KR102284012B1 - Curable coloring resin composition - Google Patents

Abstract

(ｉｉ)　식(Ａ1)에서 나타나는 화합물

(ｉｉｉ) 황색 안료, 오렌지색 안료 및 적색 안료로 이루어지는 군으로부터 선택되는 적어도 1종의 안료A colorant (A), a resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E) are included, and the colorant (A) is a group consisting of (a), (a) and (a). It is related with the colored curable resin composition which is a coloring agent containing at least 1 sort(s) selected from.
(ｉ) a compound represented by formula (A2)

(ｉｉ) Compound represented by formula (A1)

(ｉｉｉ) at least one pigment selected from the group consisting of a yellow pigment, an orange pigment, and a red pigment

Description

Colored curable resin composition {CURABLE COLORING RESIN COMPOSITION}

The present invention relates to a colored curable resin composition.

A colored curable resin composition is used for manufacture of the color filter used for display apparatuses, such as a liquid crystal display panel, an electroluminescent panel, and a plasma display panel. It is known for the said colored curable resin composition to use a pigment or dye as a coloring agent (nonpatent literature 1).

Soji Suzuki, “Until an easy-to-understand liquid crystal display is complete”, first edition, Ilgan Kogyo Shimbun, March 2005, p. 112

An object of the present invention is to provide a colored cured product having more excellent brightness and contrast, and a colored curable resin composition from which a color filter containing the same can be obtained.

The present invention provides the following [1] to [9].

[1] A colorant (A), a resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E) are included, and the colorant (A) is (a), (a) and (b). ), a colored curable resin composition comprising at least one selected from the group consisting of.

(ｉ)　Compound represented by formula (A2)

Wherein (A2) of, R ²¹ ~ R ²⁴ are, each independently, a hydrogen atom, a monovalent C 1 -C 8 aliphatic hydrocarbon group or a 6 to 10 carbon atoms in the monovalent aromatic hydrocarbons (? J), the aliphatic hydrocarbon The hydrogen atom contained in the group and the aromatic hydrocarbon group may be substituted with a ^{hydroxyl group, -O 33 or a halogen atom.} R ³³ represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a methyl group.

R ²⁷ represents an ethylene group, a propane-1, 3-diyl group, or a propane-1, 2-diyl group.

R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

n represents the integer of 1-4. When n is an integer of 2 or more, a plurality of R ²⁷ may be the same as or different from each other. ]

(ｉｉ)　A compound represented by formula (A1)

[In formula (A1), R ¹ to R ¹⁸ each independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a nitro group, or -S ₂ R ²⁹ .

R ²⁹ represents -OH, -NRH ³⁰ or -R ³² .

R ³⁰ is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclohexyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, -RS ³¹ -O-R ³² , -R ³¹ -OCO-O- R ³² , -R ³¹ -O-OCO-R ³² , or an aralkyl group having 7 to 10 carbon atoms.

R ³¹ represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R ³² represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a methyl group, an ethyl group, or an amino group.

M ¹ shows a Cr or Co.

Y represents Na or K. ]

(ｉｉｉ) at least one pigment selected from the group consisting of a yellow pigment, an orange pigment, and a red pigment

[2] Coloring agent (A) is colored curable resin composition as described in said [1] which is a coloring agent containing (a), (a), and (a).

[3] Coloring agent (A) is colored curable resin composition as described in said [1] which is a coloring agent containing (a) and (a).

[4] Coloring agent (A) is colored curable resin composition as described in said [1] which is a coloring agent containing (a) and (a).

[5] Pigment is C.I. Pigment Yellow 138, C. I. Pigment Yellow 139, C. I. Pigment Yellow 150, C. I. Pigment Red 177, C. I. Pigment Red 242 and C. I. The colored curable resin composition according to the above [1] to [4], which is at least one selected from the group consisting of Pigment Red 254.

[6] The colored curable resin composition according to the above [1] to [5], further comprising a boron complex (F) or a zinc complex (G).

[7] The colored curable resin composition according to the above [1] to [6], wherein ^{M 1 is Cc.}

[8] A color filter formed of the colored curable resin composition as described in [1] to [7] above.

[9] A display device including the color filter of [8] above.

ADVANTAGE OF THE INVENTION According to the colored curable resin composition of this invention, the color filter more excellent in brightness and contrast can be obtained.

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a photopolymerizable compound (C), a photoinitiator (D) and a solvent (E), wherein the colorant (A) is (a), At least 1 type selected from the group which consists of (a) and (a) is included.

(ｉ)　A compound represented by formula (A2) (hereinafter sometimes referred to as “compound (A2)”)

In formula (A2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, the aliphatic hydrocarbon group and the aromatic hydrogen atoms contained hydrocarbon groups may be substituted, a hydroxy group, -OR ³³ or halogen atoms. R ³³ represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a methyl group.

R ²⁷ represents an ethylene group, a propane-1, 3-diyl group, or a propane-1, 2-diyl group.

R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

n represents the integer of 1-4. When n is an integer of 2 or more, a plurality of R ²⁷ may be the same as or different from each other. ]

(ｉｉ)　A compound represented by formula (A1) (hereinafter referred to as “compound (A1)” in some cases)

[In formula (A1), R ¹ to R ¹⁸ each independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a nitro group, or -S ₂ R ²⁹ .

R ²⁹ represents -OH, -NRH ^30, or -R ³² .

R ³⁰ is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclohexyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, -RS ³¹ -O-R ³² , -R ³¹ -OCO-O- R ³² , -R ³¹ -O-OCO-R ³² , or an aralkyl group having 7 to 10 carbon atoms.

R ³¹ represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R ³² represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a methyl group, an ethyl group, or an amino group.

M ¹ shows a Cr or Co.

Y represents Na or K. ]

(ｉｉｉ) at least one pigment selected from the group consisting of a yellow pigment, an orange pigment, and a red pigment

<Compound (A1)>

^{In R 1} to R ¹⁸ , R ³⁰ , and R ³² in formula (A1), examples of the monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a d-propyl group, an isopropyl group, a d-butyl group, and a dvb group. -Butyl group, ｔｅｒｔ-Butyl group, d-pentyl group, d-hexyl group, d-heptyl group, d-octyl group, decyl group, 1-methylbutyl group, 1, 1, 3, 3-tetramethylbutyl group , 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group, 1, 1, 5, 5-tetramethylhexyl group, etc. are mentioned.

In the formula (A1), 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 db-butyl group, and a bf-butyl group.

In Formula (A1), as a C1-C8 divalent aliphatic hydrocarbon group, a methylene group, an ethylene group, a propane-1, 3-diyl group, a propane-1, 2-diyl group, a butane-1, 4-diyl group , butane-1,3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, etc. are mentioned. .

In Formula (A1), as a cyclohexyl group which may be substituted by the C1-C4 alkyl group, 2-methylcyclohexyl group, 2-ethylcyclohexyl group, 2-propylcyclohexyl group, 2-isopropylcyclohexyl group , 2-butylcyclohexyl group, 4-methylcyclohexyl group, 4-ethylcyclohexyl group, 4-propylcyclohexyl group, 4-isopropylcyclohexyl group, 4-butylcyclohexyl group, etc. are mentioned.

In formula (A1), -R ³¹ -O-R ^{32 is a} methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a propoxyethyl group, a methoxypropyl group, an ethoxypropyl group, Propoxypropyl group, 2-oxo-4-methoxybutyl group, octyloxypropyl group, 3-ethoxypropyl group, 3-(2-ethylhexyloxy)propyl group, etc. are mentioned.

In formula (A1), -R ³¹ -OCO-O-R ³² is a methoxycarbonylmethyl group, a methoxycarbonylethyl group, an ethoxycarbonylmethyl group, an ethoxycarbonylethyl group, a propoxycarbonylmethyl group, and a propoxy group. A carbonylethyl group, a butoxycarbonylmethyl group, a butoxycarbonylethyl group, etc. are mentioned.

In formula (A1), -R ³¹ -O-OCO-R ^{32 is an} acetyloxymethyl group, an acetyloxyethyl group, an ethylcarbonyloxymethyl group, an ethylcarbonyloxyethyl group, a propylcarbonyloxymethyl group, a propylcarbonyloxyethyl group, A butylcarbonyloxymethyl group, a butylcarbonyloxyethyl group, etc. are mentioned.

