TW201604244A - Compound and colored curable resin composition - Google Patents

Abstract

The present invention provides a compound represented by the formula (Z). (In the formula (Z), R1 is an acryloyl-containing group, a methylacryloyl-containing group or a Si-containing group; R 2 is a hydrogen atom, a cyano group or a carbamoyl group; R3 is an alkyl group having from 1 to 4 carbon atoms and capable of having halogen atoms; R 4 , R 5 , R 6 , R 7 and R 8 are respectively a hydrogen atom, an alkyl group having from 1 to 8 carbon atoms, an alkoxy group having from 1 to 8 carbon atoms, an alkoxyalkyl group having from 2 to 8 carbon atoms, a hydroxyl group, a cyano group, a nitro group, a carboxyl group or -SO3M, and M is a hydrogen atom or an alkali-metal atom.

Description

Compound and color hardening resin composition

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

The dye is used, for example, for color display using reflected light or transmitted light in the fields of fiber materials, liquid crystal display devices, inkjet, and the like. As the dye, a compound represented by the following formula (d0) is described in JP-A-2004-2630 (Example 1).

The invention includes the following invention.

[1] a compound represented by the formula (Z),

[In the formula (Z), R ¹ represents a group containing an acryl fluorenyl group, a group containing a methacryl fluorenyl group or a group containing a fluorene atom; R ² represents a hydrogen atom, a cyano group or an amine carbaryl group; and R ³ represents an An alkyl group having a halogen atom having 1 to 4 carbon atoms; and 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, and an alkoxy group having 1 to 8 carbon atoms. Alkoxy group having 2 to 8 carbon atoms, a hydroxyl group, a cyano group, 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 halogen 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 - contained in the alkanediyl group may be substituted with -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; and R ^12A , R ^13A and R ^14A each independently represent a hydrogen atom, a hydroxyl group, An alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; * means a bonding bond with a nitrogen atom].

[3] The compound according to [1], wherein the group containing an acrylonitrile group or a group containing a methacryl group is a group represented by the formula (Z2), *- ^R15A - R ^16A (Z2)

^Wherein R ^15A represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ - contained in the alkanediyl group may be substituted with -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 acryl group or a methacryl group; * represents Bonding bond of nitrogen atom].

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

[5] The coloring agent according to [4], which further comprises a pigment.

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

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

[8] The coloring agent 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 the compound according to any one of [1] to [3], a resin, a polymerizable compound, and a polymerization initiator.

[10] A color filter comprising the color-curable resin composition according to [9].

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

In the case where a color filter is formed from the color-curable resin composition containing the compound of the present invention, sublimation of the colorant can be suppressed.

<The compound represented by the formula (Z) (hereinafter, sometimes referred to as a compound (Z))>

[In the formula (Z), R ¹ represents a group containing an acryl fluorenyl group, a group containing a methacryl fluorenyl group or a group containing a fluorene atom; R ² represents a hydrogen atom, a cyano group or an amine carbaryl group; and R ³ represents an An alkyl group having a halogen atom having 1 to 4 carbon atoms; and 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, and an alkoxy group having 1 to 8 carbon atoms. Base, alkoxyalkyl group having 2 to 8 carbon atoms, hydroxyl group, cyano group, nitro group, carboxyl group or -SO ₃ M, 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 a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a third butyl group.

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 dichloro group. Fluoromethyl. Preferred is a fluoroalkyl group having 1 to 4 carbon atoms.

R ^{3 is} preferably an alkyl group having 1 to 3 carbon atoms which may be substituted by a fluorine atom, more preferably a methyl group or a trifluoromethyl group, and still more preferably a methyl group.

The alkyl group having 1 to 8 carbon atoms represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ may be either a chain or a ring, and examples thereof include a methyl group, an ethyl group and a n-propyl group. Base, isopropyl, n-butyl, t-butyl, tert-butyl, pentyl, hexyl, heptyl, 2-ethylhexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, ring Hexyl and methylcyclohexyl.

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, an ethoxy group, a propoxy group, a butoxy group and a pentyloxy group. , hexyloxy, heptyloxy and octyloxy.

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 and a methoxypropyl group. , methoxybutyl, methoxypentyl, 1-ethoxypropyl, 2-ethoxypropyl, 1-ethoxy-1-methylethyl, 1-methyl-2-B Oxyethyl, 1-(1-methylethoxy)propyl, 2-(1-methylethoxy)propyl, 1-(1-methylethoxy)-1-methyl Base, 2-(1-methylethoxy)-1-methylethyl, 3-ethoxypropyl.

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 and 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.

The group containing a propylene group or a group containing a methacryl group means having at least 1 Examples of the propylene fluorenyl group or the methacryl fluorenyl group include a group having a propylene fluorenyl group or a methacryl fluorenyl group, a substituted hydrocarbon group, and the like.

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

The carbon number of the group containing the methacryl fluorenyl group represented by R ¹ is usually 5 to 20, preferably 5 to 15, more preferably 5 to 10.

The group containing an acrylonitrile group is preferably a group containing an acryloxy group.

The group containing a methacryl fluorenyl group is preferably a group containing a methacryloxy group.

The group containing an acryl fluorenyl group represented by R ¹ or a group containing a methacryl fluorenyl group is preferably a group represented by the formula (Z2).

*-R ^15A -R ^16A (Z2)

^Wherein R ^15A represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ - contained in the alkanediyl group may be substituted with -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 acryl group or a methacryl group; * represents Nitrogen bonding bond]

Examples of the alkanediyl group having 1 to 10 carbon atoms represented by R ^15A include a methylene group, an ethylidene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, and an isopropyl group. , isobutyl, 2-methyltrimethylene, isopentyl, isohexyl, isooctyl and 2-ethylhexyl, preferably alkanediyl having 1 to 6 carbon atoms, more preferably Alkanediyl having 1 to 4 carbon atoms.

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 decyl group, a decyl group, and a dodecane group. Carbon, hexadecyl, eicosyl, isopropyl, isobutyl, t-butyl, tert-butyl, isopentyl, neopentyl, 2-ethylhexyl, etc. An alkyl group; an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a 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 methacryl group include a group represented by the group (ii-14) represented by (ii-1).

The group containing a ruthenium atom means a group containing a ruthenium atom as a constituent element of the group, and examples thereof include a group having a ruthenium atom and a hydrocarbon group which may be substituted.

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

The group containing a ruthenium atom represented by R ¹ is preferably a group represented by the formula (Z1).

^Wherein R ^11A represents an alkanediyl group having 1 to 10 carbon atoms, and -CH ₂ - contained in the alkanediyl group may be substituted with -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; and R ^12A , R ^13A and R ^14A each independently represent a hydrogen atom, a hydroxyl group, An alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; * means a bonding bond with a nitrogen atom]

Examples of the alkanediyl group having 1 to 10 carbon atoms represented by R ^11A include the same examples 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.

The saturated hydrocarbon group having a monovalent number of carbon atoms of 1 to 20 represented by R ¹⁰ may be the same as the saturated hydrocarbon group having a monovalent number of carbon atoms of 1 to 20 represented by R ¹¹ .

