KR20150145716A - Compound and colored curable resin composition - Google Patents

Abstract

[식 (Z) 중, R¹은, 아크릴로일기를 포함하는 기, 메타크릴로일기를 포함하는 기 또는 규소 원자를 포함하는 기를 나타낸다.
R²는 수소 원자, 시아노기 또는 카르바모일기를 나타낸다.
R³은, 할로겐 원자를 갖고 있어도 되는 탄소수 1∼4의 알킬기를 나타낸다.
R⁴, R⁵, R⁶, R⁷ 및 R⁸은, 각각 독립적으로 수소 원자, 탄소수 1∼8의 알킬기, 탄소수 1∼8의 알콕시기, 탄소수 2∼8의 알콕시알킬기, 히드록시기, 시아노기, 니트로기, 카르복실기 또는 -SO₃M을 나타내고, M은 수소 원자 또는 알칼리 금속 원자를 나타낸다.]A compound represented by the formula (Z).

[In the formula (Z), R ¹ represents a group containing an acryloyl group, a group containing a methacryloyl group or a group containing a silicon atom.
R ² represents a hydrogen atom, a cyano group or a carbamoyl group.
R ³ represents an alkyl group having 1 to 4 carbon atoms which may have a halogen atom.
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, A nitro group, a carboxyl group or -SO ₃ M, and M represents a hydrogen atom or an alkali metal atom.

Description

COMPOUND AND COLORED CURABLE RESIN COMPOSITION [0001]

The present invention relates to a compound and a colored curable resin composition.

Dyes have been used for color display by using reflected light or transmitted light in the fields of, for example, textile materials, liquid crystal displays, inkjets, and the like. As such a dye, Japanese Patent Application Laid-Open No. 2004-2630 (Example 1) describes a compound represented by the following formula (d0).

The present invention includes the following inventions.

[1] A compound represented by the formula (Z).

[In the formula (Z), R ¹ represents a group containing an acryloyl group, a group containing a methacryloyl group or a group containing a silicon atom.

R ² represents a hydrogen atom, a cyano group or a carbamoyl group.

R ³ represents an alkyl group having 1 to 4 carbon atoms which may have a halogen atom.

R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, A nitro group, a carboxyl group or -SO ₃ M, and M represents a hydrogen atom or an alkali metal atom.

[2] The compound according to [1], wherein the group containing a silicon atom is a group represented by the formula (Z1).

^Wherein R ^11A represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ - included in the alkanediyl group is selected from the group consisting of -O-, -CO-, -NR ¹⁰ -, -OCO-, -COO-, -OCONH-, -CONH- or -NHCO-.

R ¹⁰ represents a hydrogen atom or a monovalent saturated hydrocarbon group of 1 to 20 carbon atoms.

R ^12A , R ^13A and R ^14A each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

* Represents the bonding bond with the nitrogen atom.

[3] The compound according to [1], wherein the group containing an acryloyl group or the group containing a methacryloyl group is a group represented by the formula (Z2).

^Wherein R ^15A represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ - included in the alkanediyl group is -O-, -CO-, -NR ¹¹ -, -OCO-, - -COO-, -OCONH-, -CONH- or -NHCO-.

R ¹¹ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

R ^16A represents an acryloyl group or a methacryloyl group.

* Represents the bonding bond with the nitrogen atom.

[4] A colorant comprising the compound according to any one of [1] to [3].

[5] A colorant according to [4] further comprising a pigment.

[6] The colorant according to [5], wherein the pigment is at least one selected from the group consisting of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment.

[7] The colorant according to [5] or [6], wherein the pigment is at least one selected from the group consisting of a chlorinated copper phthalocyanine pigment, a copper phthalocyanine pigment, and a zinc bromide phthalocyanine pigment.

[8] The colorant according to any one of [5] to [7], wherein the pigment is at least one selected from the group consisting of C. I. Pigment Green 36 and C. I. Pigment Green 58.

[9] A colored curable resin composition comprising a compound, a resin, a polymerizable compound and a polymerization initiator according to any one of [1] to [3].

[10] A color filter formed from the colored curable resin composition according to [9].

[11] A liquid crystal display device comprising a color filter according to [10].

When a color filter is formed from a colored curable resin composition containing the compound of the present invention, sublimation of the coloring agent can be suppressed.

<Compounds represented by formula (Z) (hereinafter sometimes referred to as compound (Z))>

[In the formula (Z), R ¹ represents a group containing an acryloyl group, a group containing a methacryloyl group or a group containing a silicon atom.

R ² represents a hydrogen atom, a cyano group, or a carbamoyl group.

R ³ represents an alkyl group having 1 to 4 carbon atoms which may have a halogen atom.

R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, A nitro group, a carboxyl group or -SO ₃ M, and M represents a hydrogen atom or an alkali metal atom.

R ² is preferably a cyano group.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ³ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.

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

Examples of the alkyl group having 1 to 4 carbon atoms having a halogen atom include a trifluoromethyl group, a pentafluoroethyl group, a trichloromethyl group, a tribromomethyl group, a pentachloroethyl group, a pentabromoethyl group and a dichlorofluoromethyl group have. Preferably a fluorinated alkyl group having 1 to 4 carbon atoms.

As R ³ , an alkyl group having 1 to 3 carbon atoms which may be substituted with a fluorine atom is preferable, a methyl group and a trifluoromethyl group are more preferable, and a methyl group is more preferable.

The alkyl group having 1 to 8 carbon atoms represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be any of chain and cyclic groups, and examples thereof include a methyl group, A cyclohexyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, a cyclopentyl group, A cyclohexyl group and a methylcyclohexyl group.

Examples of the alkoxy group having 1 to 8 carbon atoms represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ include a methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, And octyloxy group.

Examples of the alkoxyalkyl group having 2 to 8 carbon atoms represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a methoxybutyl group, a methoxypentyl group, Ethoxyethyl group, 1-methyl-2-ethoxyethyl group, 1- (1-methylethoxy) propyl group, 2- Ethoxy) propyl group, 1- (1-methylethoxy) -1-methylethyl group, 2- (1-methylethoxy) -1-methylethyl group and 3-ethoxypropyl group.

Examples of the alkali metal atom represented by M include a lithium atom, a sodium atom and a potassium atom.

M is preferably a hydrogen atom or a sodium atom, more preferably a hydrogen atom.

Examples of -SO ₃ M represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ include -SO ₃ H and -SO ₃ Na.

A group containing an acryloyl group or a group containing a methacryloyl group means a group having at least one acryloyl group or methacryloyl group and includes an acryloyl group or a methacryloyl group and an optionally substituted hydrocarbon group And the like.

The number of carbon atoms of the group containing an acryloyl group represented by R ¹ is usually 4 to 20, preferably 4 to 15, and more preferably 4 to 10.

The number of carbon atoms of the methacryloyl group represented by R ¹ is usually 5 to 20, preferably 5 to 15, and more preferably 5 to 10.

The group containing an acryloyl group is preferably a group containing an acryloyloxy group.

The group containing a methacryloyl group is preferably a group containing a methacryloyloxy group.

As a group containing an acryloyl group or a group containing a methacryloyl group represented by R ¹ , a group represented by the formula (Z2) is preferable.