In formula (A1), -OS ₂ R ^{29 is a} sulfo group; a sulfamoyl group;

N-Methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-GVV-butylsulf Pamoyl group, N-ｔｅｒｔ-butylsulfamoyl group, N-pentylsulfamoyl group, N-(1-ethylpropyl)sulfamoyl group, N-(1, 1-dimethylpropyl)sulfamoyl group, N-(1, 2-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(1-methylbutyl)sulfamoyl group, N-(2-methylbutyl)sulfamoyl group, N-( 3-methylbutyl)sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group, N-(3,3-dimethylbutyl)sulfamo Diary, N-heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(1,4-dimethylpentyl)sulfamoyl group, N-octylsulfamoyl group, N-(2-ethylhexyl) substituted with an aliphatic hydrocarbon group such as a sulfamoyl group, a N-(1,5-dimethyl)hexylsulfamoyl group, a N-(1,1,2,2-tetramethylbutyl)sulfamoyl group, and a N-allylsulfamoyl group Sulfamo diary;

N-(2-methoxyethyl)sulfamoyl group, N-(2-ethoxyethyl)sulfamoyl group, N-(1-methoxypropyl)sulfamoyl group, N-(3-methoxypropyl)sulfamo Diary, N-(3-ethoxypropyl)sulfamoyl group, N-(3-propoxypropyl)sulfamoyl group, N-(3-isopropoxypropyl)sulfamoyl group, N-(3-hexyloxypropyl) -Rs, such as a sulfamoyl group, a N-(2-ethylhexyloxypropyl) sulfamoyl group, a N-(3-n-butoxypropyl) sulfamoyl group, and a N-(4-octyloxybutyl) sulfamoyl group ³¹ -O-R ³² substituted sulfamoyl group;

N-(methoxycarbonylmethyl)sulfamoyl group, N-(methoxycarbonylethyl)sulfamoyl group, N-(ethoxycarbonylmethyl)sulfamoyl group, N-(ethoxycarbonylethyl)sulfamo Diary, N-(propoxycarbonylmethyl)sulfamoyl group, N-(propoxycarbonylethyl)sulfamoyl group, N-(butoxycarbonylmethyl)sulfamoyl group, N-(butoxycarbonylethyl) a sulfamoyl group ^{substituted with -R 31} -OCO-O-R ^{32 such} as a sulfamoyl group;

N-(acetyloxymethyl)sulfamoyl group, N-(acetyloxyethyl)sulfamoyl group, N-(ethylcarbonyloxymethyl)sulfamoyl group, N-(ethylcarbonyloxyethyl)sulfamoyl group, N- (propylcarbonyloxymethyl)sulfamoyl group, N-(propylcarbonyloxyethyl)sulfamoyl group, N-(butylcarbonyloxymethyl)sulfamoyl group, N-(butylcarbonyloxyethyl)sulfamoyl group, etc. sulfamoyl group substituted with -R ³¹ -O-OCO-R ^32;

N-cyclohexylsulfamoyl group, N-(2-methylcyclohexyl)sulfamoyl group, N-(3-methylcyclohexyl)sulfamoyl group, N-(4-methylcyclohexyl)sulfamoyl group, N-( 4-butylcyclohexyl) a sulfamoyl group substituted with a cyclohexyl group having a substituent such as a sulfamoyl group;

N-benzylsulfamoyl group, N-(1-phenylethyl)sulfamoyl group, N-(2-phenylethyl)sulfamoyl group, N-(3-phenylpropyl)sulfamoyl group, N-(4-phenylbutyl) ) sulfamoyl group, N-[2-(2-naphthyl)ethyl]sulfamoyl group, N-[2-(4-methylphenyl)ethyl]sulfamoyl group, N-(3-phenyl-1-propyl)sulf The sulfamoyl group substituted by aralkyl groups, such as pamoyl group and N-(3-phenyl-1-methylpropyl) sulfamoyl group, etc. are mentioned.

Formula (A1) from the, as -SO ₂ R ^32, methyl sulfonyl group, ethyl sulfonyl, propyl sulfonyl, isopropyl sulfonyl, butyl sulfonyl group, n-, sec- butyl sulfonyl group, tert- butyl sulfonyl, pentyl sulfonyl Nyl group, hexylsulfonyl group, heptylsulfonyl group, octylsulfonyl group, 1-methylbutylsulfonyl group, 1, 1, 3, 3-tetramethylbutylsulfonyl group, 1, 5-dimethylhexylsulfonyl group, 1,6-dimethylheptyl group A sulfonyl group, 2-ethylhexylsulfonyl group, 1, 1, 5, 5- tetramethylhexyl sulfonyl group, etc. are mentioned. Among them, a methylsulfonyl group and an ethylsulfonyl group are preferable, and a methylsulfonyl group is more preferable.

Since the tendency that the heat resistance is possible to form a more excellent pattern, etc., of the R ¹ ~ R ^{18, 1} At least it is preferable that a nitro group.

In addition, ^{at least one of R 1} to R ⁵ and at least one of R ⁶ to R ¹⁰ are preferably -OS ₂ R ^{29 .} - When _{having a plurality of SOS 2} R ²⁹ , a plurality of R ²⁹ may be the same as or different from each other.

-SO ₂ R ²⁹ are, -SO ₃ H, -SO ₂ NHR ³⁰ or a -SO ₂ R ^32, preferably from -SO ₂ R ^32. Among them, it is preferably -SO ₂ CH _3.

If the compounds of the invention having a -SO ₂ R ^32, it is preferable that at least one of R ¹¹ ~ R ¹⁴ and at least one of R ¹⁵ ~ R ¹⁸ is -SO ₂ R ^32. - When _{having a plurality of SOS 2} R ³² , a plurality of R ³² may be the same as or different from each other.

Preferable examples of the anion moiety of compound (A1) include anions represented by formulas (1-b1) to (1-b60).

Compound (A1) can be produced by reacting a compound represented by the formula (1d) (hereinafter sometimes referred to as "compound (1d)") with a chromium compound or a cobalt compound in an organic solvent.

[In formula (1d), R ¹ to R ⁵ , R ¹¹ to R ^{14 ,} and R ¹⁹ have the same meanings as described above. ]

Examples of the chromium compound include chromium formate, chromium acetate, chromium chloride, chromium fluoride, and the like, and chromium formate and chromium acetate are preferred. Examples of the cobalt compound include cobalt formic acid and cobalt acetate.

Examples of the organic solvent used in the reaction include dichloromethane, chloroform, tetrahydrofuran, toluene, acetonitrile, and the like, and the amount used is not limited. Reaction temperature is 70-100 degreeC normally. The usage-amount of compound (1l) is 2-4 mol normally with respect to 1 mol of a chromium compound or a cobalt compound.

As a preferable example of compound (1d), the compound represented by Formula (1-a1) - Formula (1-a64) is mentioned.

Compound (1b) is a diazonium salt represented by formula (1b) (hereinafter sometimes referred to as "diazonium salt (1b)") and a pyrazole compound represented by formula (1b) (hereinafter referred to as "pyrazole compound (1b)") ') can be produced by a method of reacting. The diazonium salt (1a) is obtained, for example, by diazotizing an amine represented by the formula (1a) (hereinafter, sometimes referred to as "amine (1a)") with nitrite, nitrite or nitrite ester. .

[In formulas (1a) and (1b), R ¹¹ to R ¹⁴ have the same meanings as above. ^1- A represents an inorganic or organic anion. ]

As said inorganic anion, a fluoride ion, a chloride ion, an embrittlement ion, an iodide ion, a perchlorate ion, a hypochlorite ion etc. are mentioned, for example. Examples of the organic anions, for example, CH ₃ COO ^-, and the like ^-, C ₆ H ₅ COO. Preferably, chloride ion, chwihwamul ion, CH ₃ COO ^-, and the like.

The reaction between the diazonium salt (1d) and the pyrazole compound (1c) is usually carried out in an aqueous solvent, and examples of the aqueous solvent include N-methylpyrrolidone and the like. -5 degreeC - 60 degreeC are preferable and, as for reaction temperature, 0 degreeC - 30 degreeC are more preferable. 1 hour - 12 hours are preferable, and, as for reaction time, 1 hour - 4 hours are more preferable.

[In formula (1b), R ¹ to R ⁵ and R ¹⁹ have the same meaning as above. ]

Compound (1d) to have a -SO ₂ R ^29, a -SO ₂ R ²⁹ can also be produced by using the amine (1a) having a -SO ₂ NHR ³⁰ of the case, -SO ₂ NHR ^30, but, a sulfo group After carrying out the reaction using the amine (1a) having, it is preferable to prepare the sulfo group by sulfonamidation. For example, an azo compound having a sulfo group (hereinafter referred to as "compound (1d)") is synthesized from the compound (1d), and the sulfo group (-S0 ₃ H) is sulfonyl halide with a thionyl halide compound. (-S0 ₂ X; X is a halogen atom) to obtain a sulfonyl halide compound, and then reacting the sulfonyl halide compound with an amine (R ³⁰ N H ₂ ) to sulfonamidize the sulfo group to produce compound (1g). can

Examples of the thionyl halide compound include thionyl fluoride, thionyl chloride, thionyl sulfide, and thionyl iodide, preferably thionyl chloride and thionyl sulfide, and particularly preferably is thionyl chloride. It is preferable that the usage-amount of a thionyl halide is 1-10 mol with respect to 1 mol of compound (1 g). In addition, when water rushes into the reaction system, it is preferable to use an excessive amount of a thionyl halide compound.