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

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

R ^12A , R ^13A and R ^{14A are} preferably all the same groups.

R ^12A , R ^13A and R ^{14A are} preferably each independently 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 ruthenium atom include the groups described below.

The group in which -CH ₂ - contained in R ^11A is substituted with -O- includes a group represented by the following (* represents a bond to a nitrogen atom).

The group in which -CH ₂ - contained in R ^11A is substituted with -CO- includes a group represented by the following (* represents a bond to a nitrogen atom).

The group in which -CH ₂ - contained in R ^11A is substituted with -NR ¹¹ - may, for example, be a group represented by the following (* represents a bond to a nitrogen atom).

The group in which -CH ₂ - contained in R ^11A is substituted with -OCO- includes a group represented by the following (* represents a bond to a nitrogen atom).

The group in which -CH ₂ - contained in R ^11A is substituted with -COO- includes a group represented by the following (* represents a bond).

The group in which -CH ₂ - contained in R ^11A is substituted with -OCONH- includes a group represented by the following (* represents a bond to a nitrogen atom).

The group in which -CH ₂ - contained in R ^11A is substituted with -CONH- includes a group represented by the following (* represents a bond to a nitrogen atom).

The group in which -CH ₂ - contained in R ^11A is substituted with -NHCO- includes a group represented by the following (* represents a bond to a nitrogen atom).

The group containing a ruthenium atom is preferably a group represented by the following.

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

The compound (Z) can be produced by coupling a diazonium salt represented by the formula (z2) 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 nitrous acid, nitrite or nitrite.

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 anion include halide ions such as fluoride ions, chloride ions, bromide ions, and iodide ions; perchlorate ions and hypochlorite ions.

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

Preferred are chloride ions, bromide ions and CH ₃ COO ^- .

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

The compound (Z) wherein R ¹ is a group containing a ruthenium 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 a diazo coupling of 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).

^Wherein R ¹¹³ represents a divalent linking group; R ¹¹⁴ and R ¹¹⁵ each independently represent a hydrophilic group; R ¹¹⁶ represents a group containing a halogen atom; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent the same meaning as above]

Examples of the divalent linking group represented by R ¹¹³ include a methylene group, an exoethyl group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an exoisopropyl group, and an isobutylene group. Alkyldiyl having 1 to 10 carbon atoms such as 2-methyltrimethylene, isopentyl, isohexyl, isooctyl and 2-ethylhexyl. The -CH ₂ - contained in the alkanediyl group may also 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. Wherein R ¹¹⁴ and R ¹¹⁵ do not represent the same group.

The group containing a ruthenium atom represented by R ¹¹⁶ represents a group including a ruthenium atom as a constituent element of the group.

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

The reaction of the compound represented by the formula (z5) with 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 from 1 hour to 12 hours, more preferably from 1 hour to 4 hours.

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

At the time of the reaction, in order to carry out the reaction smoothly, it is preferred to add an acidic catalyst. Examples of the acidic catalyst include mineral acids such as sulfuric acid and hydrochloric acid.

The amount of the catalyst used is arbitrary, and it is preferably 0.01 to 4 moles, more preferably 0.8 to 2 moles, per mole of the compound 1 represented by the formula (z6).

The method for obtaining the compound (Z) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, it is preferred to mix the reaction mixture with an acid such as acetic acid or the like and water, and to remove the precipitated crystals by filtration. The above acid is preferably prepared by previously preparing an aqueous acid solution and then adding the reaction mixture to the above aqueous solution. The temperature at which the reaction mixture is added 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. Further, after the reaction mixture is added to the aqueous acid solution, it is preferably stirred at the same temperature for about 0.5 to 2 hours. The crystals removed by filtration are preferably washed with water or the like and then dried. Further, it may be further purified by a known method such as recrystallization as needed.

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

Wherein R ¹¹¹ represents a divalent linking group; R ¹¹⁰ represents a group containing an acryldenyl group or a group containing a methacryl group; R ¹¹² represents a halogen atom; R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent the same meaning as described above]

Examples of the divalent linking group represented by R ¹¹¹ include a methylene group, an exoethyl group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an exoisopropyl group, and an isobutylene group. Alkyldiyl having 1 to 10 carbon atoms such as 2-methyltrimethylene, isopentyl, isohexyl, isooctyl and 2-ethylhexyl. The -CH ₂ - contained in the alkanediyl group may also 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.

Examples of the group containing a propylene group represented by R ¹¹⁰ or a group containing a methacryl group include a group having at least one propylene group or a methacryl group as a constituent unit of the group.

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

The reaction of the compound represented by the formula (z8) with 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 from 1 hour to 12 hours, more preferably from 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, based on the compound 1 mol represented by the formula (z8).

At the time of the reaction, in order to carry out the reaction smoothly, it is preferred to add an acidic catalyst. Examples of the acidic catalyst include mineral acids such as sulfuric acid and hydrochloric acid.

The amount of the catalyst used is arbitrary, and it is preferably 0.01 to 4 moles, more preferably 0.8 to 2 moles, per mole of the compound 1 represented by the formula (z6).

The method for obtaining the compound (Z) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, it is preferred to mix the reaction mixture with an acid such as acetic acid or the like and water, and to remove the precipitated crystals by filtration. The above acid is preferably prepared by previously preparing an aqueous acid solution and then adding the reaction mixture to the above aqueous solution. Temperature at which the reaction mixture is added It 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. Further, after the reaction mixture is added to the aqueous acid solution, it is preferably stirred at the same temperature for about 0.5 to 2 hours. The crystals removed by filtration are preferably washed with water or the like and then dried. Further, it may be further purified by a known method such as recrystallization as needed.

<colorant>

Compound (Z) can be used as a dye. Further, the coloring agent containing the compound (Z) is also within the scope of the invention of the present invention.

Two or more compounds (Z) may be used as the colorant. The colorant may also contain a dye or pigment other than the compound (Z).

The dye other than the compound (Z) is preferably a yellow dye or a red dye, and particularly preferably a yellow dye. As a yellow dye, the dye which has a coumarin skeleton is mentioned, for example.

The pigment is not particularly limited, and a known pigment can be used, and examples thereof include a pigment classified as a pigment in a Colour Index (published by The Society of Dyers and Colourists).