^Wherein R ^15A represents an alkanediyl group having 1 to 10 carbon atoms and -CH ₂ - included in the alkanediyl group is -O-, -CO-, -NR ¹¹ -, -OCO-, -COO -, -OCONH-, -CONH- or -NHCO-.

R ¹¹ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.

R ^16A represents an acryloyl group or a methacryloyl group.

* Represents the bonding bond with the nitrogen atom.

Examples of the alkanediyl group having 1 to 10 carbon atoms represented by R ^15A include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, isopropylene, isobutylene, , An isopentylene group, an isohexylene group, an iso-octylene group and a 2-ethylhexylene group, and an alkanediyl group having 1 to 6 carbon atoms is preferable, and an alkanediyl group having 1 to 4 carbon atoms is more preferable.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, An alkyl group having 1 to 20 carbon atoms such as an isocyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group and a 2-ethylhexyl group;

And alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group.

R ¹¹ is preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, more preferably a methyl group or a hydrogen atom.

Examples of the group containing an acryloyl group or a methacryloyl group include groups represented by groups (ii-1) to (ii-14).

The group containing a silicon atom means a group containing a silicon atom as a constituent of the group and includes a group having a silicon atom and a hydrocarbon group which may be substituted.

The number of carbon atoms of the group containing a silicon atom represented by R ¹ is usually 1 to 30, preferably 1 to 20.

As the group containing a silicon atom represented by R ¹ , a group represented by the formula (Z1) is preferable.

^Wherein R ^11A represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ - included in the alkanediyl group is selected from the group consisting of -O-, -CO-, -NR ¹⁰ -, -OCO-, -COO-, -OCONH-, -CONH- or -NHCO-.

R ¹⁰ represents a hydrogen atom or a monovalent saturated hydrocarbon group of 1 to 20 carbon atoms.

R ^12A , R ^13A and R ^14A each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

* Represents the bonding bond with the nitrogen atom.

Examples of the alkanediyl group having 1 to 10 carbon atoms represented by R ^11A include the same groups as the alkanediyl group having 1 to 10 carbon atoms represented by R ^15A . R ^11A is preferably an alkanediyl group having 1 to 6 carbon atoms, more preferably an alkanediyl group having 1 to 4 carbon atoms.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁰ include the same monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹¹ .

The alkyl group having 1 to 4 carbon atoms represented by R ^12A , R ^13A and R ^14A may be any of a chain and a cyclic group, and examples thereof include a methyl group, ethyl group, n-propyl group, isopropyl group, , a tert-butyl group, a cyclopropyl group, and a cyclobutyl group.

Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ^12A , R ^13A and R ^14A include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, .

R ^12A , R ^13A and R ^14A are preferably the same group.

R ^12A , R ^13A and R ^14A are each independently preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.

Examples of the group containing a silicon atom include the groups described below.

As the group in which -CH ₂ - contained in R ^11A is substituted with -O-, there may be mentioned groups shown below (* represents a bond with a nitrogen atom).

As the group in which -CH ₂ - contained in R ^11A is substituted with -CO-, there may be mentioned groups shown below (* represents a bond with a nitrogen atom).

As the group in which -CH ₂ - contained in R ^11A is substituted with -NR ¹¹ -, there may be mentioned groups shown below (* represents a bond with a nitrogen atom).

As the group in which -CH ₂ - contained in R ^11A is substituted with -OCO-, there may be mentioned groups shown below (* represents a bond with a nitrogen atom).

As the group in which -CH ₂ - contained in R ^11A is substituted with -COO-, there may be mentioned the groups shown below (* indicates binding loss).

As the group in which -CH ₂ - contained in R ^11A is substituted with -OCONH-, there may be mentioned the groups shown below (* represents a bond with a nitrogen atom).

As the group substituted with -CH ₂ - by -CONH- included in R ^11A , there may be mentioned groups shown below (* represents a bond with a nitrogen atom).

As the group in which -CH ₂ - included in R ^11A is substituted with -NHCO-, there may be mentioned groups shown below (* represents a bond with a nitrogen atom).

As the group containing a silicon atom, a group shown below is preferable.

Specific examples of the compound (Z) include a compound represented by the formula (Z-1) to a compound represented by the formula (Z-68).

The compound (Z) can be produced by subjecting a diazonium salt represented by the formula (z2) to a coupling reaction with a compound represented by the formula (z3).

The diazonium salt represented by the formula (z2) can be obtained, for example, by diazotizing a compound represented by the formula (z1) with acetic acid, acetic acid salt or acetic acid ester.

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ have the same meanings as defined above. A ¹ represents an inorganic anion or an organic anion.]

Examples of the inorganic ions include halide ions such as fluoride ions, chloride ions, bromide ions, and iodide ions; Perchlorate ion, hypochlorite ion, and the like.

Examples of organic anions include carboxylate anions such as CH ₃ COO ^- and PhCOO ^- (wherein Ph represents a phenyl group).

Preferably a chloride ion, a bromide ion and CH ₃ COO ^- .

Compound (Z) can be produced by reacting a diazonium salt represented by formula (z2) with a compound represented by formula (z3) in an aqueous solvent such as N-methylpyrrolidone. The reaction temperature is preferably from -5 to 60 캜, more preferably from 0 캜 to 30 캜. The reaction time is preferably 1 to 12 hours, more preferably 1 to 4 hours.

The compound (Z) wherein R ¹ is a group containing a silicon atom can be obtained, for example, by reacting a compound represented by the formula (z5) with a compound represented by the formula (z6). The compound represented by the formula (z5) can be produced by diazotizing a diazonium salt represented by the formula (z2) and a compound represented by the formula (z4) to produce a compound represented by the formula (z5) have.

Wherein R &lt; ¹¹³ &gt; represents a divalent linking group.

R ¹¹⁴ and R ¹¹⁵ each independently represent a hydrophilic group.

R ¹¹⁶ represents a group containing a silicon atom.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined above.

Examples of the divalent linking group represented by R ¹¹³ include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an isopropylene group, an isobutylene group, a 2-methyltrimethylene group, And an alkanediyl group having 1 to 10 carbon atoms such as an isohexylene group, an isooctylene group and a 2-ethylhexylene group. -CH ₂ - included in the alkanediyl group may be substituted with -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -CONH- or -NHCO- .

Examples of the hydrophilic group represented by R ¹¹⁴ and R ¹¹⁵ include a hydroxyl group and a carboxyl group. Provided that R ¹¹⁴ and R ¹¹⁵ do not represent the same group.

The group containing a silicon atom represented by R &lt; ¹¹⁶ &gt; represents a group containing a silicon atom as a constituent of the group.

* -R ¹¹³ -R ¹¹⁶ (* represents a bond to the nitrogen atom) corresponds to R ¹ in the compound (Z).

The reaction between the compound represented by the formula (z5) and the compound represented by the formula (z6) is preferably carried out in the presence of a halogenated solvent such as chloroform. The reaction temperature is preferably -10 ° C to 100 ° C, more preferably 0 ° C to 50 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours.

The amount of the compound represented by the formula (z6) is usually 1 mol or more and 8 mol or less, preferably 1 mol or more and 4 mol or less per mol of the azo compound represented by the formula (z5).

In the reaction, it is more preferable to add an acidic catalyst in order to proceed the reaction smoothly. Examples of the acidic catalysts include mineral acids such as sulfuric acid and hydrochloric acid.