The sulfonyl halide is done in a solvent. Examples of the solvent include ethers such as 1,4-dioxane (particularly preferably cyclic ethers); chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, trichloroethylene, Halogenated hydrocarbons, such as perchlorethylene, dichloropropane, amyl chloride, 1,2-dibromoethane, etc. can be used. The amount of the solvent used is, for example, 3 parts by weight or more (preferably 5 parts by weight or more) and 10 parts by weight or less (preferably 8 parts by weight or less) with respect to 1 part by weight of compound (1g).

In addition, in the sulfonyl halide, it is preferable to use both N and N-dialkylformamide (eg, N, N-dimethylformamide, N, N-diethylformamide, etc.). When using N,N-dialkylformamide, the usage-amount is 0.05-1 mol with respect to 1 mol of a thionyl halide compound, for example. When compound (1g) and N,N-dialkylformamide are mixed in advance in a solvent and then a thionyl halide compound is added, heat generation can be suppressed.

The reaction temperature in the sulfonyl halide is, for example, 0°C or higher, preferably 30°C or higher, and 70°C or lower, more preferably 30°C or higher and 60°C or lower. The reaction time is, for example, 0.5 hours or more, preferably 3 hours or more and 8 hours or less, more preferably 3 hours or more and 5 hours or less.

The sulfonyl halide compound prepared as described above ^{may be reacted with an amine (R 30} N H ₂ ) after isolation, or may be reacted with an amine (R ³⁰ N H ₂ ) as it is in the reaction mixture without isolation. In the case of isolation, for example, the reaction mixture and water may be mixed, and the precipitated crystal may be filtered off. Determination of the alcohol obtained sulfonyl halide compound is, prior to reaction with the amine (R ³⁰ NH _2), they may be washed in water and dried as necessary.

Examples of the amine (R ³⁰ NH ₂ ) include n-propylamine, n-butylamine, n-hexylamine, dimethylhexylamine (1,5-dimethylhexylamine, etc.), tetramethylbutylamine (1, 1, 3, 3). -tetramethylbutylamine etc.), ethylhexylamine (2-ethylhexylamine etc.), aminophenylbutane (3-amino-1-phenylbutane etc.), isopropoxypropylamine etc. are contained. The amount of the amine (R ³⁰ N H ₂ ) to be used is 2 moles or more and 10 moles or less, preferably 2 moles or more and 7 moles or less, with respect to 1 mole of the sulfonyl halide compound.

The order of addition of the sulfonyl halide compound and the amine (R ³⁰ N H ₂ ) is not particularly limited, but it is preferable to add (drop) the ^{amine (R 30} N H _{2 ) to the sulfonyl halide compound.} Further, sulfonyl halide compound and a reaction of an amine (R ³⁰ NH ₂₎ is preferably carried out in a solvent. As a solvent, the same solvent as when preparing a sulfonyl halide compound can be used.

In addition, the reaction of the sulfonyl halide compound and the amine (R ³⁰ N H ₂ ) is preferably performed in the presence of a basic catalyst. Examples of the basic catalyst include tertiary amines (aliphatic tertiary amines such as triethylamine and triethanolamine; aromatic tertiary amines such as pyridine) and secondary amines (aliphatic secondary amines such as diethylamine; piperyl) cyclic aliphatic secondary amines such as din); and the like. Among these, tertiary amines, especially aliphatic tertiary amines such as triethylamine are preferable. The amount of the basic catalyst used is 1.1 mol or more and 6 mol or less, preferably 1.1 mol or more and 5 mol or less with respect to 1 mol of the ^{amine (R 30} N H _{2 ).}

^{When adding an amine (R 30} H ₂ ) and a basic catalyst to the sulfonyl halide compound, the addition timing of the basic catalyst is not particularly limited, and either before or after the addition of the ^{amine (R 30} N H _{2 ) may be used,} You may add at the same timing as an amine (R ³⁰ N H _{2 ).} Further, and it may be added after previously mixing with the reactive amine, and the amine (R ³⁰ NH ₂₎ may be added separately.

The reaction temperature of the sulfonyl halide compound and the amine (R ³⁰ N H ₂ ) is, for example, 0°C or higher and 50°C or lower, preferably 0°C or higher and 30°C or lower. In addition, the reaction time is 1 to 5 hours.

The method for obtaining compound (1d), which is the target compound, from the reaction mixture is not particularly limited, and various known methods can be employed. For example, it is preferable to mix the reaction mixture with an acid (eg, acetic acid, etc.) and water, and filter the precipitated crystals. It is preferable to add the reaction mixture to the aqueous solution after preparing an aqueous solution of the acid in advance. The temperature at the time of adding the reaction mixture is preferably 10°C or more and 50°C or less, more preferably 20°C or more and 50°C or less, and still more preferably 20°C or more and 30°C or less. Moreover, after adding the reaction mixture to the aqueous solution of an acid, it is preferable to further stir for about 0.5 to 2 hours at the said temperature. The filtered crystals are preferably washed with water or the like and then dried. Moreover, you may further refine|purify by well-known methods, such as recrystallization, as needed.

<Compound (A2)>

In the formula (A2), examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a d-propyl group, an isopropyl group, a n-butyl group, a db-butyl group, a dbb-butyl group, a d-pentyl group, and a n - A hexyl group, an n-heptyl group, an n-octyl group, etc. are mentioned.

As a C6-C10 monovalent|monohydric aromatic hydrocarbon group in Formula (A2), a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group are mentioned.

As R ³³ , a C1-C4 alkyl group is preferable, a methyl group and an ethyl group are more preferable, and a methyl group is still more preferable.

Since the color density becomes higher, as the R ²¹ ~ R ^24, 1-valent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may contain a hydrogen atom or a substituent is preferable, and more preferably a hydrogen atom or an ethyl.

R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a methyl group. Among them, a hydrogen atom is preferable.

As R ²⁷ , an ethylene group and a propane-1,2-diyl group are preferable, and an ethylene group is more preferable.

As R ^{28 , a} hydrogen atom is preferable.

n is an integer of 1-4, Preferably it is an integer of 2-4, More preferably, it is 3 or 4.

As -(R ²⁷ -O)n-R ²⁸ , since the solubility of compound (A2) in an organic solvent tends to improve, 2-(2-hydroxyethoxy)ethyl group and 2-[2-(2) -Hydroxyethoxy)ethoxy]ethyl group is preferable, and 2-[2-(2-hydroxyethoxy)ethoxy]ethyl group is more preferable.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a cancellation atom, and an iodine atom.

Preferable examples of the cation derived from the xanthene compound in the compound (A2) include cations represented by formulas (1-b1) to (1-b48).

Compound (A2) can be synthesized using a commercially available xanthene dye (eg, "Rhodamin 6G" manufactured by Daoka Chemical Industry Co., Ltd.).

The content of the total of the compound (A1) and the compound (A2) is preferably 1% by weight or more and 99% by weight or less, more preferably 1% by weight or more and 80% by weight or less, and 3% by weight or more in the colorant (A). 70 weight% or less is more preferable.

1:9-9:1 are preferable and, as for the content weight ratio of compound (A1) and compound (A2), 3:7-7:3 are more preferable.

<Pigment>

The colorant (A) is

(ｉｉ) instead of compound (A1) or together with compound (A1),

(a) At least 1 sort(s) of pigment selected from the group which consists of a yellow pigment, an orange pigment, and a red pigment is included.

As a yellow pigment, C.I. Pigment Yellow 1 (Hereinafter, description of C.I. Pigment Yellow is abbreviate|omitted and only the number will be described.), 3, 12, 13, 14, 15, 16, 17. , 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and the like.

As the orange pigment, C. I. Pigment Orange 13 (hereinafter, C. I. Pigment Orange is omitted and only numbers are described.), 31, 36, 38, 40, 42, 43, 51 , 55, 59, 61, 64, 65, 71, 73, and the like.

As a red pigment, C. I. Pigment Red 9 (Hereinafter, description of C. I. Pigment Red is abbreviate|omitted and only the number will be described.), 97, 105, 122, 123, 144, 149, 166. , 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, and the like.

Especially, it is preferable to contain at least 1 sort(s) chosen from C.I. Pigment Yellow 138, 139, 150, and C. I. Pigment Red 177, 242, and 254. By including said pigment, optimization of a transmission spectrum is easy and chemical-resistance becomes favorable.

These pigments may be used individually or in mixture of 2 or more types.

The coloring agent (A) may also contain organic pigments other than a yellow pigment, an orange pigment, and a red pigment, As such other pigment, For example, C. I. Pigment Violet 1 (hereinafter, C. I. Pigment Violet) The description is omitted, and only the number will be described.), and violet pigments such as 19, 23, 29, 32, 36, 38, and the like.

If necessary, the pigment may be subjected to rosin treatment, surface treatment using a pigment derivative introduced with acidic or basic groups, etc., graft treatment to the pigment surface with a polymer compound, etc., atomization treatment by sulfuric acid atomization method, etc., or to remove impurities Washing treatment with an organic solvent, water, etc., removal treatment by an ion exchange method of ionic impurities, etc. may be performed.

The pigment preferably has a uniform particle size.

When the coloring curable resin composition of this invention contains a pigment as a coloring agent (A), it may also contain a pigment dispersing agent. By containing a pigment dispersant and performing a dispersion process, the pigment dispersion liquid of the state in which the pigment was uniformly disperse|distributed in the solution can be obtained.

