [2]

[4] A coated film formed by using the colored photosensitive resin composition according to [3].

[5] A display device comprising the coating film described in [4].

The present invention is a compound represented by the formula (I) (hereinafter sometimes referred to as " compound (I) "). In the present specification, C _ab means that the number of carbon atoms is a or more and b or less.

In the formula (I), Z ^1, Z ² and Z ³ are, each independently, a divalent C _{1 -16} aliphatic hydrocarbon group which may have a substituent, -CH contained in Z ^1, Z ² and Z ³ ₂ - may be substituted with -CO- or -O-.

R ¹ and R ² each independently represent a hydrogen atom, a monovalent C _1-16 aliphatic hydrocarbon group which may have a substituent or a C _{2 -18} acyl group which may have a substituent.

A ¹ and A ² are, each independently, represents a divalent aromatic C _{6 -14} hydrocarbon group which may have a substituent.

B ¹ and B ² each independently represent a monovalent C _{6 -14} aromatic hydrocarbon group which may have a substituent or a C _{3 -14} aromatic heterocyclic group which may have a substituent.

Z ^1, Z ² and Z ³ are, each independently, represents a divalent C _{1 -16} aliphatic hydrocarbon group which may have a substituent. The number of carbon atoms of the substituent is not included in the carbon number of the C _{1 -16} aliphatic hydrocarbon group, and the number thereof is preferably 2 to 10, more preferably 2 to 8.

Examples of the divalent C _{1 -16} aliphatic hydrocarbon groups, C _{1 -16} may be mentioned an alkanediyl group, a methylene group, an ethylene group, a propane-diyl, butane-diyl, pentane-diyl, hexane-diyl, heptane-diyl, octane A dodecyl group, a decanediyl group, a tetradecanediyl group, and a hexadecanediyl group.

-CH ₂ - included in the C _{1 -16} aliphatic hydrocarbon group may be substituted with -CO- or -O-. C _{1 -16} aliphatic hydrocarbon groups include a hydrogen atom that may be substituted with a halogen atom, the fluorine atom.

Z ¹ and Z ² is preferably an alkanediyl include -O- and optionally C _{1 -8} seen that group, and is included to -O- and more preferably C _{5 -7} an alkanediyl group which may. Preferred _{group, - (CH 2) 3 -} , - (CH 2) 2 -O- (CH 2) 2 -, - (CH 2) 2 -O- (CH 2) 2 -O- (CH 2) 2 - or -CH ₂ -CH (CH ₃₎ - a.

Inclusive, C _1-8 alkanediyl group is more preferred, and even C _{1 -8} and that the alkanediyl group is preferably C ₄ and _-8 alkanediyl group in the - Z is ^3, -C (= C) More preferable. Preferred groups are - (CH ₂ ) ₂ -, - (CH ₂ ) ₄ - or -CH ₂ -C (= CH ₂ ) -.

R ¹ and R ² each independently represent a hydrogen atom, a monovalent C _1-16 aliphatic hydrocarbon group which may have a substituent or a C _{2 -18} acyl group which may have a substituent.

The monovalent C _{1 -16} aliphatic hydrocarbon group may be any of linear, branched or cyclic. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number thereof is preferably from 6 to 10, more preferably from 1 to 4.

Examples of the monovalent C _{1 -16} aliphatic hydrocarbon group, for example, methyl group, ethyl group, n- propyl group, isopropyl group, n- butyl group, isobutyl group, sec- butyl group, tert- butyl group, a methylbutyl group (E.g., 1,1,3,3-tetramethylbutyl), methylhexyl (1,5-dimethylhexyl), ethylhexyl (2-ethylhexyl), cyclopentyl, A methylcyclohexyl group (such as a 2-methylcyclohexyl group), and a cyclohexylalkyl group.

Hydrogen atoms contained groups monovalent C _{1 -16} aliphatic hydrocarbon is optionally substituted by a C _{1 -8} alkoxy group, or a carboxyl group. Examples of a C _{1 -8} C _{1 -16} aliphatic hydrocarbon group substituted with alkoxy, e.g. propoxy-propyl (3- (isopropoxy) propyl group, etc.), and alkoxy-propyl (3- (2-ethylhexyloxymethyl) Propyl group, etc.). Examples of a C _{1 -16} aliphatic hydrocarbon group substituted by a carboxy group, for example, there may be mentioned 2- (carboxy) ethyl group, 3- (carboxy) propyl and 4- (carboxy) butyl group.

Hydrogen atoms contained C _2-18 acyl groups are, or may be substituted with a monovalent C _{1 -8} saturated aliphatic hydrocarbon group, or C _1-8 alkoxy. The carbon number of the C _{2 -18} acyl group which may have a substituent is counted including the carbon number of the substituent, and the number thereof is 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.

R ¹ and R ² are preferably a hydrogen atom, a C _{1 -4} aliphatic hydrocarbon group or a C _{2 -5} acyl group. Preferred groups include a hydrogen atom, -C (= O) -CH ₃ Or -C (= O) -C ₂ H ₅ .

A ¹ and A ² are, each independently, represents a divalent aromatic C _{6 -14} hydrocarbon group which may have a substituent.

_{Examples of the} divalent C _{6 -14} aromatic hydrocarbon group include a phenylene group and a naphthylene group, and a phenylene group is preferable.

The substituent of the divalent C _{6 -14} aromatic hydrocarbon group, there may be mentioned halogen atoms, C _{1 -8} alkyl group, C _{1 -8} alkoxy group, a nitro group, a sulfo group, a sulfamoyl group and a substituted sulfamoyl group such as N- .

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an oxo atom, and a fluorine atom, a chlorine atom or a bromine atom is preferable.

_{Examples of the} C _1-8 alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, More preferably an alkyl group having 1 to 2 carbon atoms, and a methyl group is particularly preferable.

_{Examples of the} C _1-8 alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert- Preferably an alkoxy group having 1 to 4 carbon atoms, more preferably an alkoxy group having 1 to 2 carbon atoms, and particularly preferably a methoxy group.

As the N-substituted sulfamoyl group, -SO ₂ NHR ⁶ group or -SO ₂ NR ⁶ R ⁷ group is preferable. However, R ⁶ and R ⁷ are each independently a, C _1-16 aliphatic which may be substituted with a hydrocarbon group or an optionally substituted C _{2 -18} represents an acyl group which is.