The amount of these catalysts to be used is arbitrary, but is preferably from 0.01 to 4 mol, more preferably from 0.8 to 2 mol, per mol of the compound represented by the formula (z6).

The method of obtaining the compound (Z) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, it is preferable that the reaction mixture is mixed with an acid (e.g., acetic acid etc.) and water, and the precipitated crystals are collected by filtration. It is preferable that the acid is prepared by preparing an aqueous solution of an acid in advance and then adding the reaction mixture to the aqueous solution. The temperature at the time of adding the reaction mixture is usually 10 ° C or more and 50 ° C or less, preferably 20 ° C or more and 50 ° C or less, preferably 20 ° C or more and 30 ° C or less. After the reaction mixture is added to the aqueous solution of the acid, the mixture is preferably stirred at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water or the like and then dried. If necessary, it may be further purified by a known method such as recrystallization.

The compound (Z) wherein R ¹ is a group containing an acryloyl group or a group containing a methacryloyl group can be obtained, for example, by reacting a compound represented by the formula (z8) with a compound represented by the formula (z9) have. The compound represented by the formula (z8) can be produced by reacting the diazonium salt represented by the formula (z2) with the compound represented by the formula (z7).

Wherein R &lt; ¹¹¹ &gt; represents a divalent linking group.

R ¹¹⁰ represents a group containing an acryloyl group or a group containing a methacryloyl group.

R ¹¹² represents a halogen atom.

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are as defined above.

Examples of the divalent linking group represented by R ¹¹¹ include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an isopropylene group, an isobutylene group, a 2-methyltrimethylene group, And an alkanediyl group having 1 to 10 carbon atoms such as an isohexylene group, an isooctylene group and a 2-ethylhexylene group. -CH ₂ - included in the alkanediyl group may be substituted with -O-, -CO-, -NR ¹¹ -, -OCO-, -COO-, -OCONH-, -CONH- or -NHCO- .

Examples of the halogen atom represented by R ¹¹² include a chlorine atom and a bromine atom.

The group containing an acryloyl group or the group containing a methacryloyl group represented by R ¹¹⁰ includes a group having at least one acryloyl group or methacryloyl group as a structural unit of a group.

* - R ¹¹¹ -R ¹¹⁰ (* represents a bond to a nitrogen atom) corresponds to R ¹ in the compound (Z).

The reaction between the compound represented by the formula (z8) and the compound represented by the formula (z9) is preferably carried out in the presence of a halogenated solvent such as chloroform. The reaction temperature is preferably -10 ° C to 100 ° C, more preferably 0 ° C to 50 ° C. The reaction time is preferably 1 hour to 12 hours, more preferably 1 hour to 4 hours.

The amount of the compound represented by the formula (z9) is usually 1 mol or more and 8 mol or less, preferably 1 mol or more and 4 mol or less per 1 mol of the compound represented by the formula (z8).

In the reaction, it is more preferable to add an acidic catalyst in order to proceed the reaction smoothly. Examples of the acidic catalyst include mines such as sulfuric acid and hydrochloric acid.

The amount of these catalysts to be used is arbitrary, but is preferably from 0.01 to 4 mol, more preferably from 0.8 to 2 mol, per mol of the compound represented by the formula (z6).

The method of obtaining the compound (Z) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, it is preferable that the reaction mixture is mixed with an acid (e.g., acetic acid etc.) and water, and the precipitated crystals are collected by filtration. It is preferable that the acid is prepared by preparing an aqueous solution of an acid in advance and then adding the reaction mixture to the aqueous solution. The temperature at which the reaction mixture is added is usually 10 ° C or higher and 50 ° C or lower, preferably 20 ° C or higher and 50 ° C or lower, preferably 20 ° C or higher and 30 ° C or lower. Further, after the reaction mixture is added to the aqueous solution of the acid, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water or the like and then dried. If necessary, it may be further purified by a known method such as recrystallization.

<Colorant>

Compound (Z) can be used as a dye. Colorants comprising compound (Z) also fall within the scope of the present invention.

As the coloring agent, two or more compounds (Z) may be used. The coloring agent may contain a dye or pigment other than the compound (Z).

As the dyes other than the compound (Z), a yellow dye or a red dye is preferable, and a sulfur dye is particularly preferable. Examples of the yellow dye include dyes having a coumarin skeleton.

The pigment is not particularly limited and a known pigment can be used. For example, a pigment classified in the Color Index (Pigment) by The Society of Dyers and Colourists is a pigment.

Examples of the pigment include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 194, 214;

Orange pigments such as C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, Pigments;

Blue pigments such as C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60;

C. I. violet pigments such as Pigment Violet 1, 14, 19, 23, 29, 32, 33, 36, 37, 38;

Green pigments such as C. I. Pigment Green 7, 10, 15, 25, 36, 47, 58;

Brown pigments such as C. I. Pigment Brown 23, 25;

And C. I. Pigment Black 1, 7 black pigments.

In the colorant, the pigment is preferably a phthalocyanine pigment, and more preferably at least one pigment selected from the group consisting of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment.

Examples of the halogenated copper phthalocyanine pigments include a fluorinated copper phthalocyanine pigment, a chlorinated copper phthalocyanine pigment, and a copper phthalocyanine pigment.

Examples of the zinc halide phthalocyanine pigment include a fluorinated zinc phthalocyanine pigment, a chlorinated zinc phthalocyanine pigment, and a zinc bromide phthalocyanine pigment.

More preferably, the pigment is at least one member selected from the group consisting of chlorinated copper phthalocyanine pigments, copper bromophthalocyanine pigments and zinc bromide phthalocyanine pigments, and particularly preferably selected from the group consisting of CI Pigment Green 36 and 58 At least one species.

These pigments are preferably used for green pigments, and by including the pigments described above, the transmission spectrum is easily optimized, and the light resistance and chemical resistance of the color filter are improved.

The pigment may be subjected to a surface treatment using a rosin treatment, a pigment derivative in which an acidic group or a basic group is introduced, a graft treatment on a pigment surface with a polymer compound or the like, an atomization treatment such as a sulfuric acid atomization method or an organic solvent A cleaning treatment with water or the like, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed. The particle diameters of the pigments are preferably uniform.

The pigment may be a pigment dispersion in a state of being uniformly dispersed in a pigment dispersant solution by containing a pigment dispersant and carrying out a dispersion treatment. Each of the pigments may be dispersed singly or plural kinds may be mixed and dispersed.

Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigments. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), SOLSPERSE (manufactured by Zeneca), EFKA (manufactured by CIBA) AJISPER (manufactured by Ajinomoto Fine Techno Co., Ltd.) and Disperbyk (manufactured by BYK Chemicals, Inc.).

When a pigment dispersant is used, the amount thereof is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the pigment. When the amount of the pigment dispersant is within the above range, a more uniformly dispersed pigment dispersion tends to be obtained.

The content of the compound (Z) is preferably 0.01% by mass or more and 90% by mass or less, more preferably 0.1% by mass or more and 80% by mass or less, and still more preferably 1% By mass or less, and more preferably 2% by mass or more and 60% by mass or less.

When the pigment is included, the content thereof is preferably 10% by mass or more and 99.99% by mass or less, more preferably 20% by mass or more and 99.9% by mass or less, and still more preferably 35% by mass or less, relative to the total amount of the colorant. Or more and 99 mass% or less, and more preferably 40 mass% or more and 98 mass% or less.