As said pigment dispersant, surfactant, such as a cationic type, an anionic type, a nonionic type, an amphoteric type, a polyester type, a polyamine type, an acryl type, etc. are mentioned, for example. These pigment dispersants may be used individually or in combination of 2 or more type. As the pigment dispersant, as a trade name, PPA (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by Kyoei Shaka Chemical Co., Ltd.), SPS (manufactured by Zeneca Co., Ltd.), EMOTO P (manufactured by Fine-P), Techno (Co., Ltd. product), DNｉｓｐｅｒｂｙｋ (manufactured by BYK-Chemie), etc. are mentioned.

When using a pigment dispersant, the usage-amount becomes like this with respect to 100 weight part of pigments, Preferably it is 100 weight part, More preferably, they are 5 weight part or more and 50 weight part or less. When the usage-amount of a pigment dispersant exists in said range, there exists a tendency for the pigment dispersion liquid of a uniformly dispersed state to be obtained.

With respect to solid content in colored curable resin composition, content of a coloring agent (A) becomes like this. Preferably it is 5 to 60 weight%, More preferably, it is 8 to 55 weight%, More preferably, it is 10 to 50 weight%. Here, solid content means the sum total of the component except the solvent in colored curable resin composition. When the content of the colorant (A) is in the above range, the color density when a color filter is used is sufficient, and since a required amount of the binder polymer can be contained in the composition, a pattern having sufficient mechanical strength can be formed.

<Other dyes>

The coloring agent (A) may contain a dye different from the compound (A1) and the compound (A2) together. Examples of the dye include oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. For example, dyes classified as dyes in the Color Index (published by The Society of Dyers and Colorists) The compound and the well-known dye described in the dyeing note (dye dyeing yarn) are mentioned.

Specifically, C. I. Solvent Yellow 4 (hereinafter, C. I. Solvent Yellow will be omitted and only numbers will be described.), 14, 15, 23, 24, 38, 62, 63, 68 , 82, 94, 98, 99, 162;

C. I. Solvent Red 45 (hereinafter, C. I. Solvent Red will be omitted and only numbers will be described.), 49, 125, 130;

C. I. Solvent Orange 2 (hereinafter, the description of C. I. Solvent Orange will be omitted and only the number will be described.), 7, 11, 15, 26, 56; C. I. solvent dyes such as;

C. I. Acid Yellow 1 (hereinafter, C. I. Acid Yellow will be omitted and only numbers will be described.), 3, 7, 9, 11, 17, 23, 25, 29, 34 , 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140 , 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212 , 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C. I. Acid Red 1 (hereinafter, C. I. Acid Red will be omitted and only numbers will be described.), 4, 8, 14, 17, 18, 26, 27, 29, 31 , 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138 , 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270 , 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426;

C. I. Acid Orange 6 (hereafter, C. I. Acid Orange will be omitted and only numbers will be described.), 7, 8, 10, 12, 26, 50, 51, 52, 56 , 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

C. I. Acid Violet 6B (Hereinafter, C. I. Acid Violet will be omitted and only numbers will be described.), 7, 9, 17, 19; C. I. Acid dyes such as ,

C. I. Direct Yellow 2 (hereinafter, C. I. Direct Yellow will be omitted and only numbers will be described.), 33, 34, 35, 38, 39, 43, 47, 50, 54, 58 , 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;

C. I. Direct Red 79 (hereinafter, C. I. Direct Red will be omitted and only numbers will be described.), 82, 83, 84, 91, 92, 96, 97, 98, 99, 105 , 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250 ;

C.I. Direct Orange 34 (hereafter, C. I. Direct Orange will be omitted and only numbers will be used.), 39, 41, 46, 50, 52, 56, 57, 61, 64, 65 , 68, 70, 96, 97, 106, 107;

C.I. Direct Violet 47 (hereafter, C. I. Direct Violet will be omitted and only numbers will be described.), 52, 54, 59, 60, 65, 66, 79, 80, 81, 82 , 84, 89, 90, 93, 95, 96, 103, 104;

C.I. Mort Yellow 5 (hereinafter, C. I. Mort Yellow will be omitted and only the number will be described.), 8, 10, 16, 20, 26, 30, 31, 33, 42 , 43, 45, 56, 61, 62, 65;

C. I. All treads 1 (hereinafter, C. I. all treads are omitted and only numbers are written), 2, 3, 4, 9, 11, 12, 14, 17, 18 , 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86 , 88, 90, 94, 95;

C. I. Mort Orange 3 (hereafter, C. I. Mort Orange is omitted and only numbers are written.), 4, 5, 8, 12, 13, 14, 20, 21, 23 , 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

C. I. All Violet 1 (hereafter, C. I. All Violet will be omitted and only numbers will be written), 2, 4, 5, 7, 14, 22, 24, 30, 31 , 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;

<Boron Complex (F)>

The colored curable resin composition of this invention may contain the boron complex (F).

Examples of the boron complex (F) include an anion represented by the following formula (4).

[In formula (4), W ₁ and W ₂ each independently represent a group formed by two monovalent proton-donating substituents releasing a proton. ]

In the formula (4), as a group formed by two monovalent proton-donating substituents releasing protons, catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, and which may have a substituent 2,2'-biphenol, 3-hydroxy-2-naphthoic acid which may have a substituent, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxyl which may have a substituent It is preferable that it is hydroxy-2-naphthoic acid, binaphthol which may have a substituent, salicylic acid which may have a substituent, benzylic acid which may have a substituent, or mandelic acid which may have a substituent.

As salicylic acid which may have the said substituent, for example, salicylic acid, 3-methylsalicylic acid, 3-pipsalicylic acid, 3-pipsalicylic acid, 3-aminosalicylic acid, 3-chlorosalicylic acid, 4-bromosalicylic acid, 3-Methoxysalicylic acid, 3-Nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3,5-di-d-pipsalicylic acid, 3,5-dibromosalicylic acid, 3,5-dichlorosalicylic acid Chilic acid, 3,5,6-trichlorosalicylic acid, 3-hydroxysalicylic acid (2,3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2,4-dihydroxybenzoic acid), 5-hydroxy and hydroxysalicylic acid (2,5-dihydroxybenzoic acid) and 6-hydroxysalicylic acid (2,6-dihydroxybenzoic acid).

As benzylic acid which may have said substituent, for example,

and the like.

As mandelic acid which may have said substituent, for example,

and the like.

Examples of the anion represented by formula (4) include anions represented by the following formulas (A), such as anion (BC-1) to anion (BC-28), and formulas (BC-25) to (BC-28), respectively. anions (BC-25) to anions (BC-28) appearing in ) are mentioned. In addition, the anion (BC-1) to the anion (BC-24) have the substituents shown in Table 1 as _{R 61} , R ₆₂ , R ₆₃ and R _{64 .}

negative ions R ⁶¹ R ⁶² R ⁶³ R ⁶⁴ Anion (BC-1) H H H H Anion (BC-2) 0H H H H Anion (BC-3) H OH H H Anion (BC-4) H H OH H Anion (BC-5) H H H OH Anion (BC-6) C1 H H H Anion (BC-7) H C1 H H Anion (BC-8) H H Cl H Anion (BC-9) H H H Cl Anion (BC-10) Br H H H Anion (BC-11) H Br H H Anion (BC-12) H H Br H Anion (BC-13) H H H Br Anion (BC-14) NH ₂ H H H Anion (BC-15) H NH ₂ H H Anion (BC-16) H H NH ₂ H Anion (BC-17) H H H NH ₂ Anion (BC-18) H tBu H TBu Anion (BC-19) H Cl H Cl Anion (BC-20) H Br H Br Anion (BC-21) H I H I Anion (BC-22) H OH OH H Anion (BC-23) OH H OH H Anion (BC-24) Cl Cl H Cl

Among them, as an anion represented by Formula (4), an anion (BC-1), an anion (BC-2), an anion (BC-3), an anion (BC-25), an anion (BC-26), an anion (BRC) -27) is preferable, the anion (BC-1), the anion (BC-2), and the anion (BC-25) are more preferable, and the anion (BC-1) and the anion (BC-2) are more preferable. If they are these anions, the salt of this invention tends to be excellent in the solubility to organic solvent.

0.1 weight part or more and 20 weight part or less are preferable with respect to 100 weight part of coloring agents (A), and, as for content of boron complex (F), 0.5 weight part or more and 10 weight part or less are more preferable.

<Zinc complex (G)>

The colored curable resin composition of this invention may contain the zinc complex (G) further.

As zinc complex (G), the zinc complex represented by Formula (5) is mentioned, for example.

[In formula (5), R ⁷¹ to R ⁷⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyl group. ]

^{Examples of the alkyl group having 1 to 4 carbon atoms in R 71} to R ⁷⁴ in Formula (5) include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a bb-butyl group, and a can be lifted As a specific example of the zinc complex represented by Formula (5), the complex which has the substituent shown in Table 2 is mentioned. Especially, (5)-18 is preferable at the point which heat resistance improves.