B ¹ and B ² are, each independently, a monovalent C which may have a monovalent C _{6 -14} hydrocarbon group, or an aromatic substituent which may have a substituent, an aromatic heterocyclic _3-14.

_{Examples of the} C _{6 -14} aromatic hydrocarbon group include the groups shown below.

_{Examples of the} C _{3 -14} aromatic heterocyclic group include the groups shown below.

[R represents a hydrogen atom or a methyl group]

C _{6 - l4} aromatic hydrocarbon group and C _{3 -14} hydrogen atom contained in the aromatic heterocyclic group is optionally substituted by a hydroxyl group, an oxo group, a C _{1 -16} aliphatic hydrocarbon group, a cyano group, an amino group or N- substituted amino group do.

As the N-substituted amino group, -NHR ⁸ group or -SO ₂ NR ⁸ R ⁹ group is preferable. 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 _{3 -14} aromatic heterocyclic group which may have a substituent. Examples of the monovalent C _1-16 aliphatic hydrocarbon group and monovalent C _{3 -14} aromatic heterocyclic group include the same groups as described above.

B ¹ and B ² each independently represent a group represented by formula (II).

In formula (II), R ³ represents a monovalent C _{1 -16} aliphatic hydrocarbon group which may have a hydrogen atom or a substituent.

R ⁴ represents a monovalent C _{1 -16} aliphatic hydrocarbon group which may have a substituent.

The pyridone ring of the group represented by the formula (II) may be of a keto type or a phenolic type.

Examples of the monovalent C _{1 -16} aliphatic hydrocarbon group include the same groups as described above.

R ³ is a methyl group such as a methyl butyl group (1,1,3,3-tetramethyl butyl group), a methylhexyl group (1,5-dimethylhexyl group etc.), an ethylhexyl group (2-ethylhexyl group etc.) Chain aliphatic hydrocarbon group such as a cyclohexyl group (such as a 2-methylcyclohexyl group) and an alkoxypropyl group (such as a 3- (2-ethylhexyloxy) propyl group).

R ⁴ is preferably a methyl group.

Examples of the compound (I) include the compounds represented by the formulas (I-1) to (I-18). A ¹ , A ² , Z ^1, and Z ^{2 in the table} represent the combined hands on the right hand side closer to Z ³ .

Examples of the salt of the compound (I) include a sulfonic acid salt and a carboxylic acid salt. The cation to form these salts is not particularly limited. In view of the solubility in solvents, alkali metal salts such as lithium salts, sodium salts and potassium salts; Inorganic amine salts such as ammonium salts; And organic amine salts such as ethanolamine salts and alkylamine salts. Particularly, an alkali metal salt (preferably a sodium salt) is useful when it is contained in a polarizing film substrate. Further, the organic amine salt is useful when it is contained in the resin curing compound, and because it is a non-metallic salt, it is also useful in the field where insulation is important.

The compound (I) can be usually produced by reacting the compound represented by the formula (IA) and the compound represented by the formula (I-A ') with the compound represented by the formula (IB) at 0 to 150 ° C in a solvent have.

Z ¹ , Z ² , Z ³ , R ¹ , R ² , A ¹ , A ² , B ¹ and B ² in the formulas (IA), (I-A ' .

R ³¹ and R ³² each independently represent -OR ³³ or a halogen atom. R ³³ represents a C _{1 -16} aliphatic hydrocarbon group.

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

The amount of the compound represented by the formula (IB) to be used is preferably 0.5 to 3 moles, more preferably 0.5 to 1 mole, per 1 mole of the total amount of the compound represented by the formula (IA) and the compound represented by the formula desirable. When water is contained in the solvent, the amount of the compound represented by the formula (IB) to be used is 0.6 to 3 moles relative to 1 mole of the total amount of the compound represented by the formula (IA) and the compound represented by the formula (I-A ' desirable.

When R ³¹ and R ³² of the compound represented by the formula (IB) 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 formula (IA) and the compound represented by formula (IA ').

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) is usually 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 alkyl amides such as N, N-dimethylformamide, N, N-dibutylformamide, N, N-dimethylacetamide and N-methylpyrrolidone. When two or more solvents are used in combination do. The amount of the solvent to be used is preferably from 1 to 20 parts by mass, more preferably from 2 to 10 parts by mass, based on 1 part by mass of the total amount of the compound represented by the formula (IA) and the compound represented by the formula (I-A ' .

The reaction of the compound represented by the formula (IA) and the compound represented by the formula (IA ') with the compound represented by the formula (IB) is preferably carried out in a nitrogen atmosphere or an argon atmosphere, The reaction may be carried out.

The reaction temperature is preferably 0 to 150 占 폚, more preferably 10 to 130 占 폚. 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 (IA), the compound represented by the formula (I-A '), the compound represented by the formula (IB) and the solvent is not particularly limited, but the compound represented by the formula (IA) (IB) is added (added dropwise) to a solution comprising a compound represented by the formula (II) and a solvent. In the case of using an acid catalyst, it is preferable to add (drop) the compound represented by the formula (IB) to a solution comprising a compound represented by the formula (IA), a compound represented by the formula (I-A '), an acid catalyst and a solvent .

The method for obtaining the desired compound (I) from the reaction mixture obtained as described above is not particularly limited and various known methods may be employed. For example, the reaction mixture may be purified by extraction with an organic solvent . For example, the compound (I) can be obtained by mixing the reaction mixture with an organic solvent and water, eluting the compound (I) in an organic phase, and distilling off the organic phase separated by a separating rod or the like. The extraction temperature is preferably 10 to 50 占 폚, more preferably 20 to 30 占 폚. The extraction is preferably carried out at the above-mentioned temperature for 0.5 to 4 hours with stirring. The compound (I) after extraction is usually washed with an alkaline aqueous solution, an acidic aqueous solution or the like, and then dried. If necessary, it may be further purified by a known method such as recrystallization.

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, and ammonia.

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, sulfuric acid and the like.

Compound (I) can be produced by coupling reaction between a compound represented by formula (I-C), a compound represented by formula (I-D) and a compound represented by formula (I-D '). Compound (I) can be obtained by reacting a salt of a compound represented by formula (IC) with a compound represented by formula (ID) and a compound represented by formula (I-D ') in an aqueous solvent at 20 to 60 ° C, Can be manufactured.