Examples of the pigment include CI Pigment Yellow 1, Pigment Yellow 3, Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 15, Pigment Yellow 16, Pigment Yellow 17, Pigment Yellow 20, Pigment Yellow 24, Pigment Yellow 31 , Pigment Yellow 53, Pigment Yellow 83, Pigment Yellow 86, Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 109, Pigment Yellow 110, Pigment Yellow 117, Pigment Yellow 125, Pigment Yellow 128, Pigment Yellow 137, Pigment Yellow 138, Pigment Yellow pigments such as yellow 139, pigment yellow 147, pigment yellow 148, pigment yellow 150, pigment yellow 153, pigment yellow 154, pigment yellow 166, pigment yellow 173, pigment yellow 180, pigment yellow 194, pigment yellow 214, etc. CI pigment orange 13 , Pigment Orange 31, Pigment Orange 36, Pigment Orange 38, Pigment Orange 40, Pigment Orange 42, Pigment Orange 43, Pigment Orange 51, Pigment Orange 55, Pigment Orange 59, Pigment Orange 61, Pigment Orange 64, Pigment Orange 65, Pigment Orange pigment such as orange 71 and pigment orange 73; CI Pigment Red 9, Pigment Red 97, Pigment Red 105, Pigment Red 122, Pigment Red 123, Pigment red 144, pigment red 149, pigment red 166, pigment red 168, pigment red 176, pigment red 177, pigment red 180, pigment red 192, pigment red 209, pigment red 215, pigment red 216, pigment red 224, pigment red 242, pigment red 254, pigment red 255, pigment red 264, pigment red 265 and other red pigment; CI pigment blue 15, pigment blue 15:3, pigment blue 15:4, pigment blue 15:6, pigment blue 60 and other blue Pigment; CI pigment violet 1, pigment violet 14, pigment violet 19, pigment violet 23, pigment violet 29, pigment violet 32, pigment violet 33, pigment violet 36, pigment violet 37, pigment violet 38 and other purple pigments; CI pigment green 7 , pigment green 10, pigment green 15, pigment green 25, pigment green 36, pigment green 47, pigment green 58 and other green pigments; CI pigment brown 23, pigment brown 25 and other brown pigments; CI pigment black 1, pigment black 7 and other black Pigments, etc.

In the above coloring agent, the pigment is preferably a phthalocyanine pigment, and more preferably at least one selected from the group consisting of a copper halide phthalocyanine pigment and a zinc halide phthalocyanine pigment.

Examples of the copper halide phthalocyanine pigment include a copper fluoride phthalocyanine pigment, a copper chloride phthalocyanine pigment, and a copper bromide phthalocyanine pigment.

Examples of the zinc halide phthalocyanine pigment include a zinc fluoride phthalocyanine pigment, a zinc chloride phthalocyanine pigment, and a zinc bromide phthalocyanine pigment.

The pigment is further preferably at least one selected from the group consisting of copper chloride phthalocyanine pigment, copper bromide phthalocyanine pigment, and zinc bromide phthalocyanine pigment, and more preferably selected from the group consisting of CI Pigment Green 36 and Pigment Green 58. At least one of the group consisting of.

These pigments can be preferably used for a green pigment, and by including the above pigment, it is easy to optimize the transmission spectrum, and the light filter and the chemical resistance of the color filter are excellent.

The pigment may also be subjected to rosin treatment, and an acidic or basic group may be introduced. Surface treatment of a pigment derivative or the like, graft treatment of a pigment surface by a polymer compound or the like, microparticulation treatment by a sulfuric acid micronization method, or washing with an organic solvent or water for removing impurities Treatment, ionic impurities, removal treatment by ion exchange method or the like. The particle size of the pigment is preferably uniform.

The pigment is dispersed in a pigment dispersant by a pigment dispersant to form a pigment dispersion which is uniformly dispersed in the pigment dispersant solution. The pigments may be separately subjected to dispersion treatment, or may be mixed with a plurality of types for dispersion treatment.

Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used alone or in combination of two or more. As the pigment dispersing agent, the product name is KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA Co., Ltd.), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie Co., Ltd.), and the like.

In the case of using a pigment dispersant, 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 used is in the above range, there is a tendency that a pigment dispersion liquid having a more uniform dispersed state can 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 more based on the total amount of the coloring agent. 65 mass% or less, more preferably 2 mass% or more and 60 mass% or less.

When the pigment is contained, 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%, based on the total amount of the coloring agent. The mass% or more and 99% by mass or less are more preferably 40% by mass or more and 98% by 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 a coloring agent (A). Further, the colorant (A) may contain a dye other than the compound (Z) or a pigment (P). Examples of the dye and the pigment (P) other than the compound (Z) include the above dyes and pigments.

The colored curable resin composition of the present invention preferably further comprises at least one 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 initiation aid (D1).

In the present specification, the compounds exemplified as the respective components may be used singly or in combination of plural kinds 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% based on the total amount of the solid content component. The mass% or less is more preferably 3% by mass or more and 80% by mass or less, further preferably 5% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and particularly preferably 5% by mass or less. The above is 50% by mass or less. When the content of the coloring agent (A) is within the above range, the desired spectral or color density can be obtained.

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

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

The resin [K1] is selected from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter sometimes referred to as "(a)") and cyclic ether having a carbon number of 2 to 4. Structure and ethylene a copolymer of a monomer (b) (hereinafter sometimes referred to as "(b)"); a resin [K2] (a) and (b), and a monomer copolymerizable with (a) (c) (wherein (a) is different from (b)) (hereinafter sometimes referred to as "(c)"); resin [K3] is a copolymer of (a) and (c); resin [K4 a resin obtained by reacting the copolymer of (a) and (c) with (b); a resin [K5] is a resin obtained by reacting the copolymer of (b) and (c) with (a); [K6] is a resin obtained by reacting the copolymer of (b) and (c) with (a) and further with a carboxylic anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid, fumaric acid, and methyl cis. Butenedioic acid, methyl fumaric acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acid such as 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid or 1,4-cyclohexene dicarboxylic acid; methyl-5-lower Alkene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-A Bicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2 - a bicyclic unsaturated compound containing a carboxyl group such as a olefin, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, methyl maleic anhydride, itaconic anhydride, 3 -vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , dimethyltetrahydrophthalic anhydride, unsaturated dicarboxylic anhydride such as 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; succinic acid mono [2-(methyl) propylene oxime Unsaturated mono[(meth)acryloxyalkyl] of a divalent or higher polycarboxylic acid such as a phenylethyl ester or a mono[2-(methyl) propylene methoxyethyl] phthalate An ester; an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule of α-(hydroxymethyl)acrylic acid.

Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable in terms of the aspect of the copolymerization reactivity or the solubility of the obtained resin in an aqueous alkaline solution.

(b) is, for example, a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and ethylene are not A polymerizable compound of a saturated bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

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

(b), for example, a monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), an oxetanyl group and an ethylenic group are not mentioned. The monomer (b2) having a saturated bond (hereinafter sometimes referred to as "(b2)"), the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), and the like.

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

Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidyl vinyl ether. , o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-vinylvinyl benzyl Glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2 , 5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl)styrene, 2 , 3,5-tris(glycidoxymethyl)styrene, 2,3,6- Tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidoxymethyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, and the like.

Examples of (b1-2) include vinylcyclohexene oxide, 1,2-epoxy-4-vinylcyclohexane, and 3,4-epoxycyclohexylmethyl (meth)acrylate. 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer M100, manufactured by Daicel Co., Ltd.), a compound represented by the formula (I), a compound represented by the formula (II), and the like.

[In the formulae (I) and (II), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with ^a hydroxyl 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 a carbon number of 1 to 6; * indicates the O Key button]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a third butyl group.

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

R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylidene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5. - Diyl, hexane-1,6-diyl and the like.