0.1 weight part or more and 30 weight part or less are preferable with respect to 100 weight part of coloring agents (A), and, as for content of a zinc complex (G), 0.5 weight part or more and 15 weight part or less are more preferable.

<Resin B>

The colored curable resin composition of this invention contains resin (B). Although it does not specifically limit as resin (B), It is preferable that it is alkali-soluble resin.

As resin (B), the following resin [K1] - [K4] etc. are mentioned, for example.

[K1] From the group consisting of a monomer (a) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(a)"), and unsaturated carboxylic acid and unsaturated carboxylic acid anhydride A copolymer of at least one selected (b) (hereinafter sometimes referred to as “(b)”).

[K2] (a) and (b), and a monomer (b) copolymerizable with (a) (however, it is different from (a) and (b).) copolymer

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

[K4] Resin obtained by making (a) react with the copolymer of (b) and (b).

When resin (B) contains the structural unit derived from (a), reliability, such as heat resistance and chemical-resistance of the coloring pattern obtained, can be improved more.

(a) is, for example, a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)); It refers to a polymerizable compound having an ethylenically unsaturated bond. As for (a), the monomer which has a C2-C4 cyclic ether and a (meth)acryloyloxy group is preferable.

In addition, in this specification, "(meth)acrylic acid" shows at least 1 sort(s) chosen from the group which consists of acrylic acid and methacrylic acid. Notations such as “(meth)acryloyl” and “(meth)acrylate” have the same meaning.

As (a), for example, a monomer (a1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(a1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond (a2) ( Hereinafter, it may be referred to as "(a2)"), a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (a3) (hereinafter, may be referred to as "(a3)"), and the like.

(a1) is, for example, a monomer (a1-1) having a structure in which a chain olefin is epoxidized (hereinafter sometimes referred to as "(a1-1)"), and a structure in which a cyclic olefin is epoxidized. Monomer (a1-2) (hereinafter sometimes referred to as "(a1-2)") is mentioned.

Examples of (a1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, and α-vinylbenzyl. Glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-a-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α -Methyl-p-vinylbenzylglycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxy) methyl) styrene, 2, 6-bis (glycidyloxymethyl) styrene, 2, 3, 4-tris (glycidyloxymethyl) styrene, 2, 3, 5-tris (glycidyloxymethyl) styrene; 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, etc. are mentioned. can

Examples of (a1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (eg, CELLOXIDE2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl ( Meth) acrylate (for example, Cychroma A400; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cychroma M100; Daicel Chemical Industries, Ltd.) Note) agent), the compound represented by Formula (I), the compound represented by Formula (II), etc. are mentioned.

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

And X ¹ and X ² are, each independently, a single bond, -R ^c - represents a, c ^-R * -O-, * ^-R c -S-, ^-R * c -NH-.

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

* indicates a bond with O. ]

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 d-butyl group, a bb-butyl group, and a bb-butyl group.

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

Examples of R ^a and R ^b, and preferably there may be mentioned a hydrogen atom, methyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, can be cited more preferably a hydrogen atom, a methyl group.

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

Preferred examples of X ¹ and X ² include a single bond, a methylene group, an ethylene group, a *-H ₂ -O- (* represents a bond with O) group, and an *-HC _{2 H 2} -O- group. and, more preferably, a single bond and a *-H _{2 H 2} -O- group are mentioned.

As a compound represented by Formula (I), the compound etc. which are represented by Formula (I-1) - Formula (I-15) are mentioned. Preferably, Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), Formula (I-11) - Formula (I-) 15) can be mentioned. More preferably, a formula (I-1), a formula (I-7), a formula (I-9), and a formula (I-15) are mentioned.

As a compound represented by a formula (IIP), the compound etc. which are represented by a formula (II-1) - a formula (II-15) are mentioned. Preferably, the formula (IIA-1), the formula (IIA-3), the formula (IIA-5), the formula (IA-7), the formula (IO-9), the formula (IA-11) - the formula (IIP-) 15) can be mentioned.

More preferably, the formula (IIA-1), the formula (IIA-7), the formula (II-9), and the formula (IIF-15) are mentioned.

The compound represented by Formula (I) and the compound represented by Formula (II) can be used independently, respectively, respectively. Also, they can be mixed in any ratio. When mixing, the mixing ratio is a molar ratio, preferably formula (I): formula (II), 5:95 to 95:5, more preferably 10:90 to 90:10, particularly preferably 20 :80~80:20.

As a monomer (a2) which has an oxetanyl group and an ethylenically unsaturated bond, the monomer which has an oxetanyl group and a (meth)acryloyloxy group is more preferable. As (a2), 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3 -Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryl Royloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc. are mentioned.

As the monomer (a3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable.

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

As (a), it is preferable that it is (a1) from the point which reliability, such as the heat resistance of the coloring pattern obtained and chemical-resistance, can be improved more. Moreover, (a1-2) is more preferable at the point which is excellent in the storage stability of colored curable resin composition.

Specific examples of (b) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, a-, m-, and v-vinyl benzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3, 4, 5, 6-tetrahydrophthalic acid, 1, 2, 3, 6-tetrahydrophthalic acid, dimethyltetra Unsaturated dicarboxylic acids, such as hydrophthalic acid and 1, 4- cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept -2-ene, 5-carboxy-5-methylbicyclo[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-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, etc. Bicyclo containing a carboxyl group unsaturated compounds;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3, 4, 5, 6-tetrahydrophthalic anhydride, 1, 2, 3, 6-tetrahydrophthalic anhydride, unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.2.1]hept-2-ene anhydride (hymic acid anhydride);

Unsaturated mono[(a) meth)acryloyloxyalkyl]esters;

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

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the point of copolymerization reactivity and the point of solubility to aqueous alkali solution.

As (c), for example, methyl (meth)acrylate, ethyl (meth)acrylate, d-butyl (meth)acrylate, db-butyl (meth)acrylate, dbb-butyl (meth)acrylate, 2 -Ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2 -Methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^{2, 6} ] decan-8-yl (meth)acrylate (in this technical field, as a common name, dicyclopentanyl (meth)acryl ), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acryl (meth)acrylic acid esters such as acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

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

dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;

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[2.2.2.1]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]hept-2-ene , 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.2.1]hept-2-ene, 5, 6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.2.1]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-ethylbi Cyclo[2.2.11]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.11]hept-2-ene, 5-fbf-butoxycarbonylbicyclo[2] .2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.2.1]hept-2 -ene, 5,6-bis(ｔｅｒｔ-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene,5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.2 .1] Bicyclo unsaturated compounds, such as hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl- dicarbonylimide derivatives such as 6-maleimide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridinyl)maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid Vinyl, 1, 3- butadiene, isoprene, 2, 3- dimethyl-1, 3-butadiene, etc. are mentioned.

Among these, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc. are preferable from the point of copolymerization reactivity and heat resistance. .

In resin [K1], it is preferable that the ratio of the structural unit derived from each exists in the following range among all the structural units which comprise resin [K1].

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

Structural unit derived from (b); 2-40 mol% (more preferably 5-35 mol%)

When the ratio of the structural unit of resin [K1] exists in said range, there exists a tendency for storage stability, developability, and solvent resistance of a hardening pattern to become favorable.

Resin [K1] is, for example, the method described in the document "Experimental Method of Polymer Synthesis" (Ozu Takayuki Publishing Co., Ltd. Chemical Dongin 　 1st Edition 1st Printing Published on March 1, 1972) and citations described in the document It can be prepared with reference to the literature.

Specifically, a method of stirring, heating, and keeping warm in deoxidation by injecting predetermined amounts of (a) and (b), a polymerization initiator, a solvent, and the like into a reaction vessel and replacing oxygen with nitrogen is exemplified. In addition, the polymerization initiator, a solvent, etc. used here are not specifically limited, Any thing normally used in the said field|area can be used. For example, as a polymerization initiator, an azo compound (2,2'- azobisisobutyronitrile, 2, 2'- azobis (2, 4- dimethylvaleronitrile), etc.) and an organic peroxide (benzoyl peroxide, etc.) ) is mentioned, and as a solvent, what is necessary is just to melt|dissolve each monomer, The solvent etc. which are mentioned later can be used as a solvent of curable resin composition.

In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was taken out as solid (powder) by methods, such as reprecipitation. In particular, by using the below-mentioned solvent (E) as a solvent at the time of this polymerization, the solution after reaction can be used as it is, and a manufacturing process can be simplified.

In resin [K2], it is preferable that the ratio of the structural unit derived from each exists in the following range among all the structural units which comprise resin [K2].

Structural unit derived from (a); 2-95 mol% (more preferably 5-80 mol%)

Structural unit derived from (b); 2-40 mol% (more preferably 5-35 mol%)

Structural unit derived from (c); 1-65 mol% (more preferably 1-60 mol%)

When the ratio of the structural unit of resin [K2] exists in the said range, there exists a tendency for storage stability, developability, solvent resistance of a cured pattern, heat resistance, and mechanical strength to become favorable.