In the formulas (IC) and (ID), Z ¹ , Z ² , Z ³ , R ¹ , R ² , A ¹ , A ² , B ¹ and B ² have the same meanings as defined above.

X ^- represents an inorganic or organic anion.]

Examples of inorganic or organic Anna Ian of the compound represented by the formula (IC), fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ^{_{ion, CH 3 -COO -, Ph-}} COO - , and the like, and , Preferably a chloride ion, a bromide ion, CH ₃ -COO ^- .

It is more preferable that B ¹ and B ² are the same kind of groups, and furthermore, it is more preferable that A ¹ and A ² , R ¹ and R ² , Z ¹ and Z ² are each a group of the same kind. In this case, the preparation of the compound (I) is easy.

Since the compound of the present invention exhibits high solubility, low morbidity and high spectral density, it can be used as a dye in textile materials, liquid crystal display devices and the like which display color by using reflected light or transmitted light. Further, since the compound of the present invention has maximum absorption in a wavelength range of 400 to 450 nm when the absorption spectrum is measured, it is preferably used as a yellow dye.

Soluble resin (hereinafter may be referred to as "alkali-soluble resin (B)"), a photopolymerizable compound (hereinafter referred to as "a colorant (A)") (Hereinafter may be referred to as " photopolymerizable compound (C) "), a photopolymerization initiator (hereinafter sometimes referred to as a photopolymerization initiator (D) A resin composition is obtained.

The compound (I) may be used alone or in combination of two or more.

The colorant (A) may contain, in addition to the compound (I), a dye other than the compound (I) and the pigment (A-2).

As dyes other than the compound (I), there may be mentioned a dye (Solvent), an acid, a basic, a reactive, a direct dye ), Disperse, or Vat. The compounds of the present invention may be used alone or in combination of two or more. More specifically, the dyes of the following color index (CI) numbers can be mentioned, 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. Disperse Yellow 54, 76;

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

C. I. Acid Orange 56, 74, 95, 108, 149, 162;

C. I. reactive orange 16;

C. I. Direct Orange 26;

C. I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;

C. I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;

C. I. Acid Violet 102;

C. I. Solvent 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. Disperse 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, etc.

Examples of the pigment (A-2) include an organic pigment or an inorganic pigment usually used in a pigment dispersion resist. Specific examples of the inorganic pigment include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc and antimony, Oxides. Specific examples of organic pigments and inorganic pigments include compounds classified as pigments in the Color Index (published by The Society of Dyers and Colourists). More specifically, the pigment of the color index (C.I.) number as follows may be mentioned, 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 mass%, more preferably from 8 to 55 mass%, and still more preferably from 10 to 50 mass%, based on the solid content in the colored photosensitive resin composition. Here, the solid content refers to the sum of components excluding the solvent in the colored photosensitive resin composition.

When the colorant (A) further contains a dye and / or pigment (A-2) other than the compound (I), the content of the compound (I) in the colorant (A) is 3 to 80% by mass, 3 to 70 mass%, and more preferably 3 to 50 mass%.

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

The alkali-soluble resin (B) is not particularly limited and any resin may be used. It is preferable that the alkali-soluble resin (B) contains a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

Specific examples of the alkali-soluble resin (B) include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate (Meth) acrylate / methacrylate / benzyl methacrylate / N-phenylmaleimide copolymer, a compound represented by formula (b1) and a compound represented by formula (b2), a compound represented by formula (b1) And a copolymer of a compound represented by the formula (b3).

The weight average molecular weight of the alkali-soluble resin (B) in terms of polystyrene 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 alkali-soluble resin (B) is preferably from 50 to 150, more preferably from 60 to 135, still more preferably from 70 to 135.

The content of the alkali-soluble resin (B) is usually 7 to 65% by mass, preferably 13 to 60% by mass, and more preferably 17 to 55% by mass, based on the solid content of the colored photosensitive resin composition.

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

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 penta methacrylate, dipentaerythritol hexaacrylate, Dipentaerythritol hexamethacrylate, and the like. The above-mentioned photopolymerizable compound (C) may be used singly or in combination of two or more kinds.

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

Examples of the photopolymerization initiator (D) include an active radical generator and an acid generator. The active radical generator generates active radicals by being irradiated with light. 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- Phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) Phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one and the like.

A preferred acetophenone compound is 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one.

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 o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-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- Propoxyoctanoate and the like.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- Triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Methyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4- dimethoxyphenyl) ethenyl] -1,3 , 5-triazine, and the like.

Examples of the above oxime compounds include O-acyloxime compounds, and specific examples thereof include N-benzoyloxy-1- (4-phenylsulfanylphenyl) -butan-1-one-2- , N-benzoyloxy-1- (4-phenylsulfanylphenyl) -octan-1-one-2-imine, N-acetoxy- 1- [ 3-yl] ethan-1-imine, N-acetoxy-1- [ Oxy) benzoyl} -9H-carbazol-3-yl] ethan-1-imine.

As the active radical generator, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphaquinone, methyl phenylglyoxylate, And the like.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p- Toluenesulfonate, 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate , Diphenyliodonium hexafluoroantimonate and the like, and nitrobenzyltosylates, benzoin tosylates and the like.

Among the compounds described above as the above-mentioned active radical generator, there are 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 photopolymerization initiator (D) is preferably from 0.1 to 30 mass%, more preferably from 1 to 20 mass%, based on the total amount of the alkali-soluble resin (B) and the photopolymerizable compound (C). When the content of the photopolymerization initiator is within the above-mentioned range, it is preferable because a high sensitivity is obtained and the exposure time is shortened and productivity is improved.

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

Examples of the ethers include ethers such as tetrahydrofuran, tetrahydropyrane, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, Cyclohexane, cyclohexane, cyclohexane, cyclohexane, cyclohexane, cyclohexane, cyclohexane, cyclohexane, cyclohexane,

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

Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl- - 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, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, Methyl ethyl ketone, ethyl lactate, methyl lactate, ethyl lactate, butyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetate, methyl 3- Methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, Methyl propionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 3-methoxy Butyl acetate, 3-methyl-3-methoxybutyl acetate, and? -Butylolactone.