The colored curable resin composition of the present invention comprises a compound (Z), a resin (B), a polymerizable compound (C) and a polymerization initiator (D).

The colored curable resin composition of the present invention may contain two or more compounds (Z) as the colorant (A). The colorant (A) may contain a dye other than the compound (Z) or a pigment (P). Examples of the dyes and pigments (P) other than the compound (Z) include the dyes and pigments described above.

The colored curable resin composition of the present invention preferably further contains at least one kind selected from the group consisting of a solvent (E) and a leveling agent (F).

The colored curable resin composition of the present invention may further contain a polymerization initiator (D1).

In the present specification, the compounds exemplified as respective components may be used alone or in combination of two or more, unless otherwise specified.

In the colored curable resin composition of the present invention, the content of the colorant (A) is usually 1% by mass or more and 99% by mass or less, preferably 2% by mass or more and 90% by mass or less relative to the total amount of solid matter, , More preferably 5 mass% or more and 70 mass% or less, still more preferably 5 mass% or more and 60 mass% or less, and particularly preferably 5 mass% or more and 50 mass% or less % Or less. If the content of the colorant (A) is within the above range, desired spectral or color density can be obtained.

In the present specification, the "total amount of solid content" refers to the total amount of the components excluding the solvent (E) from the colored curable resin composition of the present invention. The total amount of the solid content and the content of each component in the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and an addition polymer having a structural unit derived from at least one kind selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride is more preferable. Examples of such a resin include the following resins [K1] to [K6].

(A) (hereinafter sometimes referred to as "(a)") selected from the group consisting of a resin [K1] unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having a carbon number of 2 to 4 and ethylene And a monomer (b) having an unsaturated bond (hereinafter sometimes referred to as &quot; (b) &quot;);

(Hereinafter referred to as &quot; (c) &quot;) of the resin (K2) (a) and the monomer (b) copolymerizable with the monomer (a) );

Resin [K3] Copolymer of (a) and (c);

Resin [K4] Resin (b) is reacted with the copolymer of (a) and (c);

Resin [K5] Resin (a) is reacted with the copolymer of (b) and (c);

Resin [K6] Resin (a) is reacted with the copolymer of (b) and (c) and further reacted with carboxylic acid anhydride.

Specific examples of the unsaturated monocarboxylic acid (a) include 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 tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- , 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto- [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 anhydrides such as dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-eno anhydride;

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

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 and maleic anhydride are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an aqueous alkali solution.

(b) is a polymer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one member selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond having an ethylenic unsaturated bond Compound. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

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

(b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter may be referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, (Hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)") and the like.

(b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)"), alicyclic unsaturated , And a monomer (b1-2) having a structure in which a hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

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

(meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and the like can be given as examples of (b1-2) vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane, Acrylate (for example, cyclomer M100 manufactured by Daicel Chemical Industries, Ltd.), a compound represented by formula (I) and a compound represented by formula (II).

[In the formulas (I) and (II), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group.

X ^a and X ^b 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, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.

Examples of the alkyl group in which the hydrogen atom is substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, 1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group.

Preferable examples of R ^a and R ^b are 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 propane-1,2-diyl group, a propane-1,3-diyl group, a butane- A 6-diyl group and the like.

X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, more preferably a single bond, * - CH ₂ CH ₂ -O- (wherein * represents a bond with O).

Examples of the compound represented by the formula (I) include a compound represented by any one of the formulas (I-1) to (I-15). Among them, the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I- Is preferable and a compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) is more preferable.

Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (II-15). Among them, the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II- , And compounds represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) are more preferable.

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of the compound represented by the formula (I) and the compound represented by the formula (II). When these compounds are used in combination, the content of the compound represented by formula (I) and the compound represented by formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 to 90: : 10, and more preferably from 20:80 to 80:20.

(b2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-methacryloyloxymethyloxetane, 3-methyl- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3- 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

As the monomer (b3), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of the compound (b3) include tetrahydrofurfuryl acrylate (for example, Viscot V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

(b) is preferably (b1) in that the reliability of the obtained color filter can be further improved, such as heat resistance and chemical resistance. Further, (b1-2) is more preferable because the storage stability of the colored curable resin composition is excellent.

(meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- butyl (meth) acrylate, 2-ethylhexyl Acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (Meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (referred to in the art as "dicyclopentanyl (meth) acrylate" Tricyclodecyl (meth) acrylate "), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (referred to in the art as" dicyclohexyl (Meth) acrylate "), dicyclopentanyloxime (Meth) acrylates such as ethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (Meth) acrylate, benzyl (meth) acrylate and the like;

(Meth) acrylic acid esters having a hydroxy group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

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

2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 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] 2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cicarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis 2,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene, Cyclounsaturated compounds;

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

And examples thereof include 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, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable.

In the resin [K1], the ratio of the respective structural units derived from among the whole structural units constituting the resin [K1]

(a); 2 to 60 mol%

(b); 40 to 98 mol%

, &Lt; / RTI &gt;

(a); 10 to 50 mol%

(b); 50 to 90 mol%

Is more preferable.

When the ratio of the structural unit of the resin [K1] is within the above range, there is a tendency that storage stability of the colored curable resin composition, developability in forming a colored pattern, and solvent resistance of the resulting color filter are excellent.

The resin [K1] can be synthesized by a method described in, for example, "Experimental Method of Polymer Synthesis" (published by Kagaku Dojin Co., Ltd., 1st Edition, 1st Edition, March 1, 1972, Can be prepared by reference to the literature.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator and a solvent are placed in a reaction vessel and oxygen is replaced by, for example, nitrogen, thereby forming a deoxidized atmosphere, Method. The polymerization initiator, solvent and the like to be used herein are not particularly limited and those generally used in the art can be used. Examples of the polymerization initiator include azo compounds (such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides (such as benzoyl peroxide) As the solvent, any one that dissolves the respective monomers may be used. As the solvent (E) of the colored curable resin composition of the present invention, there may be mentioned a solvent described later.

For the obtained copolymer, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by a method such as re-precipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction can be used as it is for preparing the colored curable resin composition of the present invention, The manufacturing process of the composition can be simplified.

In the resin [K2], the ratio of the structural units derived from each other is preferably such that, among all structural units constituting the resin [K2]

(a); 2 to 45 mol%

(b); 2 to 95 mol%

(c); 1 to 65 mol%

, &Lt; / RTI &gt;

(a); 5 to 40 mol%

(b); 5 to 80 mol%

(c); 5 to 60 mol%

Is more preferable.

When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, the developability in forming the colored pattern, and the solvent resistance, heat resistance and mechanical strength of the obtained color filter tend to be excellent .

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

In the resin [K3], the ratio of the structural units derived from each other is preferably such that, among all structural units constituting the resin [K3]

(a); 2 to 60 mol%

(c); 40 to 98 mol%

, &Lt; / RTI &gt;

(a); 10 to 50 mol%

(c); 50 to 90 mol%

Is more preferable.

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

Resin [K4] can be produced by obtaining a copolymer of (a) and (c) and adding a cyclic ether having 2 to 4 carbon atoms of (b) to a carboxylic acid and / or carboxylic anhydride of (a) .