As X ^a and X ^b , a single bond, a methylene group, an ethylidene group, *-CH ₂ -O-, and *-CH ₂ CH ₂ -O- may be preferably exemplified, and more preferably: a single bond , *-CH ₂ CH ₂ -O- (* indicates the bond with O).

The compound represented by the formula (I) may, for example, be a compound represented by any one of the formulae (I-1) to (I-15). Among them, preferred are the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9) or the formula (I-11) to the formula (I). The compound represented by -15) is more preferably a compound represented by the formula (I-1), the formula (I-7), the formula (I-9) or the formula (I-15).

The compound represented by the formula (II) may, for example, be a compound represented by any one of the formulae (II-1) to (II-15). Among them, preferred are formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II). The compound represented by -15) is more preferably a compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination with the compound represented by the formula (II). In the case where these are used in combination, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is on a molar basis, preferably from 5:95 to 95:5, more preferably 10 : 90~90:10, and further preferably 20:80~80:20.

As (b2), a monomer having an oxetanyl group and a (meth) acryloxy group is more preferable. Examples of (b2) include 3-methyl-3-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, and 3- Ethyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methylpropene oxime Ethyloxyoxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane, 3 -ethyl-3-propenyloxyethyl Oxetane and the like.

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

(b) is preferably (b1) in terms of further improving the reliability of heat resistance and chemical resistance of the obtained color filter. Further, in terms of excellent storage stability of the colored curable resin composition, (b1-2) is more preferable.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentane (meth)acrylate Ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]non-8-ester (in the technical field) It is commonly used as "dicyclopentanyl (meth)acrylate". Also, it is sometimes called "tricyclodecyl (meth)acrylate), tricyclo(meth)acrylate [5.2.1.0 ^2,6 ] Terpene-8-ester (commonly known in the art as "dicyclopentenyl (meth)acrylate), dicyclopentyloxy (meth)acrylate, (meth)acrylic acid) Ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (meth)acrylic acid (meth) acrylate such as benzyl ester; hydroxyl group-containing (meth) acrylate such as 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; diethyl maleate a dicarboxylic acid diester such as diethyl fumarate or diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene , 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5 -(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]g 2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di (2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[ 2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methyl double [2.2.1] Hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclo) a bicyclic unsaturated compound such as hexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenyl maleimide, N-cyclohexylmethyleneimine, N-benzyl Maleimide, N-butylimidazolyl-3-methyleneimine benzoate, N-butanediamine-4-butyleneimine Acid ester, N-butyl diimide imino-6-m-butylene imide hexanoate, N-butyl diimide imino-3-butane diimide propionate, N-( 9-Acridine-based dicarbonyl ruthenium derivatives such as maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and para Oxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3 - dimethyl-1,3-butadiene or the like.

Among these, styrene, vinyl toluene, benzyl (meth)acrylate, and trimethyl (meth)acrylate are preferred in terms of copolymerization reactivity and heat resistance [5.2.1.0 ^2,6癸-8-ester, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, bicyclo [2.2.1] g 2-ene and the like.

In the resin [K1], the ratio of the structural unit derived from each monomer to all the structural units constituting the resin [K1] is preferably

Structural unit derived from (a); 2~60 mol%

Structural unit derived from (b); 40 to 98% by mole, more preferably

Structural unit derived from (a); 10~50 mol%

The structural unit derived from (b); 50 to 90 mol%.

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

The resin [K1] can be referred to, for example, in the literature "Experimental Method for Polymer Synthesis" (Dajin Long, Press Chemical Co., Ltd., 1st Edition, 1st Brush, published on March 1, 1972) and in the literature. Manufactured by reference to the cited documents.

Specifically, a method in which a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are charged into a reaction container, for example, by replacing oxygen with nitrogen, thereby forming a deoxidizing environment and stirring Heating and keeping warm on one side. Further, the polymerization initiator, solvent and the like used herein are not particularly limited, and can be used for users in the field. For example, examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxidation. In the solvent (E) of the colored curable resin composition of the present invention, the solvent (E) may be exemplified as the solvent (Ethylene Benzoate).

The obtained copolymer may be directly used as a solution after the reaction, or may be a solution obtained by concentration or dilution, or may be taken out as a solid (powder) by a method such as reprecipitation. In particular, by using the solvent contained in the color-curable resin composition of the present invention as a solvent in the polymerization, the solution after the reaction can be directly used in the preparation of the color-curable resin composition of the present invention, so that the present invention can be simplified. A manufacturing step of the inventive color-curable resin composition.

In the resin [K2], the ratio of the structural unit derived from each monomer to all the structural units constituting the resin [K2] is preferably

Structural unit derived from (a); 2~45 mol%

Structural unit derived from (b); 2~95 mol%

a structural unit derived from (c); 1 to 65 mol%, Better

Structural unit derived from (a); 5~40 mol%

Structural unit derived from (b); 5~80 mol%

The structural unit derived from (c); 5 to 60 mol%.

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

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

In the resin [K3], the ratio of the structural unit derived from each monomer to all the structural units constituting the resin [K3] is preferably

Structural unit derived from (a); 2~60 mol%

Structural unit derived from (c); 40 to 98% by mole, more preferably

Structural unit derived from (a); 10~50 mol%

The structural unit derived from (c); 50 to 90 mol%.

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

The resin [K4] can be obtained by obtaining a copolymer of (a) and (c), and adding (a) a carboxylic acid and/or a carboxylic anhydride having (b) a carbon number of 2 to 4; Manufactured from ether.

First, a copolymer of (a) and (c) is produced in the same manner as the method described in the method for producing the resin [K1]. In this case, the ratio of the structural unit derived from each monomer is preferably the same as the ratio listed in the resin [K3].

Then, a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the above copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms which is contained in (b).

After the manufacture of the copolymer of (a) and (c), the environment inside the flask was replaced with nitrogen. Gas, and (b), a carboxylic acid or a carboxylic acid anhydride and a cyclic ether reaction catalyst (tris(dimethylaminomethyl)phenol, etc.) and a polymerization inhibitor (hydroquinone, etc.) are charged into the flask. The reaction is carried out, for example, at 60 to 130 ° C for 1 to 10 hours, whereby the resin [K4] can be produced.

The amount of use of (b) is preferably from 5 to 80 moles, more preferably from 10 to 75 moles, relative to (a) 100 moles. With this range, the storage stability of the colored curable resin composition, the developability at the time of pattern formation, and the balance between solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern tend to be good. . As the (b) for the resin [K4], it is preferably (b1), and more preferably (b1-1) in terms of the reactivity of the cyclic ether being high and the unreacted (b). ).

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

The reaction conditions such as the addition method, the reaction temperature, and the time can be appropriately adjusted in consideration of the amount of heat generated by the production equipment or the polymerization. Further, as in the case of the polymerization conditions, the addition method or the reaction temperature can be appropriately adjusted in consideration of the amount of heat generation due to the production equipment or polymerization.

Regarding the resin [K5], as the first stage, the copolymers of (b) and (c) were obtained in the same manner as in the above-mentioned production method of the resin [K1]. As in the case described above, the obtained copolymer may be used as it is, or a concentrated or diluted solution may be used, or may be taken out as a solid (powder) by a method such as reprecipitation.