Resin [K2] can be manufactured similarly to the method described as a manufacturing method of resin [K1], for example.

Specifically, a method of stirring, heating, and keeping warm under deoxidation by introducing predetermined amounts of (a), (b) and (b), a polymerization initiator and a solvent into a reaction vessel, and replacing oxygen with nitrogen. can be heard The obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was taken out as a solid (powder) by methods, such as reprecipitation.

In resin [K3], it is preferable that the ratio of the structural unit derived from each exists in the following range among all the structural units which comprise resin [K3].

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

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

Resin [K3] can be manufactured similarly to the method described as a manufacturing method of resin [K1], for example.

Resin [K4] can be obtained by obtaining a copolymer of (b) and (b), and adding the carboxy group of (b) to a cyclic ether having 2 to 4 carbon atoms in (a).

First, the copolymer of (b) and (b) is produced in the same manner as in the method described as the production method in [K1]. In this case, it is preferable that the ratio of the structural unit derived from each exists in the following range among all the structural units which comprise the copolymer of (b) and (b).

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

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

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

Following the preparation of the copolymer of (b) and (b), the atmosphere in the flask is replaced with air from nitrogen, and (a), a catalyst for reaction of a carboxyl group and a cyclic ether (e.g., tris(dimethylaminomethyl)phenol etc.) to 100 parts by weight of the total amount of (a) to (b), 0.001 to 5 parts by weight, and a polymerization inhibitor (eg, hydroquinone, etc.) to 100 parts by weight of the total amount of (a) to (b) Resin [K4] can be obtained by putting 0.001-5 weight part with respect to a flask, for example, and reacting at 60-130 degreeC for 1-10 hours. Reaction conditions, such as a preparation method, reaction temperature, and time, can take into consideration manufacturing equipment, the amount of heat generated by polymerization, etc., and can be adjusted suitably. Moreover, similarly to polymerization conditions, a preparation method and reaction temperature can be adjusted suitably in consideration of manufacturing equipment, the calorific value by polymerization, etc.

As for the usage-amount of (a) in this case, 5-80 mol% is preferable with respect to (b), More preferably, it is 10-75 mol%, More preferably, it is 15-70 mol%. By setting it as this range, there exists a tendency for the balance of storage stability, developability, solvent resistance, heat resistance, mechanical strength, and a sensitivity to become favorable.

Specifically as resin (B), 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl Resins such as acrylate/(meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/styrene/ (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decylacrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3- Resin [K2] such as (meth)acryloyloxymethyloxetane/(meth)acrylic acid/styrene copolymer; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, etc. Resin [K3]; Resin obtained by adding glycidyl (meth)acrylate to benzyl (meth)acrylate/(meth)acrylic acid copolymer tricyclodecyl(meth)acrylate/styrene/(meth)acrylic acid copolymer Resin, such as resin to which cidyl (meth)acrylate was added, and tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer to which glycidyl (meth)acrylate was added [K4] and the like. Among them, resin [K1] and resin [K2] are preferable, resin [K1] is more preferable, and 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decylacrylate/(meth ) acrylic acid copolymer is more preferred.

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 35,000, particularly preferably 6,000 to 30,000, especially Preferably it is 7,000-28,000. When molecular weight exists in said range, coating-film hardness improves, a residual film rate is also high, the solubility with respect to the developing solution of an unexposed part is favorable, and there exists a tendency for resolution to improve.

The molecular weight distribution [weight average molecular weight (Md)/number average molecular weight (Md)] of resin (B) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The acid value of the resin (B) is preferably 50 to 150 mg-KOH/g, more preferably 60 to 135 mg-KOH/g, and still more preferably 70 to 135 mg-KOH/g. Here, an acid value is a value measured as the quantity (mg) of potassium hydroxide required to neutralize 1 g of resin (B), For example, it can obtain|require by titrating using potassium hydroxide aqueous solution.

With respect to solid content of colored curable resin composition, content of resin (B) becomes like this. Preferably it is 7 to 65 weight%, More preferably, it is 13 to 60 weight%, More preferably, it is 17 to 55 weight%. When content of resin (B) exists in said range, there exists a tendency for a pattern to be formed and also to improve a resolution and a residual film rate.

<Photopolymerizable compound (C)>

The colored curable resin composition of this invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) is a compound that can be polymerized by active radicals and acids generated from the photopolymerization initiator (D) by irradiating light, for example, a compound having a polymerizable ethylenically unsaturated bond; Preferably, a (meth)acrylic acid ester compound is mentioned.

Especially, as a photopolymerizable compound (C), it is preferable that it is a photopolymerizable compound which has three or more ethylenically unsaturated bonds. As such a photopolymerizable compound, for example, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, di Pentaerythritol hexamethacrylate etc. are mentioned. A photopolymerizable compound (C) may be used individually or in combination of 2 or more type.

It is preferable that content of a photopolymerizable compound (C) is 7 to 65 weight% with respect to solid content of colored curable resin composition, More preferably, it is 13 to 60 weight%, More preferably, it is 17 to 55 weight%. . When the content of the photopolymerizable compound (C) is in the above range, curing occurs sufficiently, the film thickness ratio before and after development is improved, and undercuts are less likely to enter the pattern, which is preferable because adhesion tends to be good.

<Photoinitiator (D)>

The colored curable resin composition of this invention contains a photoinitiator (D).

As said photoinitiator (D), if it is a compound which generate|occur|produces an active radical, an acid, etc. by the action of light, and initiates polymerization, it will not specifically limit, A well-known polymerization initiator can be used.

The photoinitiator (D) is preferably a compound that generates an active radical by the action of light, and at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an oxime compound, and a biimidazole compound. A photoinitiator containing a species is more preferable, and the photoinitiator containing an oxime compound is still more preferable.

Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, and 2-dimethylamino-1-(4-morpholinophenyl). )-2-benzylbutan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-(4-methylphenylmethyl)butan-1-one, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketones and oligomers of 2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, preferably 2-methyl-2-morpholino- 1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, etc. are mentioned. You may use commercial items, such as Irgacure 369 and 907 (above, the BFA company make).

Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4). -Methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl) To methyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl) tenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2, 4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6 -[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc. are mentioned.

As an acylphosphine oxide compound, 2, 4, 6- trimethylbenzoyl diphenyl phosphine oxide etc. are mentioned. You may use commercial items, such as Irgacure 819 (made by BAS).

Examples of the oxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one- 2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9- ethyl-6-b2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoylb-9H-carbazol-3-yl]ethane-1-imine; there is. You may use commercial items, such as Irgacure OB-01, OB-02 (above, the BFA company make), and N-1919 (made by ADSEA company).

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)- 4,4',5,5'-tetraphenylbiimidazole (For example, refer to Japanese Patent Application Laid-Open Nos. 6-75372, 6-75373, etc.), 2,2'-bis(2-chloro Phenyl)-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'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4 ', 5, 5'-tetra(trialkoxyphenyl)biimidazole (For example, refer to Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), 4, 4', 5, 5' - The imidazole compound in which the phenyl group is substituted by the carboalkoxy group (For example, refer to Unexamined-Japanese-Patent No. 7-10913 etc.) etc. are mentioned. Preferably 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4 ',5,5'-tetraphenylbiimidazole and 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole are mentioned.

Examples of the acid generator that generates an acid by light include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-acetoxyphenyldimethyl Sulfonium p-toluenesulfonate, 4-acetoxyphenyl Emethyl E benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, di Onium salts, such as phenyliodonium p-toluenesulfonate and diphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate, etc. are mentioned.

The photoinitiator (D) may be a compound which simultaneously generates an active radical and an acid by light, such as a triazine compound.

Moreover, as a photoinitiator (D), Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, p-benzoyl methyl benzoate, 4- Phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(ｔｅｒｔ-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc. Benzophenone compounds; Quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound, etc. can It is preferable to use these in combination with the below-mentioned photoinitiation adjuvant (D1) (especially amines).

To [ content of a photoinitiator (D) / 100 weight part of total amounts of resin (B) and a photopolymerizable compound (C)), Preferably it is 0.1-30 weight part, More preferably, it is 1-20 weight part. When content of a photoinitiator exists in said range, it will become highly sensitive, exposure time will be shortened and productivity will improve.

<Photopolymerization initiation aid (D1)>

The photopolymerization start adjuvant (D1) may further be contained in the colored curable resin composition of this invention. The photopolymerization initiation adjuvant (D1) is usually used in combination with a photoinitiator (D), and is a compound or sensitizer used to promote polymerization of a photopolymerizable compound whose polymerization is initiated by the photoinitiator.

As a photoinitiation adjuvant (D1), an amine compound, an alkoxyanthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylamino methyl benzoate, 4-dimethylamino ethyl benzoate, 4-dimethylamino isoamyl benzoate, 2-dimethylaminoethyl benzoate, and 4-dimethylamino 2-ethylhexyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4 '-bis(ethylmethylamino)benzophenone etc. are mentioned, Especially, 4, 4'-bis(diethylamino)benzophenone is preferable. You may use commercial items, such as EFA-F (made by Hodogaya Chemical Industry Co., Ltd.).