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

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

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

The colored photosensitive resin 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 surfactants include surfactants having a siloxane bond. Specific examples of the silicone oil include diole silicone DC3PA, diole silicone SH7PA, diole silicone DC11PA, diole silicone SH21PA, diole silicone SH28PA, diole silicone SH29PA, diole silicone SH30PA, polyether-modified silicone oil SH8400 (Manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 [Moment], KP321, KP323, KP324, KP326, KP340, KP341 Japan Performance Company, Japan Joint Company].

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Specific examples of such a solvent include Fluoride (trade name) FC430, Fluoride FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (trade name) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, (Trade name) manufactured by Mitsubishi Chemical Corporation), Sphrone (trade name) S381, manufactured by Mitsubishi Chemical Corporation), Megafac R30 (manufactured by DIC Corporation), Eftot (trade name) EF301, Efopto EF303, Efopto EF351 and Efopto EF352 BM-1000 (all trade names, manufactured by BM Chemie), and the like were added to the above-prepared dispersion liquid, and the like, .

Examples of the silicone surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples include Megapac (registered trademark) R08, Megapack BL20, Megapack F475, Megapack F477, Megapack F443 (manufactured by DIC Corporation) and the like.

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

The content of the surfactant (G) is preferably 0.00001 to 0.1% by mass, more preferably 0.00005 to 0.01% by mass, based on the colored photosensitive resin composition. When the content of the surfactant (G) is in the above range, the flatness tends to be good.

The colored photosensitive resin composition of the present invention can be suitably used for forming a color filter or a colored pattern, and it is possible to obtain a colored pattern and a color filter having good color density, brightness, contrast, sensitivity, resolution, heat resistance and the like. It is also possible to use an optical film, an array substrate, a color filter substrate, and the like having these color filters or coloring patterns as a part of their constituent parts, and also in a group consisting of these color filters or color patterns, optical films, array substrates and color filter substrates For example, a known liquid crystal display device, an organic EL device, a solid-state image pickup device, and other devices related to various colored images.

As a method of forming a color filter or a pattern using the colored photosensitive resin composition of the present invention, for example, a method of forming a colored photosensitive resin composition of the present invention on a substrate or a separate resin layer (for example, Another coloring photosensitive resin composition layer, or the like), removing volatile components such as a solvent to form a colored layer, and exposing and developing the colored layer through a photomask; and a method in which an ink jet apparatus And the like.

The film thickness of the coating film in this case is not particularly limited and can be appropriately adjusted depending on the material to be used and the purpose of use, and is preferably from 0.1 to 30 mu m, more preferably from 1 to 20 mu m, even more preferably from 1 To 6 m.

Examples of the application method of the colored photosensitive resin 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. It may also be coated using a coater such as a dip coater, a bar coater, a spin coater, a slit & spin coater, a slit coater (die coater, curtain flow coater, or spinless coater). Among them, it is preferable to apply by using a spin coater.

The removal or drying of the solvent includes, for example, natural drying, air drying, and vacuum drying. 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.

Example

Hereinafter, the present invention will be described more specifically by way of examples. The present invention is not limited by the following examples. In the examples and comparative examples, "% " and " part "

Example 1

To 25.0 parts of o-toluidine-4-sulfonic acid tetrahydrate represented by the formula (a-1), 250 parts of water and 50 parts of N-methylpyrrolidone were added, and the pH was adjusted to 7 to 8 with 30% aqueous sodium hydroxide solution under ice- . The following operation was performed under ice-cooling. 18.4 parts of sodium nitrite was added, and the mixture was stirred for 30 minutes. And 64.8 parts of 35% hydrochloric acid was added in small portions to make a brown solution, followed by stirring for 2 hours. And 16.7 parts of amide sulfuric acid in 170 parts of water was added to the reaction solution and stirred to obtain a suspension containing the diazonium salt.

173 parts of water and 19 parts of N-methylpyrrolidone were added to 19.3 parts of 1-butyl-3-cyano-4-methyl-6-hydroxypyrid-2-one represented by the formula (c-1) And adjusted to pH 8 to 9 with a 30% aqueous solution of sodium hydroxide.

The following operation was performed under ice-cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and the suspension containing the diazonium salt was added dropwise over 2 hours while adjusting the pH to 8 to 9 with 30% sodium hydroxide aqueous solution. After completion of the dropwise addition, stirring was continued for another 2 hours to obtain a dark solution. 140 parts of purified salt were added to the reaction solution and stirred for 5 hours. The yellow solid obtained by filtration was dried under reduced pressure at 60 캜 to obtain 35.8 parts (yield: 91%) of the compound represented by the formula (d-1).

0.35 g of the obtained compound (d-1) 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 / Absorption spectra were measured using a spectrophotometer [quartz cell, cell length 1 cm]. This compound exhibited an absorbance of 3.1 (arbitrary unit) at? Max = 441 nm.

5.0 parts of the compound (d-1), 25 parts of acetonitrile and 1.8 parts of N, N-dimethylformamide were fed into a flask equipped with a stirrer, a cooling tube and a stirrer. Thionyl chloride 2.8 parts were added dropwise. After completion of dropwise addition, the temperature was raised to 40 占 폚, and the reaction was carried out at the same temperature for 2 hours, followed by cooling 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 filtered, washed well with tap water, and dried at room temperature for 1 hour. A flask equipped with a cooling tube and a stirrer was prepared separately, and then 1.9 parts of 3-amino-1-propanol and 20 parts of N-methylpyrrolidone were added thereto. While keeping the temperature below 20 ° C with stirring, Over a period of 1 hour. After the yellow solid was added, the temperature of the solution 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 mixed solution was added to 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 filtered, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 4.2 parts (yield: 73%) of a compound represented by the formula (III-1).

0.35 g of the obtained compound (III-1) was dissolved in ethyl lactate to make a volume of 250 cm 3, and 2 cm 3 of the solution was diluted with deionized water to make a volume of 100 cm 3 (concentration: 0.028 g / L) (Quartz cell, optical path length: 1 cm) was used to measure the absorption spectrum. This compound exhibited an absorbance of 2.8 (arbitrary unit) at? Max = 435 nm.