The ratio of the structural unit derived from (b) and (c) to the total number of moles of all the structural units constituting the above copolymer is preferably

Structural unit derived from (b); 5~95 mol%

Structural unit derived from (c); 5 to 95% by mole, more preferably

Structural unit derived from (b); 10~90% by mole

The structural unit derived from (c); 10 to 90 mol%.

Further, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) and the carboxylic acid or carboxyl group (a) having the copolymer of (b) and (c) are obtained. The acid anhydride is reacted, whereby the resin [K5] can be obtained.

The amount of (a) used in the reaction with the above copolymer is preferably from 5 to 80 moles per 100 moles of (b). As the (b) for the resin [K5], it is preferably (b1), and more preferably (b1-1) in terms of the reactivity of the cyclic ether being high and not remaining unreacted. ).

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

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

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer and (meth)acrylic acid 3,4-epoxytricyclo[5.2. 1.0 ^2.6 ]Resin such as oxime ester/(meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (meth)acrylic acid shrinkage ester / styrene / (meth) acrylic acid copolymer, (meth) acrylate, 3,4-epoxy-tricyclo [5.2.1.0 ^2.6] decyl acrylate / (meth) acrylic acid / N- cyclohexyl maleate醯imine copolymer, 3,4-epoxytricyclo(5.sup.3-epoxy)[5.2.1.0 ^2.6 ] decyl ester / (meth) acrylate / vinyl toluene copolymer, 3-methyl-3- (methyl Resin such as acryloxymethyloxetane/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(A) Resin such as acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylate copolymer [K3]; benzyl (meth) acrylate / (methyl) Resin obtained by adding acrylic acid copolymer to glycidyl (meth)acrylate, p-(meth) propylene A resin obtained by adding a tricyclodecyl methacrylate/styrene/(meth)acrylic acid copolymer to glycidyl (meth)acrylate, p-trimethyl decyl (meth) acrylate / benzyl (meth) acrylate / ( a resin such as a resin obtained by adding a methyl (meth)acrylic acid copolymer to a glycidyl (meth)acrylate [K4]; a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate and ( a resin obtained by reacting methyl methacrylate, a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate/styrene/glycidyl methacrylate with (meth)acrylic acid [K5] And a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate is reacted with (meth)acrylic acid to obtain a resin, and the obtained resin is further subjected to tetrahydrophthalic anhydride. Resin such as resin [K6] obtained by reaction.

The resin (B) is preferably one selected from the group consisting of a resin [K1], a resin [K2], and a resin [K3], and more preferably selected from the group consisting of a resin [K2] and a resin [K3]. One of them. When it is such a resin, the coloring curable resin composition is excellent in developability. From the viewpoint of the adhesion between the colored pattern and the substrate, the resin [K2] is further preferable.

The polystyrene-equivalent weight average molecular weight of the resin (B) is usually 3,000 to 100,000, preferably 5,000 to 50,000, more preferably 5,000 to 35,000, still more preferably 5,000 to 30,000, still more preferably 6,000 to 30,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is also high, the solubility of the unexposed portion in the developer is good, and the resolution of the colored 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 from 1.1 to 6, more preferably from 1.2 to 4.

The acid value of the resin (B) is usually from 20 mg-KOH/g to 170 mg-KOH/g, preferably from 30 mg-KOH/g to 170 mg-KOH/g, more preferably from 40 mg-KOH/g to 170 mg-KOH/g. Further, it is preferably 50 mg-KOH/g to 170 mg-KOH/g. Among them, it is preferably 50 mg-KOH/g to 150 mg-KOH/g, more preferably 60 mg-KOH/g to 150 mg-KOH/g, further preferably 60 mg-KOH/g to 135 mg-KOH/g, particularly preferably It is 70 mg-KOH/g to 135 mg-KOH/g. Here, the acid value is the amount of potassium hydroxide (mg) required to neutralize 1 g of the resin (B). The measured value can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

In the colored curable resin composition of the present invention, the content of the resin (B) is preferably from 7% by mass to 65% by mass, more preferably from 10% by mass to 60% by mass, based on the total amount of the solid content component. It is preferably 13% by mass to 60% by mass, particularly preferably 17% by mass to 55% by mass. When the content of the resin (B) is in the above range, the coloring pattern is likely to be formed, and the resolution of the colored pattern and the residual film ratio tend to be improved.

The polymerizable compound (C) is a compound which can be polymerized by an active radical and/or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and the like. (Meth) acrylate compound.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexyl carbitol acrylate. And 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like, and the above (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, and neopentyl glycol di(a). Acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, and the like.

The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of the polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and Dipentaerythritol hexa(meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, tetrakis pentaerythritol hexa (meth) acrylate, Tris(2-(meth)acryloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra(meth) acrylate, ethylene glycol modified dipentaerythritol hexa(meth) acrylate, propylene glycol Modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth) acrylate, caprolactone modification Pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like.

The polymerizable compound (C) is more preferably dipentaerythritol penta (meth) acrylate or dipentaerythritol hexa (meth) acrylate.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, 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 from 1 to 70% by mass, and preferably from 2 to 65% by mass, based on the total amount of the solid content component. It is preferably 5 to 65% by mass, and more preferably 7 to 65% by mass, more preferably 10 to 60% by mass, still more preferably 13 to 60% by mass, still more preferably 17 to 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 by mass. 80:20.

When the content of the polymerizable compound (C) is in the above range, the residual film ratio at the time of formation of the colored 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 which generates an active radical, an acid or the like by the action of light or heat, and the polymerization can be started. A known polymerization initiator can be used.

As the polymerization initiator (D), an alkylphenone compound, three a compound, a mercaptophosphine oxide compound, an O-mercaptopurine compound, a biimidazole compound, and the like.

The above O-indenyl ruthenium compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * indicates a keying key.

Examples of the above O-indenyl ruthenium compound include N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imide and N-benzylformamide. 1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclopentyl Propane-1-keto-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzomethyl)-9H-indazol-3-yl]ethane -1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolyl) Methoxy)benzylidene}-9H-indazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzene Mercapto)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylidene-1-(9-ethyl-6-(2-methyl) Benzhydryl)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (above, manufactured by BASF Corporation), and N-1919 (manufactured by ADEKA Co., Ltd.) can also be used. Wherein, the O-indenyl hydrazine compound is preferably selected from the group consisting of N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzyl hydrazine 1-(4-phenylthiophenyl)octane-1-one-2-imine and N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclopentyl At least one of the group consisting of propan-1-one-2-imine, more preferably N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2 - Imine.

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

As a compound having a partial structure represented by the formula (d2), for example, 2-methyl-2- Lolinyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1-(4- Phenylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Polinyl)phenyl]butan-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (above, manufactured by BASF Corporation) can also be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4- (2-hydroxyethoxy)phenyl]propane 1-ketone, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethyl Oxyacetophenone, benzoin dimethyl ketal, and the like.