Examples of the alkoxyanthracene compound include 9, 10-dimethoxyanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9, 10-diethoxyanthracene, and 9, 10-dibu Toxanthracene, 2-ethyl-9, 10-dibutoxyanthracene, etc. are mentioned.

As a thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy acid Oxanthone etc. are mentioned.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenyl Sulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. are mentioned.

A photoinitiation adjuvant (D1) may be used individually or in combination of 2 or more type.

When using these photopolymerization initiation adjuvant (D1), the usage-amount with respect to 100 weight part of total amounts of resin (B) and polymeric compound (C), Preferably it is 0.01-50 weight part, More preferably, 0.1 ~40 parts by weight. Moreover, with respect to 1 mol of a photoinitiator (D), Preferably it is 0.01-10 mol, More preferably, it is 0.01-5 mol. When the amount of the polymerization initiation auxiliary (D1) is in this range, a pattern can be formed with high sensitivity and the productivity of the pattern tends to improve.

<Solvent (E)>

The colored curable resin composition of this invention contains a solvent (E).

The solvent (E) is not specifically limited, The solvent normally used in the said field|area can be used. For example, ester solvents (solvents containing -OCO-), ether solvents other than ester solvents (solvents containing -O-), ether ester solvents (solvents containing -OCO- and -O-), esters It can be used by selecting from solvents other than ketone solvents (solvents containing -OC-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

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

As the ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol 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-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetol, methylanisole and the like.

Examples of the ether ester solvent include methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, and methyl 3-ethoxypropionate. , 3-ethyl ethoxypropionate, 2-methoxymethylpropionate, 2-methoxyethylpropionate, 2-methoxypropionate propyl, 2-ethoxypropionate methyl, 2-ethoxypropionate ethyl, 2-methoxy-2- Methyl methyl propionate, 2-ethoxy-2-methyl ethyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono and propyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

As a ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclo pentanone, cyclohexanone, isophorone, and the like.

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

As an aromatic hydrocarbon solvent, benzene, toluene, xylene, mesitylene, etc. are mentioned.

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

These solvents may be used individually or in combination of 2 or more types.

Among the above solvents, from the viewpoint of applicability and drying properties, organic solvents having a boiling point of 120°C or more and 180°C or less in 1 μm are preferable. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy -4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone, etc. are preferable, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethyl lactate, 3-ethoxypropionic acid Ethyl etc. are more preferable. When these solvents are included, it is excellent in the flatness at the time of application|coating.

With respect to colored curable resin composition, content of the solvent (E) in colored curable resin composition becomes like this. Preferably it is 70 to 95 weight%, More preferably, it is 75 to 92 weight%. In other words, solid content of colored curable resin composition becomes like this. Preferably it is 5 to 30 weight%, More preferably, it is 8 to 25 weight%. When the content of the solvent (E) is in the above range, flatness at the time of application becomes good, and since color density does not run short when a color filter is formed, there exists a tendency for a display characteristic to become favorable.

<Surfactant (H)>

The colored curable resin composition of the present invention may further contain a surfactant (H).

As surfactant (H), a silicone type surfactant, a fluorine type surfactant, the silicone type surfactant which has a fluorine atom, etc. are mentioned. These may have a polymerizable group in a side chain.

As a silicone type surfactant, the surfactant etc. which have a siloxane bond are mentioned. Specifically, soil urea silicon DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, polyether modified silicone oil SH8400 (trade name: Sat urea, Dow Corning Co., Ltd. No.), KP321, KP322 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu chemical Co., Ltd. No.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (Momentive, performance, meote Materials, Japan concurrence priest ) and the like.

As said fluorine-type surfactant, the surfactant etc. which have a fluorocarbon chain are mentioned. Specifically, FLUORAD (trade name) FFC430, East FFC431 (manufactured by SUMITOMO 3M Co., Ltd.), MEGAFAC (brand name) F142D, East F171, East F172, East F173, East F177, East F183, East R30, East 718 KS (manufactured by DIRC), FTOP (trade name) EF301, Dong EFM 303, Dong EFM351, Dong EFM352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (trade name) SCS105 (trade name) SCS 105 (Asa SOC105) Glass Co., Ltd. product), E5844 (made by Daikin Fine Chemical Research Institute), etc. are mentioned.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples thereof include MEGAFAC (registered trademark) R08, BLC20, F475, F477, and F443 (manufactured by DLC Co., Ltd.).

These surfactants may be used individually or in combination of 2 or more types.

With respect to colored curable resin composition, content of surfactant (H) becomes like this. Preferably they are 0.001 weight% or more and 0.2 weight% or less, Preferably they are 0.002 weight% or more and 0.1 weight% or less, More preferably, they are 0.01 weight% or more and 0.05 weight % or less. When content of surfactant (H) exists in said range, the flatness of a coating film can be made favorable.

If the colored curable resin composition of the present invention is a composition comprising a colorant (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photoinitiator (D), a solvent (E), and a surfactant (H), it is applied It is excellent in property, and it is possible to obtain a coloring pattern excellent in solvent resistance and spectroscopy.

The colored curable resin composition of this invention may contain various additives, such as a filler, another high molecular compound, an adhesion promoter, antioxidant, a ultraviolet absorber, a light stabilizer, and a chain transfer agent, as needed.

As a method of forming a colored pattern using the colored curable resin composition of the present invention, for example, the colored curable resin composition of the present invention is applied to a substrate or other resin layer (for example, another colored curable resin composition layer formed previously on the substrate, etc.) ), a method of forming a colored layer by removing/drying volatile components such as a solvent, exposing the colored layer through a photomask to develop, and a method using an inkjet device that does not require a photolithography method, etc. are mentioned. .

The film thickness of the coating film in this case is not specifically limited, It can adjust suitably according to the material used, a use, etc., For example, 0.1-30 micrometers, Preferably it is 1-20 micrometers, More preferably, it is 1-6 micrometers.

Examples of the coating method of the colored cured photoresin composition include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CPA coating method, and a die coating method. Moreover, you may apply|coat using coaters, such as a dip coater, a bar coater, a spin coater, a slit & spin coater, a slit coater (it may also call a die coater, a curtain flow coater, and a spinless coater).

As for the removal/drying of a solvent, natural drying, ventilation drying, reduced pressure drying, heat drying etc. are mentioned, for example. 10-120 degreeC is preferable and, as for specific drying temperature, 25-100 degreeC is more preferable.

10 second - 60 minutes are preferable, and, as for drying time, 30 second - 30 minutes are more preferable.

It is preferable to perform reduced pressure drying in the range of 20-25 degreeC under the pressure of 50-150Pa.

The coating film after drying is exposed through a photomask for forming the target pattern.

The pattern shape on the photomask at this time is not specifically limited, The pattern shape according to the intended use is used.

As a light source used for exposure, the light source which generate|occur|produces the light of the wavelength of 250-450 nm is preferable. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned, and it is cut using a filter which cuts a specific wavelength range, or is selectively taken out using a bandpass filter which takes out a specific wavelength range. Alternatively, exposure may be carried out.

It is preferable to use a device such as a mask aligner or a stepper because parallel rays can be uniformly irradiated to the entire exposure surface or the mask and the substrate can be precisely aligned.

After exposure, a pattern can be obtained by making it contact with a developing solution, dissolving a predetermined part, for example, an unexposed part, and developing. As a developing solution, the aqueous solution of an alkaline compound (potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide, etc.) etc. are mentioned. The developing solution may contain a surfactant.

The developing method may be any of a paddle method, a dipping method, and a spray method. Moreover, you may incline a board|substrate at arbitrary angles at the time of image development. It is preferable to wash with water after image development.

Moreover, you may post-baking as needed. As for a post-baking, 150-230 degreeC and the range for 10-240 minutes are preferable, for example.

ADVANTAGE OF THE INVENTION According to the colored curable resin composition of this invention, heat resistance and light resistance can obtain a favorable coating film, a pattern, and a high-quality color filter. In addition, display devices having these color filters or patterns as part of their constituent parts, for example, known liquid crystal display devices, organic EL devices, solid-state imaging devices, and other devices related to various colored images, are well-known. available in the form.

Next, the present invention will be more specifically described by way of Examples. In the examples, % and parts indicating the content or the amount used are by weight unless otherwise specified.

In the following, the structure of the compound was confirmed by gravimetric analysis (LLC;

[Synthesis Example 1]

After adding 65 parts of water to 7.5 parts of 2-amino-4-methylsulfonyl-6-nitrophenol (CASN04-5), 1.3 parts of sodium hydroxide was added and it was made to melt|dissolve. Under ice-cooling, 6.1 parts of a 35% sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) aqueous solution was added, and then, 19.4 parts of 35% hydrochloric acid was added little by little to dissolve and stirred for 2 hours, followed by diazo A suspension containing an nium salt was obtained. Next, an aqueous solution prepared by dissolving 5.6 parts of amide sulfuric acid (manufactured by Wagwang 純藥工業) in 26 parts of water was slowly added to inactivate excess sodium nitrite.