The following reaction was carried out in a nitrogen atmosphere. 8.0 parts of N-methylpyrrolidone was added to 4.0 parts of the compound (III-1), and the reaction solution was adjusted by stirring for 30 minutes. While stirring the reaction solution at room temperature, 1.1 parts of succinate chloride was added dropwise. After completion of the dropwise addition, stirring was continued for another 8 hours. After the reaction solution was poured into 500 parts of water, 240 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 1000 parts of water, 1000 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 subjected to solvent distillation to obtain 4.0 parts of a compound represented by the formula (I-2). Yield 92%.

The structure of the compound (I-2) was determined by mass spectrometry. JMS-700 (manufactured by Nihon Denshi Co., Ltd.) was used as the mass spectrometer.

Mass spectrometry: ionisation mode = FD +: m / z = 1004

0.35 g of Compound (I-2) was dissolved in ethyl lactate to make a volume of 250 cm 3, and 2 cm 3 of the solution was diluted with deionized water to make a volume of 100 cm 3 (concentration: 0.028 g / L) Quartz cell, optical path length: 1 cm) was used to measure the absorption spectrum. This compound exhibited an absorbance of 2.5 (arbitrary unit) at? Max = 435 nm.

Example 2

After adding 200 parts of water and 50 parts of N-methylpyrrolidone to 25.0 parts of m-toluidine-4-sulfonic acid represented by the formula (a-2), the mixture was adjusted to pH 7-8 with 30% aqueous sodium hydroxide solution under ice-cooling. The following operation was performed under ice-cooling. 27.6 parts of sodium nitrite was added, and the mixture was stirred for 30 minutes. And 97.3 parts of 35% hydrochloric acid was added in small portions to make a brown solution, followed by stirring for 2 hours. And 25.1 parts of amide sulfuric acid in 250 parts of water was added to the reaction solution and stirred to obtain a suspension containing the diazonium salt.

260 parts of water and 28.9 parts of N-methylpyrrolidone were added to 28.9 parts of 1-butyl-3-cyano-4-methyl-6-hydroxypyrid-2-one represented by the formula (c-1) And adjusted to pH 8 to 9 with a 30% aqueous solution of sodium hydroxide.

The following operation was performed under ice-cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and the suspension containing the diazonium salt was added dropwise over 2 hours while adjusting the pH to 8 to 9 with 30% sodium hydroxide aqueous solution. After completion of the dropwise addition, stirring was continued for another 2 hours to obtain a dark solution. 140 parts of purified salt were added to the reaction solution and stirred for 5 hours. The yellow solid obtained by filtration was dried at 60 캜 under reduced pressure to obtain 46.7 parts (yield: 79%) of a compound represented by the formula (d-2).

0.35 g of the compound (d-2) 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 / Absorption spectra were measured using a photometer [quartz cell, cell length 1 cm]. This compound exhibited an absorbance of 3.2 (arbitrary unit) at? Max = 435 nm.

5.0 parts of the compound (d-2), 25 parts of acetonitrile and 1.8 parts of N, N-dimethylformamide were fed into a flask equipped with a stirrer, a cooling tube and a stirrer. Thionyl chloride 2.8 parts were added dropwise. After completion of dropwise addition, the temperature was raised to 40 占 폚, and the reaction was carried out at the same temperature for 2 hours, followed by cooling 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 filtered, washed well with tap water, and dried at room temperature for 1 hour. A flask equipped with a cooling tube and a stirrer was prepared separately, and 1.9 parts of 1-amino-2-propanol and 20 parts of N-methylpyrrolidone were added thereto. While keeping the temperature below 20 ° C with stirring, Over a period of 1 hour. After the yellow solid was added, the temperature of the solution 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 mixed solution was added to 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 filtered, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 4.4 parts (yield: 77%) of a compound represented by the formula (III-2).

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 / L) Quartz cell, optical path length: 1 cm) was used to measure the absorption spectrum. This compound exhibited an absorbance of 2.7 (arbitrary unit) at? Max = 432 nm.

The following reaction was carried out in a nitrogen atmosphere. To 25.0 parts of the compound (III-2), 50.0 parts of N-methylpyrrolidone was added, and the reaction solution was adjusted by stirring for 30 minutes. While stirring the reaction solution at room temperature, 5.0 parts of adipic acid chloride was added dropwise. After completion of the dropwise addition, stirring was continued for another 8 hours. The reaction solution was poured into 1000 parts of water, 500 parts of ethyl acetate was added, and the mixture was stirred for 30 minutes. The organic phase was separated using a separating rod, and then washed again with 2000 parts of water, 2000 parts of 10% sodium carbonate aqueous solution, 2000 parts of 10% acetic acid aqueous solution and 2000 parts of ion-exchanged water. The separated organic phase was subjected to solvent distillation to obtain 24.7 parts of a compound represented by the formula (I-5). Yield 88%.

The structure of the compound (I-5) was determined by mass spectrometry. JMS-700 (manufactured by Nihon Denshi Co., Ltd.) was used as the mass spectrometer.

Mass spectrometry: ionization mode = FD +: m / z = 1032

0.35 g of Compound (I-5) 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 exhibited an absorbance of 2.3 (arbitrary unit) at? Max = 431 nm.

Example 3

After adding 200 parts of water to 10.0 parts of m-toluidine-4-sulfonic acid represented by the formula (a-2), the mixture was adjusted to pH 7 to 8 with 30% aqueous sodium hydroxide solution under ice cooling. The following operation was performed under ice-cooling. 11.1 parts of sodium nitrite was added, and the mixture was stirred for 30 minutes. 39.0 parts of 35% hydrochloric acid was added in small portions to make a brown solution, which was then stirred for 2 hours. And 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 14.0 parts of 1- (2-ethylhexyl) -3-cyano-4-methyl-6-hydroxypyrid-2-one represented by the formula (c-2), 125 parts of water and N-methylpyrrolidone 25.0 The mixture was stirred under ice-cooling and adjusted to pH 8 to 9 with a 30% aqueous solution of sodium hydroxide.

The following operation was performed under ice-cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and the suspension containing the diazonium salt was added dropwise over 2 hours while adjusting the pH to 8 to 9 with 30% sodium hydroxide aqueous solution. After completion of the dropwise addition, stirring was continued for another 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 / Absorption spectra were measured using a photometer [quartz cell, cell length 1 cm]. This compound exhibited an absorbance of 2.9 (arbitrary unit) at? Max = 433 nm.