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

The biimidazole compound is, for example, a compound represented by the 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 tolylmethyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and a phenyl group is preferred.

Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is 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, and a butoxy group, and a methoxy group is preferred.

As the biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-di) Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (refer to Japanese Patent Laid-Open No. Hei 6-75372, Japanese Patent Laid-Open No. Hei 6-75373, etc.), 2, 2'-double (2-Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra Alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'- Bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (refer to Japanese Patent Publication No. Sho 48-38403, Japanese Patent Laid-Open No. 62-174204 The imidazole compound in which the phenyl group at the 4,4'5,5'-position is substituted with a carbonyl alkoxy group (see Japanese Patent Laid-Open Publication No. Hei 7-10913, etc.). Among them, preferred are compounds represented by the following formulas and mixtures thereof.

As the above three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-sunflower-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.

The above fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide.

As the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl phthalate; -Phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(t-butylcarbonyl peroxide) benzophenone a benzophenone compound such as 2,4,6-trimethylbenzophenone; an anthracene compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine, camphorquinone; 10-butyl-2-chloropurine Pyridone, benzoin, methyl phenylglyoxylate, titanocene compound, and the like. These are preferably used in combination with the following polymerization starting assistants (D1), especially amines.

The polymerization initiator (D) preferably contains a compound selected from the group consisting of alkyl phenones, three A polymerization initiator which is at least one of a group consisting of a compound, a mercaptophosphine oxide compound, an O-mercaptophosphonium compound, and a biimidazole compound is more preferably a polymerization initiator containing an O-mercaptopurine compound.

In the color hardening resin composition of the present invention, the content of the polymerization initiator (D) The total amount of the resin (B) and the polymerizable compound (C) is preferably 0.1 to 40 parts by mass, more preferably 0.1 to 30 parts by mass, even more preferably 1 to 30 parts by mass.

The polymerization initiation aid (D1) is a compound for promoting polymerization of a polymerizable compound which starts polymerization by a polymerization initiator, or a sensitizer. In the case of containing the polymerization starting assistant (D1), it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include an amine compound, an alkoxy fluorene compound, a thioxanthone compound, and a carboxylic acid compound.

The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate or 4-dimethyl Isoamyl benzoate benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)benzophenone (commonly known as Michlerone), 4,4'-bis(diethylamino)benzophenone, 4,4'-double (B The methylamino) benzophenone or the like is preferably 4,4'-bis(diethylamino)benzophenone. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

The above alkoxy fluorene compound may, for example, be 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene or 2-ethyl -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

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

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methoxybenzenesulfide. Acetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthalene sulfuric acid, N-naphthylglycine, Naphthyloxyacetic acid and the like.

In the color hardening resin composition of the present invention, the polymerization initiation aid is used. In the case of the agent (D1), the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). When the amount of the polymerization initiation aid (D1) is within this range, the coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

The solvent (E) is not particularly limited, and a solvent generally used in the field can be used. Examples of the solvent (E) include an ester solvent (a solvent containing -COO- in the molecule and containing no -O-), an ether solvent (a solvent containing -O- in the molecule and containing no -COO-), and an ether ester solvent. (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- and no -COO- in the molecule), alcohol solvent (containing OH in the molecule and not containing -O-, -CO - and -COO-solvent), aromatic hydrocarbon solvent, guanamine solvent, dimethyl hydrazine, and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, ring Hexanol acetate, γ-butyrolactone, and the like.

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, and two. Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Tetrahydrofuran, tetrahydropyran, 1,4-two Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether, methyl Anisole and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, propyl 2-methoxypropionate, 2-ethoxy Methyl propyl propionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropanoate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxy Butyl acetate, 3-methyl-3-methoxyacetic acid butyl ester, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate Ester, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and the like.

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

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

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

Examples of the guanamine 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, preferred are 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-methoxyacetic acid butyl ester, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-di Methylformamide, N-methylpyrrolidone, etc., more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxyacetic acid butyl ester, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethyl Mercaptoamine, N-methylpyrrolidone, and the like.

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 component of the colored curable resin composition is preferably from 5 to 30% by mass, more preferably from 8 to 25% by mass. If solvent (E) When the content is in the above range, the flatness at the time of coating becomes good, and the color density is sufficient when the color filter is formed, so that the display characteristics tend to be good.

Examples of the leveling agent (F) include a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom. These may also have a polymerizable group in the side chain.

Examples of the polyoxymethylene-based surfactant include a surfactant having a decane bond in the molecule. Specific examples include: Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name, manufactured by Toray Dow Corning Co., Ltd.), 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 (manufactured by Momentive Performance Materials Japan Contracting Company) .

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain in the molecule. Specific examples include Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC Corporation), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Precision Chemical Research Co., Ltd.).

Examples of the polyfluorene-based surfactant having a fluorine atom include a surfactant having a decane bond and a fluorocarbon chain in the molecule. Specific examples: Megafac (registrar Standard) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac 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%, and more preferably 0.001 mass, based on the total amount of the coloring curable resin composition. % or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less, more preferably 0.005% by mass or more and 0.07% by mass or less. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be made good.

The colored curable resin composition of the present invention may optionally contain additives such as a filler, other polymer compound, adhesion promoter, antioxidant, light stabilizer, chain transfer agent, and the like as known in the art.

The colored curable resin composition of the present invention can be used, for example, by a coloring agent (A) such as a compound (Z), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and optionally The solvent (E), the leveling agent (F), the polymerization starting aid (D1), and other components are prepared by mixing.

When the pigment (P) is contained, the pigment (P) is preferably partially or wholly mixed with one of the solvent (E), and dispersed by using a bead mill or the like until the average particle diameter of the pigment (P) is 0.2 μm or less. about. At this time, part or all of the above pigment dispersant and resin (B) may be blended as needed. The target colored curable resin composition can be prepared by mixing the remaining components in a pigment dispersion obtained in this manner so as to have a specific concentration.

The compound (Z) is preferably prepared by dissolving in part or all of the solvent (E) in advance. Preferably, the solution is filtered using a filter having a pore diameter of about 0.01 to 1 μm.

Preferably, the mixed color-curable resin composition is filtered by a filter having a pore diameter of about 0.01 to 10 μm.

<Method of Manufacturing Color Filter>

The color filter of the present invention is formed by the color hardening resin composition of the present invention. to make. The color filter may be a coating film having a colored pattern, or may be a colored coating film described below.

The method of producing a colored pattern by the colored curable resin composition of the present invention includes a photolithography method, an inkjet method, a printing method, and the like. Among them, photolithography is preferred.

The photolithography method is a method in which the colored curable resin composition is applied onto a substrate and dried to form a colored composition layer, and the colored composition layer is exposed to light through a photomask to be developed. In the photolithography method, a colored coating film which is a cured product of the coloring composition layer can be formed without using a photomask and/or without developing.

The film thickness of the color filter is not particularly limited, and may be appropriately adjusted depending on the purpose, use, and the like, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, or soda-lime glass coated with cerium oxide; or polycarbonate, polymethyl methacrylate or polyparaphenyl may be used. A resin plate such as ethylene dicarboxylate; an aluminum, silver, silver/copper/palladium alloy film or the like formed on the substrate. Other color filter layers, resin layers, transistors, circuits, and the like may also be formed on the substrates.