First, the copolymer of (a) and (c) is prepared in the same manner as the method described as the method of producing the resin [K1]. In this case, the proportion of the structural units derived from each is preferably the same as that of the resin [K3].

Next, a cyclic ether having 2 to 4 carbon atoms of (b) is allowed to react with a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer.

Subsequently to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced by air from nitrogen, and (b) a reaction catalyst of carboxylic acid or carboxylic acid anhydride and cyclic ether (tris ) Phenol, etc.) and a polymerization inhibitor (hydroquinone, etc.) are placed in a flask and reacted at 60 to 130 占 폚 for 1 to 10 hours, for example.

(b) is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). By setting the content within this range, there is a tendency that the balance between the storage stability of the colored curable resin composition, the developability in forming the pattern, and the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern become good. (B1) is more preferable, and (b1-1) is more preferable for the resin (K4) because the reactivity of the cyclic ether is high and unreacted (b)

The amount of the reaction catalyst to be used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (c).

The reaction conditions such as the preparation method, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment or the amount of heat generated by polymerization. In addition, the preparation method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production equipment or polymerization, as well as the polymerization conditions.

Resin [K5] is a first step, and a copolymer of (b) and (c) is obtained in the same manner as in the above-mentioned production method of Resin [K1]. In the same manner as described above, the solution after the reaction may be used as it is, or a solution obtained by concentrating or diluting the solution may be used, or a solid (powder) obtained by re-precipitation or the like may be used.

The ratio of the structural units derived from (b) and (c) is preferably in the range of

(b); 5 to 95 mol%

(c); 5 to 95 mol%

, &Lt; / RTI &gt;

(b); 10 to 90 mol%

(c); 10 to 90 mol%

Is more preferable.

The carboxylic acid or carboxylic acid anhydride of (a) is reacted with a cyclic ether derived from (b) contained in the copolymer of (b) and (c) under the same conditions as in the production of resin [K4] , Whereby resin [K5] can be obtained.

The amount of (a) to be reacted with the copolymer is preferably 5 to 80 moles per 100 moles of (b). (B1) is more preferable, and (b1-1) is more preferable for the resin (K5) because the reactivity of the cyclic ether is high and unreacted (b)

The resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride. A carboxylic acid anhydride is reacted with a hydroxyl group generated by the reaction of the cyclic ether and the carboxylic acid or the carboxylic acid anhydride.

Examples of the carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6 -Tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride. The amount of the carboxylic acid anhydride to be used is preferably 0.5 to 1 mole based on 1 mole of the amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth) A resin [K1] such as a methacrylic acid copolymer; (Meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 (meth) acrylate / glycidyl .1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / N- cyclohexyl maleimide copolymer, the resin composition comprising 3,4-tricyclo [5.2.1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / Vinyltoluene copolymer, and a resin [K2] such as 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; A resin such as benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) ]; A resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / styrene / (K4) such as a resin obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; A resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, a resin obtained by reacting tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) A resin [K5] such as a resin obtained by reacting (meth) acrylic acid with a copolymer; A resin such as a resin obtained by reacting a (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate and tetrahydrophthalic anhydride in addition to the resin [K6] have.

The resin (B) preferably contains one kind selected from the group consisting of the resin [K1], the resin [K2] and the resin [K3], more preferably from the group consisting of the resin [K2] and the resin [K3] One species is selected. When these resins are used, the colored curable resin composition is excellent in developing property. From the viewpoint of the adhesion between the coloring pattern and the substrate, the resin [K2] is more preferable.

The weight average molecular weight of the resin (B) in terms of polystyrene is usually from 3,000 to 100,000, preferably from 5,000 to 50,000, more preferably from 5,000 to 35,000, still more preferably from 5,000 to 30,000, 30,000. When the molecular weight is within the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility of the unexposed portion in the developing solution is good, and the resolution of the coloring pattern tends to be improved.

The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value of the resin (B) is usually from 20 mgKOH / g to 170 mgKOH / g, preferably from 30 mgKOH / g to 170 mgKOH / g, more preferably from 40 mgKOH / KOH / g to 170 mg-KOH / g, and more preferably 50 mg-KOH / g to 170 mg-KOH / g. KOH / g to 150 mg-KOH / g, more preferably 60 mg-KOH / g to 150 mg-KOH / g, and even more preferably 60 mg-KOH / g to 135 mg- More preferably 70 mg-KOH / g to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

In the colored curable resin composition of the present invention, the content of the resin (B) is preferably 7% by mass to 65% by mass, more preferably 10% by mass to 60% by mass, relative to the total amount of solid matter, , Preferably 13% by mass to 60% by mass, and particularly preferably 17% by mass to 55% by mass. When the content of the resin (B) is within the above range, coloring pattern formation is easy, and the resolution and residual film ratio of the coloring pattern tends to be improved.

The polymerizable compound (C) is a compound capable of polymerizing with an active radical and / or an acid generated from the polymerization initiator (D), and includes a compound having a polymerizable ethylenically unsaturated bond, ) Acrylic acid ester compound.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N -Vinylpyrrolidone, and the above-mentioned (a), (a) and (c).

Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di Acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate.

The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds. Examples of the polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (metha) acrylate, tripentaerythritol hexa (Meth) acrylate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (metha) acrylate, propylene glycol-modified pentaerythritol tetra Modified dipentaerythritol hexa (meth) acrylate , Caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (metha) acrylate.

As the polymerizable compound (C), dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are more preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 to 1,500 or less.

In the colored curable resin composition of the present invention, the content of the polymerizable compound (C) is preferably 1 to 70% by mass, more preferably 2 to 65% by mass, based on the total solid content, , More preferably from 10 to 60 mass%, still more preferably from 13 to 60 mass%, still more preferably from 17 to 65 mass%, still more preferably from 7 to 65 mass% 55% by mass.

The content ratio of the resin (B) to the polymerizable compound (C) (resin (B): polymerizable compound (C)) is preferably 20:80 to 80:20, more preferably 35: 65 to 80:20.

When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a color pattern and the chemical resistance of the color filter tend to be improved.

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical or an acid by the action of light or heat and capable of initiating polymerization, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and nonimidazole compounds.

The O-acyloxime compound is a compound having a partial structure represented by formula (d1). Herein, * denotes a combined hand.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- - ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] (3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- 1- [ -9-ethyl-6- (2-methylbenzoyl) -9H-carbazole &lt; / RTI &gt; -3-yl] -3-cyclopentylpropan-1-one-2-imine. Commercially available products such as Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. Among them, the O-acyloxime compound is preferably an N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan- 2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, -Benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferable.

The alkylphenone compound is a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). Of these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- (4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) Butane-1-one and the like. IRGACURE 369, 907, 379 (manufactured by BASF Co., Ltd.) and the like may be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- 1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan- -Diethoxyacetophenone, benzyldimethylketal, and the like.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d2).

The imidazole compound is, for example, a compound represented by formula (d5).

[In the formula (d5), R ⁵¹ to R ⁵⁶ represent an aryl group having 6 to 10 carbon atoms which may have a substituent.]

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xylyl group, an ethylphenyl group and a naphthyl group, and preferably a phenyl group.

Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and preferably a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like, preferably a methoxy group.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 4 ', 5,5'-tetraphenylbiimidazole (see JP-A 6-75372 and JP-A 6-75373), 2,2'-bis (2- Chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4' Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis 4,4 ', 5', 5,5'-tetra (trialkoxyphenyl) biimidazole (see Japanese Examined Patent Publication Nos. 48-38403 and 62-174204, Imidazole compounds in which the phenyl group in the 5'-position is substituted by a carboalkoxy group (see JP-A-7-10913). Among them, compounds represented by the following formulas and mixtures thereof are preferable.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Methyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- 2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4,6-trichloromethyl- Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- - [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, camphorquinone, etc .; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiator D1 (particularly, amines) described below.

The polymerization initiator (D) is preferably a polymerization initiator comprising at least one member selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound and a nonimidazole compound, More preferably, it is a polymerization initiator comprising an O-acyloxime compound.

In the colored curable resin composition of the present invention, the content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) Preferably from 0.1 to 30 parts by mass, and more preferably from 1 to 30 parts by mass.

The polymerization initiator (D1) is a compound or a sensitizer used for promoting the polymerization of the polymerizable compound initiated by the polymerization initiator. When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiator (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethylbenzoate, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'- -Bis (ethylmethylamino) benzophenone, and among them, 4,4'-bis (diethylamino) benzophenone is preferable. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may be used.

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

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

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, Diphenylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

When the polymerization initiator (D1) is used in the colored curable resin composition of the present invention, the content thereof is preferably 0.1 to 30 parts by mass per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) Mass part, and more preferably 1 to 20 mass parts. When the amount of the polymerization initiator (D1) is within this range, it is possible to form a colored pattern with higher sensitivity, and the productivity of the color filter tends to be improved.

The solvent (E) is not particularly limited, and a solvent commonly used in the art can be used. As the solvent (E), an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- in the molecule and containing -COO-) Ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (including OH in the molecule), ether solvents (solvents containing -COO- and -O- in the molecule) , A solvent not containing -O-, -CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, 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, Methoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 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 monoethyl ether And the like Le acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 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 them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone, Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3-ethoxypropionic acid Ethyl, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone and the like are more preferable.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition. In other words, the solid content of the color-curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color density tends not to be insufficient when the color filter is formed, so that display characteristics tend to be good.

Examples of the leveling agent (F) include a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Concretely, TORAY silicone DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper solder SH8400 (trade name: manufactured by Toray Dow Corning Co.), KP321, KP322, KP323, KP324, KP326, KP340 , KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (produced by Momentive Performance Materials Japan Joint-Industrial Company).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specific examples thereof include Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Corporation), Megapack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F554 (Manufactured by Mitsubishi Materials Electronics Co., Ltd.), RS-718-K (manufactured by DIC Corporation), FTOP (registered trademark) EF301, EF303, EF351 and EF352 Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Co., Ltd.).

Examples of the silicon-containing surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megapac (registered trademark) R08, Copolymer BL20, Copolymer F475, Copolymer F477 and Copolymer F443 (manufactured by DIC Corporation).

The content of the leveling agent (F) is preferably 0.0005 mass% or more and 0.6 mass% or less, more preferably 0.001 mass% or more and 0.5 mass% or less, and preferably 0.001 mass% or less, relative to the total amount of the coloring- Or more and 0.2 mass% or less, preferably 0.002 mass% or more and 0.1 mass% or less, and more preferably 0.005 mass% or more and 0.07 mass% or less. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

The colored curable resin composition of the present invention may contain additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, if necessary.

The colored curable resin composition of the present invention can be obtained by mixing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent ), A leveling agent (F), a polymerization initiator (D1), and other components.

When the pigment P is contained, the pigment P is mixed with part or all of the solvent (E) in advance, and the pigment (P) is mixed with the solvent And then dispersed. At this time, if necessary, a part or all of the pigment dispersant and the resin (B) may be blended. The desired colored curable resin composition can be prepared by mixing the remaining components in the thus obtained pigment dispersion to a predetermined concentration.

The compound (Z) is preferably dissolved in a part or all of the solvent (E) in advance to prepare a solution. It is preferable to filter the solution with a filter having a pore diameter of about 0.01 to 1 mu m.

The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 mu m.

<Manufacturing Method of Color Filter>

The color filter of the present invention is formed from the colored curable resin composition of the present invention. The color filter may be a coating film having a colored pattern or a colored coating film described later.

Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Among them, the photolithographic method is preferable.

The photolithography method is a method in which the above-mentioned colored curable resin composition is applied to a substrate, followed by drying to form a colored composition layer, and then the colored composition layer is exposed through a photomask to perform development. In the photolithographic method, a colored coating film which is a cured product of the colored composition layer can be formed by not using a photomask at the time of exposure and / or not developing it.

The film thickness of the color filter is not particularly limited and can be appropriately adjusted according to the purpose or application, and is, for example, from 0.1 to 30 탆, preferably from 0.1 to 20 탆, more preferably from 0.5 to 6 탆.

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass and soda lime glass whose surface is coated with a silica, resin plates such as polycarbonate, polymethylmethacrylate and polyethylene terephthalate, silicon, , Silver, silver / copper / palladium alloy thin film, or the like is formed. A separate color filter layer, a resin layer, a transistor, a circuit, and the like may be formed on these substrates.

The formation of the color filter by the photolithographic method can be performed by a known apparatus or condition. For example, as follows.

First, a colored curable resin composition is coated on a substrate, followed by drying by heating (prebaking) and / or drying under reduced pressure to remove volatile components such as a solvent and drying to obtain a smooth colored composition layer.

Examples of the application method include a spin coating method, a slit coating method, and a slit and spin coating method.

The temperature in the case of heat drying is preferably 30 to 120 占 폚, more preferably 50 to 110 占 폚. The heating 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 film thickness of the coloring composition layer is not particularly limited and may be suitably selected in accordance with the film thickness of a desired color filter.

Next, the coloring composition layer is exposed through a photomask for forming a desired coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the application is used.

As the light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light having a wavelength of less than 350 nm is cut using a filter that cuts the wavelength region, or light having wavelengths around 436 nm, 408 nm, and 365 nm is extracted using a bandpass filter Or may be selectively taken out. Specific examples thereof include mercury lamps, light emitting diodes, metal halide lamps, and halogen lamps.

It is preferable to use an exposure apparatus such as a mask aligner and a stepper because it is possible to uniformly irradiate the entire exposure surface with a parallel light beam or accurately align the photomask with the substrate on which the coloring composition layer is formed.

The colored composition layer after exposure is brought into contact with a developing solution to develop a colored pattern on the substrate. By the development, the unexposed portion of the colored composition layer is dissolved and removed in the developer. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide or the like is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10 mass%, more preferably 0.02 to 5 mass%, and even more preferably 0.03 to 5 mass%. In addition, the developer may contain a surfactant.

The developing method may be any of paddle method, dipping method and spray method. Further, the substrate may be inclined at an arbitrary angle at the time of development.

After development, it is preferable to rinse with water.

In addition, post-baking is preferably performed on the obtained coloring pattern. The post bake temperature is preferably 150 to 250 占 폚, more preferably 160 to 235 占 폚. The post baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

[Example]

Next, the present invention will be described in more detail with reference to examples and the like.