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 parts was added dropwise. After completion of dropwise addition, the temperature was raised to 40 占 폚, and the reaction was carried out at the same temperature for 2 hours, followed by cooling 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 filtered, washed well with tap water, and dried at room temperature for 1 hour. A flask equipped with a cooling tube and a stirrer was prepared separately and 2.0 parts of 1-amino-2-propanol and 20 parts of N-methylpyrrolidone were added thereto. While keeping the temperature below 20 ° C with stirring, Over a period of 1 hour. After the yellow solid was added, the temperature of the solution 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 mixed solution was added to 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 filtered, 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 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 exhibited an absorbance of 2.3 (arbitrary unit) at? Max = 431 nm.

The following reaction was carried out in a nitrogen atmosphere. 2.0 parts of the compound (III-3) was added 4.0 parts of N-methylpyrrolidone, and the mixture was stirred for 30 minutes to adjust the reaction solution. While stirring the reaction solution at room temperature, 0.1 part of sebacic 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 the mixture was stirred for 30 minutes. The organic phase was collected by using a separating rod, and then washed with 500 parts of water, 500 parts of 10% sodium carbonate aqueous solution, 500 parts of 10% acetic acid aqueous solution and 500 parts of ion exchange water. The separated organic phase was subjected to solvent distillation to obtain 2.0 parts of a compound represented by the formula (I-6). Yield 85%.

The structure of compound (I-6) was determined by mass spectrometry. JMS-700 (manufactured by Nihon Denshi Co., Ltd.) was used as the mass spectrometer.

Mass spectrometry: ionization mode = FD +: m / z = 1200

0.35 g of the compound (I-6) was dissolved in ethyl lactate to make a volume of 250 cm 3, and 2 cm 3 of the solution was diluted with deionized 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 exhibited an absorbance of 2.2 (arbitrary unit) at? Max = 431 nm.

Comparative Example 1

A compound represented by the formula (III-4) was synthesized by the method described in Patent Document 1. 0.35 g of Compound (III-4) 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 / L) Quartz cell, optical path length: 1 cm) was used to measure the absorption spectrum. This compound exhibited an absorbance of 2.2 (arbitrary unit) at? Max = 425 nm.

<Evaluation of Solubility in Solvent>

The solubility of the compounds of Examples 1 to 3 and Comparative Example 1 in a solvent was determined as follows.

Each of the compounds was mixed with propylene glycol monoethyl ether acetate so as to have a mixing ratio of 5% (W / V), 10% (W / V) and 15% (W / V) After that, it was vibrated with an ultrasonic vibrator at 40 DEG C for 10 minutes. Then, the mixture was allowed to stand at room temperature for 30 minutes and then filtered to confirm the presence of insoluble matter.

(W / V) adjusted solution was insoluble in the mixed solution adjusted to have a solubility of less than 5% (×) and adjusted to 5% (W / V) (W / V) adjusted, insolubles were not present in the mixed solution adjusted to 10% (W / V), and the mixed solution adjusted to 15% (W / V) The solubility in insoluble matter in the solution was adjusted to be less than 5 to 10% (∘) and the solubility in the mixed solution adjusted to 15% (W / V) was 15% or more (⊚). The results are shown in Table 19.

From the results shown in Table 19, it can be seen that the compound of the present invention exhibits high solubility and low morbidity.

Resin Synthesis Example 1

In a 1 L flask equipped with a reflux condenser, a dropping rod and a stirrer, nitrogen was flowed at 0.02 L / min to obtain a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 100 parts by mass of 3-methoxybutyl acetate , And the mixture was heated to 70 DEG C while stirring. Subsequently, 98 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate (the compound represented by formula (B-1-1) and the compound represented by formula (B-1-2) , In a molar ratio of 50:50) were dissolved in 140 parts by mass of 3-methoxy-1-butanol to prepare a solution. The solution was added to 70 Lt; 0 &gt; C. On the other hand, a solution prepared by dissolving 27 parts by mass of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 240 parts by mass of 3-methoxybutyl acetate was added to the flask / RTI &gt; After completion of the dropwise addition of the polymerization initiator solution, the solution was maintained at 70 캜 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% by mass and an acid value of 111 mg-KOH / g . The obtained resin B1 had a weight average molecular weight (Mw) of 7500 and a molecular weight distribution of 1.7.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin B1 thus obtained were measured under the following conditions using the GPC method.

Device ; K2479 (manufactured by Shimadzu Corporation)

column ; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0 mL / min

Detector; RI

The ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained as described above was defined as a molecular weight distribution.

The components used in the following examples are as follows, and the following may be omitted.

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

(I-5) Colorant: The compound synthesized in Example 2

(I-6) Colorant: The compound synthesized in Example 3

(III-4) Colorant: The compound synthesized in Comparative Example 1

(B-1) Resin: Resin solution B1 obtained in Resin Synthesis Example 1

(B-2) Resin: HN-123 (manufactured by Daoka Chemical Industry Co., Ltd., average molecular weight: 10700, acid value: 70 mgKOH / g) 33.8% propylene glycol monomethyl ether acetate solution

(C-1) Polymerizable compound: 50% propylene glycol monoethyl ether acetate solution of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

(D-1) Photopolymerization initiator: OXE-01 (manufactured by Chiba Specialty Chemicals Co., Ltd.) (oxime compound)

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

(E-1) Solvent: propylene glycol monomethyl ether acetate

(E-2) Solvent: N, N-dimethylformamide

Example 4

[Preparation of colored photosensitive resin composition]

(I-2) 0.30 parts by mass

(B-1) 1.67 parts by mass

(C-1) 1.48 parts by mass

(D-1) 0.22 parts by mass

(G-1) 0.10 parts by mass

(E-1) 6.23 parts by mass

To obtain a colored photosensitive resin composition.

[Preparation of colorless composition]

(B-2) 40.2 parts by mass

(C-1) 11.6 parts by mass

(D-1) 0.58 parts by mass

(G-1) 1.00 parts by mass

(E-1) 46.6 parts by mass

To obtain a colorless composition.