The formation of the color filter by photolithography can be carried out using known or conventional devices or conditions. For example, it can be produced in the following manner.

First, the colored curable resin composition is applied onto a substrate, and dried by heating (prebaking) and/or under reduced pressure to remove volatile components such as a solvent, and dried to obtain a smooth colored composition layer.

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

The temperature at the time of heat drying is preferably from 30 to 120 ° C, more preferably from 50 to 110 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.

In the case of drying under reduced pressure, it is preferably at a pressure of 50 to 150 Pa at 20~ It is carried out at a temperature range of 25 °C.

The film thickness of the colored composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the desired color filter.

The colored composition layer is then exposed through a reticle that forms the desired color pattern. The pattern on the photomask is not particularly limited, and a pattern according to the use can be used.

As the light source for exposure, a light source that emits light having a wavelength of 250 to 450 nm is preferable. For example, light having a wavelength of less than 350 nm may be cut off using a filter that cuts off the wavelength region, or light in the vicinity of 436 nm, around 408 nm, and around 365 nm may be selectively extracted using a band pass filter that extracts the wavelength regions. Specific examples thereof include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp.

In order to uniformly illuminate the entire exposed surface with parallel rays or to accurately position the substrate with the substrate on which the colored composition layer is formed, an exposure device such as a mask aligner and a stepper is preferably used.

The coloring pattern is formed on the substrate by developing the exposed coloring composition layer in contact with the developing solution. The unexposed portion of the colored composition layer is removed by dissolving in a developing solution by development. As the developer, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferred. The concentration of the basic compound in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, still more preferably 0.03 to 5% by mass. Further, the developer may also contain a surfactant.

The developing method may be any one of a liquid coating method, a dipping method, and a spray method. Further, the substrate can be tilted at an arbitrary angle during development.

It is preferred to carry out water washing after development.

Preferably, the obtained colored pattern is further post-baked. The post-baking temperature is preferably from 150 to 250 ° C, more preferably from 160 to 235 ° C. The post-baking time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.

[Examples]

Next, the present invention will be more specifically described by way of examples and the like.

In the examples and comparative examples, the % and the parts indicating the content or the amount used are based on mass unless otherwise specified.

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

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. Under ice cooling, 7.1 parts of sodium nitrite and 208 parts of water were added to the obtained mixture, followed by the addition of 7.1 parts of 35% hydrochloric acid. Thereafter, the obtained mixture was stirred for 2 hours to obtain a suspension containing a 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 using sodium hydroxide. To the obtained 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, whereby a yellow suspension was obtained, which was further stirred for 1 hour. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 38.5 parts of the compound of formula (d3).

Identification of compounds represented by 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-(trimethyldecyl)ethanol were added to 100 parts of dehydrated chloroform. Further, 2.3 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide and 1.5 parts of 4-dimethylaminopyridine were added to the obtained mixture, and the mixture was stirred at 30 ° C. Mix for 6 hours. Water was added to the obtained reaction mixture, the organic layer was extracted, and chloroform was evaporated to give a yellow solid. The mixture was dried under reduced pressure at 60 ° C for 24 hours to obtain 4.2 parts of the compound represented by the formula (1-1).

Identification of compounds represented by formula (1-1)

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

Exact Mass: 501.1

Example 2

In the first embodiment, the compound represented by the formula (1-2) is obtained in the same manner as the compound represented by the formula (d4), except for the compound represented by the formula (d1).

Identification of compounds represented by 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. Under ice cooling, 7.1 parts of sodium nitrite 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 a diazonium salt.

19.4 parts of the compound represented by the formula (d6) was suspended in 404 parts of water using sodium hydroxide Adjust the pH to 9.0. The suspension containing the diazonium salt obtained above was added dropwise over 15 minutes using a pump. After completion of the dropwise addition, the mixture was further stirred for 30 minutes, whereby a yellow suspension was obtained. Stir for 1 hour. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 34.8 parts of the compound of formula (d7).

Identification of compounds represented by 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 the addition of 3.1 parts of methacrylic anhydride, and the mixture was kept at 50 ° C for 3 hours. After the completion of the reaction, 300 parts of water was added, and the organic layer was extracted and the chloroform was evaporated to give a yellow solid. It was dried under reduced pressure at 60 ° C for 24 hours to obtain 3.8 parts of the compound represented by the formula (1-9).

Identification of compounds represented by formula (1-9)

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

Exact Mass: 441.3

Example 4

In the third embodiment, a compound represented by the formula (d8) is used instead of the compound represented by the formula (d5), and a compound represented by the formula (1-10) is obtained in the same manner.

Identification of compounds represented by formula (1-10)

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

Exact Mass: 477.1

Synthesis Example 1

An appropriate amount of nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated to 85 ° C while stirring. Then, using a drip pump, 19 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]non-8-ester and acrylic acid 3 were added dropwise to the flask over a period of about 5 hours. a mixture of 4-epoxytricyclo[5.2.1.0 ^2,6 ]癸-9-ester (containing 50:50 by molar ratio) of 171 parts dissolved in propylene glycol monomethyl ether acetate Solution. On the other hand, using another drip pump, the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) 26 parts was dissolved in the propylene glycol monomethylate by dropwise addition to the flask over a period of about 5 hours. A solution of 120 parts of ether acetate. After completion of the dropwise addition of the polymerization initiator, it was kept 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 obtained resin B1 had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value of 53 mgKOH/g in terms of solid content.

[Preparation of Colored Curable Resin Composition]

Example 5

Colorant: 27 parts of CI Pigment Green 58 (pigment), 12 parts of acrylic pigment dispersant, Resin (B): Resin B1 (in terms of solid content) 9.5 parts, and Solvent (E): Propylene glycol monomethyl ether acetate 180 parts of ester

The mixing was carried out, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion liquid (3).

The coloring agent (A): 3.0 parts of the compound represented by the formula (1-1); the resin (B): the resin B1 (in terms of solid content) 40 parts; the polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD) (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 49 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one -2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 9.8 parts; solvent (E): 670 parts of propylene glycol monomethyl ether acetate; leveling agent (F) : Polyether modified polysiloxane (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts; and pigment dispersion liquid (3) were mixed to obtain a colored curable resin composition (J1).

Example 6

A colored curable resin composition (J2) was obtained in the same manner as in Example 5 except that C.I. Pigment Green 58 (pigment) was replaced by 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 replaced by the compound represented by the formula (1-2).

Example 8

Replace C.I. Pigment Green 58 (pigment) with C.I. Pigment Green 36 (pigment), in addition to A colored curable resin composition (J4) was obtained in the same manner as in Example 7.

Example 9

Colorant: 20 parts of CI Pigment Green 58 (pigment), 12 parts of acrylic pigment dispersant, Resin (B): Resin B1 (in terms of solid content) 9.5 parts, and Solvent (E): Propylene glycol monomethyl ether acetate 180 parts of ester

The mixing was carried out, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion (4).