In the examples and comparative examples, the percentages and parts representing the content or amount of use are on a mass basis unless otherwise specified.

The structure of the compound was confirmed by mass analysis (LC: Agilent 1200 type, MASS; Agilent LC / MSD 6130 type).

Example 1

After 4.0 parts of sodium hydroxide was added to 398 parts of water, 18.2 parts of the compound represented by the following formula (d1) was added. To the resulting mixture was added 7.1 parts of sodium acetic acid and 208 parts of water under ice-cooling (ice cooling), followed by the addition of 7.1 parts of 35% hydrochloric acid. Thereafter, the resulting mixture was stirred for 2 hours to obtain a suspension containing the diazonium salt.

20.8 parts of the compound represented by the formula (d2) was suspended in 404 parts of water, and the pH was adjusted to 9.0 with sodium hydroxide. To the resulting mixture, the suspension containing the diazonium salt obtained above was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was stirred for 30 minutes to obtain a yellow suspension, which was further stirred for 1 hour. The yellow solid obtained by filtration was dried at 60 DEG C under reduced pressure to obtain 38.5 parts of a compound represented by the formula (d3).

Identification (identification) of the compound represented by the formula (d3)

(Mass analysis) Ionization mode = ESI +: m / z = 401.0 [M + 1] ⁺

                          Exact Mass: 400.1

4.0 parts of the compound represented by the formula (d3) and 1.4 parts of 2- (trimethylsilyl) ethanol were added to 100 parts of dehydrated chloroform. 2.3 parts of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide and 1.5 parts of 4-dimethylaminopyridine were further added to the obtained mixture, and the mixture was stirred at 30 ° C for 6 hours. Water was added to the reaction mixture obtained, the organic layer was extracted, and chloroform was distilled off to obtain a yellow solid. And dried under reduced pressure at 60 DEG C for 24 hours to obtain 4.2 parts of a compound represented by the formula (1-1).

Identification of the compound represented by the formula (1-1)

(Mass analysis) Ionization mode = ESI +: m / z = 502.1 [M + 1] ⁺

                          Exact Mass: 501.1

Example 2

A compound represented by the formula (1-2) was obtained in the same manner as in Example 1 except that the compound represented by the formula (d4) was used instead of the compound represented by the formula (d1).

Identification of the compound represented by the formula (1-2)

(Mass analysis) Ionization mode = ESI +: m / z = 538.1 [M + 1] ⁺

                          Exact Mass: 537.1

Example 3

After 4.0 parts of sodium hydroxide was added to 398 parts of water, 18.2 parts of the compound represented by the formula (d5) was added. To the ice, 7.1 parts of sodium acetate and 208 parts of water were added, followed by 7.1 parts of 35% hydrochloric acid. Thereafter, the mixture was stirred for 2 hours to obtain a suspension containing the diazonium salt.

19.4 parts of the compound represented by the formula (d6) was suspended in 404 parts of water, and the pH was adjusted to 9.0 with sodium hydroxide. The suspension containing the diazonium salt obtained above was dropped by a pump over 15 minutes. After completion of the dropwise addition, stirring was further carried out for 30 minutes to obtain a yellow suspension. And stirred for 1 hour. The yellow solid obtained by filtration was dried under reduced pressure at 60 캜 to obtain 34.8 parts of a compound represented by the formula (d7).

Identification of the compound represented by the formula (d7)

(Mass analysis) Ionization mode = ESI +: m / z = 381.7 [M + 1] ⁺

                          Exact Mass: 380.7

Then, 3.8 parts of the compound represented by the formula (d7) and 2.0 parts of triethylamine were added to 300 parts of chloroform, followed by 3.1 parts of methacrylic anhydride, and the mixture was kept at 50 DEG C for 3 hours. After completion of the reaction, 300 parts of water was added, and the organic layer was extracted. The chloroform was distilled off to obtain a yellow solid. And dried under reduced pressure at 60 DEG C for 24 hours to obtain 3.8 parts of a compound represented by the formula (1-9).

Identification of the compound represented by the formula (1-9)

(Mass analysis) Ionization mode = ESI +: m / z = 442.3 [M + 1] ⁺

                          Exact Mass: 441.3

Example 4

A compound represented by the formula (1-10) was obtained in the same manner as in Example 3, except that the compound represented by the formula (d8) was used instead of the compound represented by the formula (d5).

Identification of compounds represented by formula (1-10)

(Mass analysis) Ionization mode = ESI +: m / z = 478.1 [M + 1] ⁺

                          Exact Mass: 477.1

Synthetic Example 1

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was allowed to flow into a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added and heated to 85 DEG C with stirring. Then, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] Decane-9-yl acrylate (content ratio: 50:50 in molar ratio) in 40 parts of propylene glycol monomethyl ether acetate was dropwise added using a dropping pump over about 5 hours. On the other hand, a solution obtained by dissolving 26 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was dropped into the flask using another dropping pump for about 5 hours. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 3 hours and then cooled to room temperature to obtain a solution of a copolymer (resin B1) having a solid content of 43.5%. The resin B1 thus obtained had a weight average molecular weight of 8000, a molecular weight distribution of 1.98, and an acid value in terms of solid content of 53 mgKOH / g.

[Preparation of colored curable resin composition]

Example 5

Colorant: C. I. Pigment Green 58 (pigment) 27 parts,

Acrylic pigment dispersant 12 parts,

Resin (B): Resin B1 (in terms of solid content) 9.5 parts, and

Solvent (E): Propylene glycol monomethyl ether acetate 180 parts

And a pigment dispersion (3) in which the pigment was fully dispersed by using a bead mill was obtained.

Colorant (A): A compound represented by the formula (1-1) 3.0 parts;

Resin (B): Resin B1 (in terms of solid content) 40 parts;

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nihon Kayaku Co., Ltd.) 49 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE-01 manufactured by BASF; O- compound) 9.8 parts;

Solvent (E): Propylene glycol monomethyl ether acetate 670 parts;

Leveling agent (F): polyether-modified silicone oil

(TORAY Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.15 part; And the pigment dispersion (3) were mixed to obtain a colored curable resin composition (J1).

Example 6

C. Coloring Curable Resin Composition (J2) was obtained in the same manner as in Example 5 except that C. I. Pigment Green 58 (pigment) was changed to C.I. Pigment Green 36 (pigment).

Example 7

A colored curable resin composition (J3) was obtained in the same manner as in Example 5 except that the compound represented by the formula (1-1) was changed to the compound represented by the formula (1-2).

Example 8

C. I. Coloring curable resin composition (J4) was obtained in the same manner as in Example 7 except that Pigment Green 58 (pigment) was changed to C.I. Pigment Green 36 (pigment).

Example 9

Colorant: C. I. Pigment Green 58 (pigment) 20 parts,

Acrylic pigment dispersant 12 parts,

Resin (B): Resin B1 (in terms of solid content) 9.5 parts, and

Solvent (E): Propylene glycol monomethyl ether acetate 180 parts

And a pigment dispersion (4) in which the pigment was sufficiently dispersed by using a bead mill was obtained.