[Formation of Coating Film of Colored Photosensitive Resin Composition]

On the glass (# 1737; Corning), the above-obtained colored photosensitive resin composition was applied by a spin-coat method, and volatile components were volatilized at 100 ° C for 3 minutes. After cooling, to the glass substrate coated with the colored photosensitive resin composition, an exposure machine (TME-150 RSK; (Manufactured by Topcon Co., Ltd.) at an exposure amount of 150 mJ / cm &lt; 2 &gt; (based on 365 nm) in an air atmosphere. Followed by baking at 220 DEG C for 2 hours to form a coating film (thickness: 2.2 mu m) of the colored photosensitive resin composition.

[Formation of Coating Film of Colorless Composition]

On the glass (# 1737; Corning), the colorless composition obtained above was applied by spin coating and the volatile components were volatilized at 100 占 폚 for 3 minutes. After cooling, to the glass substrate coated with the colorless composition, an exposure machine (TME-150 RSK; (Manufactured by Topcon Co., Ltd.) at an exposure amount of 150 mJ / cm &lt; 2 &gt; (based on 365 nm) in an air atmosphere. And fired at 220 캜 for 2 hours to form a coating film (thickness: 2.2 탆) of a colorless composition.

[Evaluation of transference]

The coated film of the colored photosensitive resin composition and the coated film of the colorless composition were opposed to each other with an interval of 70 占 퐉 therebetween and heated at 230 占 폚 for 120 minutes so that the color difference? Eab * before and after heating of the coating film of the colorless composition was measured by a colorimeter -SP-200 manufactured by OLYMPUS Co., Ltd.). The resulting coating film was subjected to the above-described dye transfer evaluation. As a result, the color difference (? Eab *) of the coating film of the colorless composition was 2.1.

Example 5

[Evaluation of transference]

A coated film of a colored photosensitive resin composition and a film of a colorless composition were prepared in the same manner as in Example 4 except that the colorant (I-2) of Example 4 was changed to the colorant (I-5) As a result, the color difference (? Eab *) of the coating film of the colorless composition was 1.9.

Example 6

[Evaluation of transference]

A coated film of a colored photosensitive resin composition and a film of a colorless composition were prepared in the same manner as in Example 4 except that the colorant (I-2) of Example 4 was changed to the colorant (I-6) As a result, the color difference (? Eab *) of the coating film of the colorless composition was 2.0.

Comparative Example 2

[Preparation of colored photosensitive resin composition]

(III-4) 0.30 parts by mass

(B-1) 1.67 parts by mass

(C-1) 1.48 parts by mass

(D-1) 0.22 parts by mass

(G-1) 0.10 parts by mass

(E-2) 6.23 parts by mass

To obtain a colored photosensitive resin composition.

[Formation and Evaluation of Coating Film]

A coated film of the colored photosensitive resin composition and a coating film of the colorless composition were prepared in the same manner as in Example 4, and the color difference (ΔEab *) of the colorless composition was 43.2.

Example 7

The following reaction was carried out in a nitrogen atmosphere. After adding 93.0 parts of N-methylpyrrolidone to 31.0 parts of the compound (III-3), the reaction solution was adjusted by stirring for 30 minutes. While stirring the reaction solution at room temperature, 5.5 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 the mixture was stirred for 30 minutes. The organic phase was separated using a separating rod, and then washed with 500 parts of water, 500 parts of 10% sodium carbonate aqueous solution, 500 parts of 10% acetic acid aqueous solution, and 500 parts of ion exchange water. The separated organic phase was subjected to solvent distillation to obtain 2.0 parts of a compound represented by the formula (I-19). Yield 85%.

The structure of the compound (I-19) was determined by mass spectrometry. JMS-700 (manufactured by Nihon Denshi Co., Ltd.) was used as the mass spectrometer.

Mass spectrum: ionization mode = FD +: m / z = 1144

0.35 g of Compound (I-19) 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 / L) Quartz cell, optical path length: 1 cm) was used to measure the absorption spectrum. This compound exhibited an absorbance of 2.2 (arbitrary unit) at? Max = 431 nm.

Example 8

After adding 1500 parts of water to 75.0 parts of m-toluidine-4-sulfonic acid represented by the formula (a-2), the mixture was adjusted to pH 7 to 8 with 30% aqueous sodium hydroxide solution under ice cooling. The following operation was performed under ice-cooling. 82.9 parts of sodium nitrite was added, and the mixture was stirred for 30 minutes. 292.1 parts of 35% hydrochloric acid was added in small portions to make a brown solution, which was then stirred for 2 hours. And 754 parts of amide sulfuric acid in 754 parts of water was added to the reaction solution and stirred to obtain a suspension containing the diazonium salt.

700 parts of water was added to 77.8 parts of 1- (2-hydroxyethyl) -3-cyano-4-methyl-6-hydroxypyrid-2-one represented by the formula (c-3) % Sodium hydroxide aqueous solution.

The following operation was performed under ice-cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and the suspension containing the diazonium salt was added dropwise over 2 hours while adjusting the pH to 8 to 9 with 30% sodium hydroxide aqueous solution. After completion of the dropwise addition, stirring was continued for another 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried under reduced pressure at 60 캜 to obtain 99.5 parts (yield: 61%) of a compound represented by the formula (d-4).

0.35 g of the compound (d-4) 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 / Absorption spectra were measured using a photometer [quartz cell, cell length 1 cm]. This compound exhibited an absorbance of 3.2 (arbitrary unit) at? Max = 433 nm.

The following reaction was carried out in a nitrogen atmosphere. To 54.9 parts of the compound (d-4), 183.3 parts of N-methylpyrrolidone was added, and the reaction solution was adjusted by stirring for 30 minutes. While stirring the reaction solution at room temperature, 20.8 parts of 2-ethylhexanoic acid chloride was added dropwise. After completion of dropwise addition, the temperature of the reaction solution was raised to 100 ° C, and stirring was continued for another 8 hours. The reaction solution was poured into 274.4 parts of a saturated saline solution and stirred for another 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 캜 under reduced pressure to obtain 71.6 parts (yield: 98%) of a compound represented by the formula (d-5).

0.35 g of compound (d-5) 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 / Absorption spectra were measured using a photometer [quartz cell, cell length 1 cm]. This compound exhibited an absorbance of 2.7 (arbitrary unit) at? Max = 433 nm.