Coloring agent (A): 2.5 parts of the compound represented by the formula (1-9); resin (B): resin B1 (in terms of solid content) 40 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD) (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 49 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one -2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 9.8 parts; solvent (E): 670 parts of propylene glycol monomethyl ether acetate; leveling agent (F) : 0.15 parts of a polyether modified polysiloxane (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.); and a pigment dispersion liquid (4) were mixed to obtain a colored curable resin composition (J5).

Example 10

A colored curable resin composition (J6) was obtained in the same manner as in Example 9 except that C.I. Pigment Green 58 (pigment) was replaced by C.I. Pigment Green 36 (pigment).

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 replaced by the compound represented by the formula (1-10).

Example 12

A colored curable resin composition (J8) was obtained in the same manner as in Example 11 except that C.I. Pigment Green 58 (pigment) was replaced by C.I. Pigment Green 36 (pigment).

Comparative example 1

Colorant: 27 parts of CI Pigment Green 58 (pigment), 12 parts of acrylic pigment dispersant, Resin (B): Resin B1 (in terms of solid content) 9.5 parts, and Solvent (E): Propylene glycol monomethyl ether acetate 180 parts of ester

The mixing was carried out, and the pigment was sufficiently dispersed using a bead mill to obtain a pigment dispersion liquid (5).

Coloring agent: 1.0 part of the compound represented by the formula (d0); resin (B): resin B1 (in terms of solid content) 40 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA ; manufactured by Nippon Kayaku Co., Ltd.) 49 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-mercaptopurine compound) 9.8 parts; solvent (E): propylene glycol monomethyl ether acetate 670 parts; leveling agent (F): polyether modification 0.15 parts of a polyoxygenated oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.); and a pigment dispersion liquid (4) were mixed to obtain a colored curable resin composition (J9).

[Measurement of film thickness]

The film thickness was measured using DEKTAK 3 manufactured by Nippon Vacuum Technology Co., Ltd.

[Preparation of Sublimation Test Resin Composition (SJS)]

Resin: methacrylic acid/benzyl methacrylate (Morby: 30/70) copolymer (manufactured by Tajika Chemical Industry Co., Ltd., average molecular weight 10700, acid value 70 mgKOH/g) 33.8% propylene glycol monomethyl ether B 40.2 parts of an acid ester solution; a polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 5.8 parts; polymerization initiator: N-benzyl methoxy-1- 4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF Japan) 0.58 parts; leveling agent: polyether modified polyoxo (Toray Silicone SH8400) ;Toray Dow Corning Co., Ltd.) 0.01 parts; solvent: propylene glycol monomethyl ether 46.6 parts; solvent: propylene glycol monomethyl ether acetate 6.8 parts

The mixture was mixed to obtain a sublimation test resin composition (SJS).

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

The resin composition for sublimation test (SJS) obtained above was applied by a spin coating method to a glass substrate (Eagle XG; manufactured by Corning Co., Ltd.) of 2 inches, and was allowed to stand at 100 ° C for 3 minutes. Volatile components are volatilized. After cooling, it was irradiated with light at an exposure amount (365 nm basis) of 150 mJ/cm ² in an atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.). The film was heated at 220 ° C for 2 hours in an oven to form a resin coating film (SJSM) for sublimation test (film thickness: 2.2 μm).

Example 13 [Production and Sublimation Evaluation of Coloring Pattern]

The color hardening resin composition obtained in Example 1 was applied by a spin coating method on a glass substrate (Eagle XG; manufactured by Corning) of 2 inches square, and then prebaked at 100 ° C for 3 minutes. A colored composition layer is formed. After cooling, the distance between the substrate on which the colored composition layer was formed and the mask made of quartz glass was set to 200 μm, and the exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used at 80 mJ/cm ² in an atmosphere. The exposure amount (365 nm reference) was exposed. Further, as the photomask, a pattern in which a line and a gap of 100 μm were formed was used. The colored composition layer after the exposure was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide for 30 seconds at 25 ° C to develop, and washed 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.

The colored coating film and the above-mentioned sublimation test resin coating film (SJSM) were opposed to each other with a space of 70 μm therebetween, and post-baked at 230 ° C for 10 minutes to obtain a colored pattern.

The color difference (ΔEab*) before and after heating of the colored pattern was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). The color difference (ΔEab*) was 3.0.

When the color difference (?Eab*) is 5.0 or more, it means that the coloring agent has sublimation property. The results are shown in Table 1. In Table 1, ○ indicates that the colorant does not have sublimation property, and × indicates that the colorant has sublimation property.

Example 14 to Example 20 and Comparative Example 2

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), respectively. The coloring pattern was obtained in such a manner that sublimation evaluation was performed. The results are shown in Table 1.

[Industrial availability]

In the case where a color filter is formed from the color-curable resin composition containing the compound of the present invention, sublimation of the colorant can be suppressed. The color filter using the color-curable resin composition containing the compound of the present invention can be 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 acryl fluorenyl group, a group containing a methacryl fluorenyl group or a group containing a fluorene atom; R ² represents a hydrogen atom, a cyano group or an amine carbaryl group; and R ³ represents an An alkyl group having a halogen atom having 1 to 4 carbon atoms; and 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, and an alkoxy group having 1 to 8 carbon atoms. Alkoxy group having 2 to 8 carbon atoms, a hydroxyl group, a cyano group, a nitro group, a carboxyl group or -SO ₃ M, and M represents a hydrogen atom or an alkali metal atom]. The compound of claim 1, wherein the group containing a ruthenium 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 - contained in the alkanediyl group may be substituted with -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; and R ^12A , R ^13A and R ^14A each independently represent a hydrogen atom, a hydroxyl group, An alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; * means a bonding bond with a nitrogen atom]. The compound of claim 1, wherein the group comprising a propylene fluorenyl group or a group comprising a methacryl fluorenyl group is a group represented by the formula (Z2), *-R ^{15A -} R ^16A (Z2) wherein R ^15A represents The alkanediyl group having 1 to 10 carbon atoms, and the -CH ₂ - contained in the alkanediyl group may be substituted with -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 a bond with a nitrogen atom] . A coloring agent comprising the compound of claim 1 or 2. The coloring agent of claim 4, which further comprises a pigment. The coloring agent according to claim 5, wherein the pigment is at least one selected from the group consisting of a copper halide phthalocyanine pigment and a zinc halide phthalocyanine pigment. The coloring agent according to claim 5 or 6, wherein the pigment is at least one selected from the group consisting of copper chloride phthalocyanine pigment, copper bromide phthalocyanine pigment, and zinc bromide phthalocyanine pigment. The coloring agent according to claim 5 or 6, wherein the pigment is at least one selected from the group consisting of C.I. Pigment Green 36 and C.I. Pigment Green 58. A colored curable resin composition comprising the compound of claim 1 or 2, a resin, a polymerizable compound, and a polymerization initiator. A color filter formed of the colored curable resin composition of claim 9. A liquid crystal display device comprising a color filter as claimed in claim 10.