Colorant (A): A compound represented by the formula (1-9) 2.5 parts;

Resin (B): Resin B1 (in terms of solid content) 40 parts;

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nihon Kayaku Co., Ltd.) 49 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE-01 manufactured by BASF; O- compound) 9.8 parts;

Solvent (E): Propylene glycol monomethyl ether acetate 670 parts;

Leveling agent (F): polyether-modified silicone oil

(TORAY Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.15 part; And the pigment dispersion (4) were mixed to obtain a colored curable resin composition (J5).

Example 10

CI Pigment Green 58 (pigment) was changed to CI Pigment Green 36 (pigment) to obtain a colored curable resin composition (J6).

Example 11

A colored curable resin composition (J7) was obtained in the same manner as in Example 9, except that the compound represented by the formula (1-9) was changed to the compound represented by the formula (1-10).

Example 12

CI Pigment Green 58 (pigment) was changed to CI Pigment Green 36 (pigment) to obtain a colored curable resin composition (J8) in the same manner as in Example 11.

Comparative Example 1

Colorant: C. I. Pigment Green 58 (pigment) 27 parts,

Acrylic pigment dispersant 12 parts,

Resin (B): Resin B1 (in terms of solid content) 9.5 parts, and

Solvent (E): Propylene glycol monomethyl ether acetate 180 parts

And a pigment dispersion (5) in which the pigment was sufficiently dispersed by using a bead mill was obtained.

Colorant: A compound represented by the formula (d0) 1.0 part;

Resin (B): Resin B1 (in terms of solid content) 40 parts;

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nihon Kayaku Co., Ltd.) 49 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE-01 manufactured by BASF; O- compound) 9.8 parts;

Solvent (E): Propylene glycol monomethyl ether acetate 670 parts;

Leveling agent (F): polyether-modified silicone oil

(TORAY Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.15 part; And the pigment dispersion (4) were mixed to obtain a colored curable resin composition (J9).

[Measurement of film thickness]

The film thickness was DEKTAK3; The film thickness was measured using a vacuum cleaner manufactured by Nippon Vacuum Technology Co., Ltd.

[Preparation of resin composition for sublimation test (SJS)] [

Resin: methacrylic acid / benzyl methacrylate (molar ratio: 30/70) copolymer (manufactured by Daoka Chemical Industry Co., Ltd., average molecular weight: 10700, acid value: 70 mgKOH / g) 33.8% propylene glycol monomethyl ether acetate solution 40.2 parts;

Polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nihon Kayaku Co., Ltd.) 5.8 parts;

Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE01, manufactured by BASF Japan) 0.58 parts;

Leveling agent: polyether-modified silicone (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.01 part;

Solvent: Propylene glycol monomethyl ether 46.6 parts;

Solvent: Propylene glycol monomethyl ether acetate 6.8 part

Were mixed to obtain a resin composition for sublimation test (SJS).

[Formation of resin coating film (SJSM) for sublimation test]

The above-obtained resin composition for sublimation test (SJS) was coated on a glass substrate (Eagle XG; Corning) having a 2-inch corner by a spin coating method and the volatile components were volatilized at 100 ° C for 3 minutes. After cooling, the substrate was irradiated with light at an exposure amount of 150 mJ / cm 2 (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK, manufactured by Topcon Co., Ltd.). And heated in an oven at 220 DEG C for 2 hours to form a resin coating film for sublimation test (SJSM) (film thickness 2.2 mu m).

Example 13 [Preparation of coloring pattern and evaluation of sublimation property]

The colored curable resin composition obtained in Example 1 was applied on a glass substrate (Eagle XG; Corning) having a 2-inch corner by spin coating, and then prebaked at 100 ° C for 3 minutes to form a colored composition layer. After cooling, an exposure amount of 80 mJ / cm &lt; 2 &gt; (80 mJ / cm &lt; 2 &gt;) was formed in an atmospheric environment by using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) with an interval of 200 mu m between the substrate on which the colored composition layer was formed and the quartz glass photomask 365 nm). As the photomask, a 100 μm line and space pattern was formed. The colored composition layer after exposure was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 캜 for 70 seconds to develop and wash with water to obtain a colored coating film. Further, the film thickness of the colored coating film was measured. The results are shown in Table 1.

This colored coating film and the resin coating film for sublimability test (SJSM) obtained above were opposed to each other with an interval of 70 탆 therebetween, and post-baking was performed at 230 캜 for 10 minutes to obtain a coloring pattern.

The color difference (? Eab *) before and after heating of the coloring pattern was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). The color difference ([Delta] Eab *) was 3.0.

When the color difference? Eab * is 5.0 or more, it indicates that the colorant has sublimation properties. The results are shown in Table 1. In Table 1, &amp; cir &amp; indicates that the colorant does not have sublimation properties, and X indicates that the colorant has sublimation properties.

Examples 14 to 20 and Comparative Example 2

A coloring pattern was obtained in the same manner as in Example 13 except that the colored curable resin composition (J1) obtained in Example 5 was replaced with the colored curable resin composition (J2) to the colored curable resin composition (J9) . The results are shown in Table 1.

When a color filter is formed from a colored curable resin composition containing the compound of the present invention, sublimation of the coloring agent can be suppressed. The color filter using the colored curable resin composition containing the compound of the present invention is preferably used for a display device such as a liquid crystal display device.

Claims (11)

A compound represented by the formula (Z).

[In the formula (Z), R ¹ represents a group containing an acryloyl group, a group containing a methacryloyl group or a group containing a silicon atom.
R ² represents a hydrogen atom, a cyano group or a carbamoyl group.
R ³ represents an alkyl group having 1 to 4 carbon atoms which may have a halogen atom.
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxyalkyl group having 2 to 8 carbon atoms, A nitro group, a carboxyl group or -SO ₃ M, and M represents a hydrogen atom or an alkali metal atom. The method according to claim 1,
Wherein the group containing a silicon atom is a group represented by the formula (Z1).

^Wherein R ^11A represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ - included in the alkanediyl group is selected from the group consisting of -O-, -CO-, -NR ¹⁰ -, -OCO-, -COO-, -OCONH-, -CONH- or -NHCO-.
R ¹⁰ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
R ^12A , R ^13A and R ^14A each independently represent a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.
* Represents the bonding bond with the nitrogen atom. The method according to claim 1,
A group containing an acryloyl group or a group containing a methacryloyl group is a group represented by the formula (Z2).

^Wherein R ^15A represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ - included in the alkanediyl group is -O-, -CO-, -NR ¹¹ -, -OCO-, - -COO-, -OCONH-, -CONH- or -NHCO-.
R ¹¹ represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
R ^16A represents an acryloyl group or a methacryloyl group.
* Represents the bonding bond with the nitrogen atom. A colorant comprising the compound according to claim 1 or 2. 5. The method of claim 4,
A colorant further comprising a pigment. 6. The method of claim 5,
Wherein the pigment is at least one selected from the group consisting of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment. The method according to claim 5 or 6,
Wherein the pigment is at least one selected from the group consisting of a chlorinated copper phthalocyanine pigment, a copper phthalocyanine pigment, and a zinc bromide phthalocyanine pigment. The method according to claim 5 or 6,
Wherein the pigment is at least one selected from the group consisting of CI Pigment Green 36 and CI Pigment Green 58. A colored curable resin composition comprising a compound, a resin, a polymerizable compound and a polymerization initiator according to claim 1 or 2. A color filter formed from the colored curable resin composition according to claim 9. A liquid crystal display device comprising the color filter according to claim 10.