71.6 parts of the compound (d-5), 215 parts of tetrahydrofuran and 22.3 parts of N, N-dimethylformamide were fed into a flask equipped with a stirrer, a cooling tube and a stirrer, 34.1 parts of o-ne was added dropwise. After completion of dropwise addition, the temperature was raised to 40 占 폚, and the reaction was carried out at the same temperature for 2 hours, followed by cooling to 20 占 폚. The cooled reaction solution was poured into 2147 parts of ice water while stirring, followed by stirring for 30 minutes. The precipitated yellow crystals were filtered, washed well with tap water, and dried at room temperature for 1 hour. A flask equipped with a cooling tube and a stirrer was prepared separately, and 28.6 parts of 1-amino-2-propanol and 286 parts of N-methylpyrrolidone were added thereto. While keeping the temperature below 20 ° C with stirring, Over a period of 1 hour. After the yellow solid was added, the temperature of the solution was raised to room temperature, and then the reaction solution was stirred for 30 minutes. 107 parts of methanol was added to the reaction solution and stirred, and the mixed solution was added to 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 filtered, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 60.0 parts (yield: 78%) of a compound represented by the formula (III-5).

0.35 g of Compound (III-5) 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 exhibited an absorbance of 2.3 (arbitrary unit) at? Max = 431 nm.

The following reaction was carried out in a nitrogen atmosphere. After adding 63.0 parts of N-methylpyrrolidone to 21.0 parts of the compound (III-5), the reaction solution was adjusted by stirring for 30 minutes. While stirring the reaction solution at room temperature, 4.7 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 600 parts of water, 240 parts of ethyl acetate was added and stirred for 30 minutes. The organic phase was separated using a separating rod, and then washed again with 1000 parts of water, 1000 parts of 10% sodium carbonate aqueous solution, 1000 parts of 10% acetic acid aqueous solution, and 500 parts of ion-exchanged water. The separated organic phase was subjected to solvent distillation to obtain 18.8 parts of a compound represented by the formula (I-20). Yield 82%.

The structure of compound (I-20) was determined by mass spectrometry. JMS-700 (manufactured by Nihon Denshi Co., Ltd.) was used as the mass spectrometer.

Mass spectrometry: ionization mode = FD +: m / z = 1260

0.35 g of Compound (I-20) 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 exhibited an absorbance of 2.1 (arbitrary unit) at? Max = 431 nm.

Example 9

The following reaction was carried out in a nitrogen atmosphere. To 11.4 parts of the compound (III-5), 34.1 parts of N-methylpyrrolidone was added and the reaction solution was adjusted by stirring for 30 minutes. While stirring the reaction solution at room temperature, 1.0 part of sebacic acid chloride was added dropwise. After completion of the dropwise addition, stirring was continued for another 8 hours. The reaction solution was poured into 300 parts of water, and then 160 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, 700 parts of a 10% sodium carbonate aqueous solution, 700 parts of an aqueous 10% acetic acid solution and 700 parts of ion-exchanged water. The separated organic phase was subjected to solvent distillation to obtain 10.1 parts of a compound represented by the formula (I-21). Yield 82%.

The structure of compound (I-21) was determined by mass spectrometry. JMS-700 (manufactured by Nihon Denshi Co., Ltd.) was used as the mass spectrometer.

Mass spectrometry: ionisation mode = FD +: m / z = 1316

0.35 g of Compound (I-21) 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 exhibited an absorbance of 2.0 (arbitrary unit) at? Max = 431 nm.

<Evaluation of Solubility in Solvent>

The solubilities of the compounds of Examples 7 to 9 in the solvent were determined in the same manner as in Example 1. [ Table 20 shows the results.

Example 10

[Evaluation of transference]

A coated film of the coloring composition and a film of the colorless composition were prepared in the same manner as in Example 4 except that the colorant (I-2) of Example 4 was changed to the colorant (I-19) , And the color difference ([Delta] Eab *) of the coating film of the colorless composition was 2.0.

Example 11

[Evaluation of transference]

A coating film of the coloring composition and a coating film of the colorless composition were prepared in the same manner as in Example 4 except that the colorant (I-2) of Example 4 was changed to the colorant (I-20) , And the color difference ([Delta] Eab *) of the coating film of the colorless composition was 2.2.

 Example 12

[Evaluation of transference]

A coating film of a coloring composition and a film of a colorless composition were prepared in the same manner as in Example 4 except that the colorant (I-2) of Example 4 was changed to the colorant (I-21) , And the color difference (? Eab *) of the coating film of the colorless composition was 2.3.

From the above results, it can be seen that the compounds of the Examples can remarkably reduce the dye transfer compared with the compounds of the Comparative Examples.

Since the compound of the present invention has high solubility in solvents and low flammability, it can be suitably used as a coloring agent contained in color filters for display devices such as liquid crystal display panels, electroluminescence, and plasma display panels.

Claims (5)

A compound represented by formula (I).

Z ¹ , Z ² and Z ³ each independently represent a divalent C _1-16 aliphatic hydrocarbon group which may have a halogen atom, and Z ¹ , Z ² and Z ³ , which are included in Z ¹ , Z ² and Z ³ , CH ₂ - may be substituted with -CO- or -O-,
R ¹ and R ² each independently represent a monovalent C _1-16 aliphatic hydrocarbon group which may have a hydrogen atom, a C _1-8 alkoxy group or a carboxy group, a C _1-8 saturated aliphatic hydrocarbon group or C _1-8 A C _2-18 acyl group which may have an alkoxy group,
A ¹ and A ² each independently represent a phenylene group which may have a C _1-8 alkyl group,
B ¹ and B ² each independently represent a group represented by formula (II).

[In the formula (II), R ³ represents a hydrogen atom, a monovalent C _1-16 aliphatic hydrocarbon group which may have a C _1-8 alkoxy group or a carboxy group,
R ⁴ represents a C _1-8 alkoxy group or a monovalent C _1-16 aliphatic hydrocarbon group which may have a carboxyl group] delete A colored photosensitive resin composition characterized by comprising a colorant containing the compound according to claim 1, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent. A coating film formed using the colored photosensitive resin composition according to claim 3. A display device comprising the coating film according to claim 4.