Next, 5.6 parts of 3-methyl-1-phenyl-5-pyrazolone (manufactured by Wakotoshi Co., Ltd.) was suspended in 70 parts of water, and pH was adjusted to 8.0 using sodium hydroxide. The suspension containing the said diazonium salt was dripped here over 15 minutes, adding 10% sodium hydroxide solution suitably so that pH may be stabilized in the range of 7 to 7.5. A yellow suspension was obtained by further stirring for 30 minutes after completion|finish of dripping. It stirred for 1 hour. The yellow solid obtained by filtration was dried at 60 degreeC under reduced pressure, and 11.7 parts (yield 87%) of the compound represented by Formula (p-2) was obtained.

10 parts of the compound of formula (p-2) was dissolved in 100 parts of dimethylformamide (manufactured by Tokyo Kasei Kogyo Co., Ltd.), and chromium ammonium sulfate (IIP) dodecahydrate (Wawang Co., Ltd.) ) and 1.1 parts of sodium acetate (manufactured by 和光純藥工業) were added, followed by heating and refluxing for 4 and a half hours. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline, and the red-orange solid obtained after filtration was dried at 60°C to obtain 13.6 parts (yield 63%) of the compound represented by the formula (f-2).

[Synthesis Example 2]

In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was flowed at 0.02 L/min to make a nitrogen atmosphere, and 305 parts of propylene glycol monomethyl ether acetate was added, and stirred at 70 ° C. heated up to Next, 60 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (a compound represented by the formula (I-1) and a compound represented by the formula (II-1), Mix in a molar ratio of 50:50.) 440 parts of propylene glycol monomethyl ether acetate are dissolved in 140 parts of propylene glycol monomethyl ether acetate to prepare a solution, and the solution is dropped into a flask kept at 70°C over 4 hours using a dripping tap. did.

On the other hand, a solution obtained by dissolving 30 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in 225 parts of propylene glycol monomethyl ether acetate was added dropwise into the flask over 4 hours using another dropping screw. . After dropping of the solution of the polymerization initiator was completed, the temperature was maintained at 70 ° C. for 4 hours, and then cooled to room temperature, the weight average molecular weight (Ml) was 9. 1 × 10 ³ , the molecular weight distribution was 2.16, the solid content was 34.8%, The acid value in terms of solid content obtained a resin (B1) solution of 81 mg-KOP/g. Resin (B1) has the structural unit shown below.

The measurement of the weight average molecular weight (Md) and number average molecular weight (Mg) of resin obtained by the synthesis example was performed on the following conditions using the GPC method.

Apparatus; K2479 (manufactured by Shimadzu Corporation)

Column; SHD

Column temperature; 40°C

Solvent; THF (tetrahydrofuran)

Flow rate: 1. 0mL/mｉｎ

Detector; Standard substance for RIA calibration; TSTS;

Ratio (Md/Mn) of the weight average molecular weight and number average molecular weight of polystyrene conversion obtained above was made into molecular weight distribution.

Example

Each component was mixed so that it might become a composition shown in Table 3, and colored curable resin composition was obtained.

unit (parts) Example 1 Example 2 Comparative Example 1 compound (A2) 1-ｃ23 4.2 3.9 compound (A3) 11.3 compound (A1) ｚ-2 1.1 pigment ¹⁾ 41.1 31.1 75.6 Boron complex (F) BC-2 2.1 2.1 pigment dispersant 40.0 50.0 32.8 Resin (B) 15.7 18.7 50.0 Photopolymerizable compound (C) 50.0 50.0 50.0 Photoinitiator (D) 13.0 Photopolymerization initiation aid (D1) 2.0 Photoinitiator (D2) 8.7 8.7 Solvent (E) E-1 ²⁾ 358.3 468.3 1117.5 E-2 6.3 6.3 13.1 E-3 95.2 195.2 199.5

^{1) The} pigment was mixed with a pigment dispersant and propylene glycol monomethyl ether acetate in the amount described in column ^{E-1 2), and dispersed in advance.}

²⁾ E-1 ²⁾ represents the sum total of propylene glycol monomethyl ether acetate content.

In addition, in Table 3, each component shows the following. In addition, resin (B) showed the weight part in conversion of solid content.

Compound (A2): The compound represented by formula (1-#23)

Compound A1: A compound represented by formula (ｚ-2)

Compound (A3): the following formula

A pigment: C. I. Pigment red 254

Resin (B): Resin B1

Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAAA (registered trademark) and DPS; Nippon Kayaku Co., Ltd.)

Photoinitiator (D): 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (Irgacure 369; manufactured by BPS)

Polymerization initiation adjuvant (D1): 2,4-diethylthioxanthone (KAAAAA (registered trademark);

Polymerization initiator (D2): 　OXE01 (manufactured by BASF)

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

Solvent (E): E-2: Propylene glycol monomethyl ether

Solvent (E): E-3: diacetone alcohol

[Production of a coloring pattern]

On a 2-inch square glass substrate (Eagle XG; the Corning company make), after apply|coating colored curable resin composition by the spin coating method, it prebaked at 100 degreeC for 3 minute(s), and the composition layer was formed. After standing to cool, the interval between the composition layer on the substrate and the quartz glass photomask having a pattern is 100 μm, and an exposure machine (TEM-150RS; TOPCON Co., Ltd.) is used in an atmospheric atmosphere at 150 m/vm ² . It was irradiated with light at an exposure dose (based on 365 nm). In addition, as a photomask, the mask in which the 100 micrometers line-and-space pattern was formed was used. After light irradiation, the coating film was developed by immersion in an aqueous developer solution containing 0.12% of a nonionic surfactant and 2% of sodium carbonate at 23°C for 80 seconds, and after washing with water, post-baking at 230°C for 20 minutes in an oven to color got a pattern.

[Film thickness measurement]

About the obtained coloring pattern, the film thickness was measured using the film-thickness measuring apparatus (DMP3; Nippon Vacuum Technology Co., Ltd. product). A result is shown in Table 3.

[Chromaticity evaluation]

About the obtained coloring pattern on the glass substrate, the spectroscopy is measured using the colorimeter (OSPS-200; manufactured by Olympus Co., Ltd.), and the X-chromaticity coordinates of the C-I (X-chromaticity , g) and tristimulus values (三刺激値) (Y) were measured. It indicates that the higher the value of Y, the higher the brightness. The results are shown in Table 3.

[Contrast Evaluation]

It exposed without using a photomask, and except not developing, operation similar to formation of a coloring pattern was performed, and the colored coating film on a glass substrate was produced. About the obtained colored coating film on the glass substrate, using a contrast colorimeter (TC-1; Tsubosaka Electric Co., Ltd. make, detector; BMC-5A, light source; F-10), the blank value was set to 30000, and the contrast was was measured. What inserted the colored coating film on a glass substrate with the polarizing film (POS-38S; made by Luceo Corporation) was made into the measurement sample. A result is shown in Table 4.

film thickness chromaticity Ｙ contrast (μm) ｘ ｙ Example 1 2.3 0.661 0.323 18.2 14700 Example 2 2.3 0.661 0.323 18.5 12700 Comparative Example 1 2.3 0.661 0.323 17.5 8920

ADVANTAGE OF THE INVENTION According to the colored curable resin composition of this invention, the color filter more excellent in brightness and contrast can be manufactured.

Claims (9)

a colorant (A), a resin (B), a photopolymerizable compound (C), a photoinitiator (D) and a solvent (E);
It further comprises a boron complex (F) of the following (iv),
The colorant (A) includes the following (i), and is a colorant comprising at least one selected from the group consisting of the following (ii) and (iii), a colored curable resin composition.

(i) the cation represented by the formula (A2)

[In the formula (A2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms,
Hydrogen atoms contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group ^{may be substituted with a hydroxyl group, -O 33} or a halogen atom, wherein R ³³ represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms,
R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a methyl group,
R ²⁷ represents an ethylene group, a propane-1, 3-diyl group, or a propane-1, 2-diyl group,
R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
n represents an integer of 1 to 4, and when n is an integer of 2 or more, a plurality of r ²⁷ may be the same as or different from each other]

(ｉｉ) Compound represented by formula (A1)

[In formula (A1), R ¹ to R ¹⁸ each independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a nitro group, or -OS ₂ R ²⁹ ;
R ²⁹ represents -OH, -NRH ³⁰ or -R ³² ;
R ³⁰ is a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclohexyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, -RS ³¹ -O-R ³² , -R ³¹ -OCO-O- R ³² , -R ³¹ -O-OCO-R ³² , or an aralkyl group having 7 to 10 carbon atoms,
R ³¹ represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms,
R ³² represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms,
R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a methyl group, an ethyl group, or an amino group;
M ¹ represents C c or C c,
Y stands for N or K]

(ｉｉｉ) at least one pigment selected from the group consisting of a yellow pigment, an orange pigment, and a red pigment

(ｉv) Boron complex represented by formula (4)

[In Formula (4), W ₁ and W ₂ each independently represent a group formed by two monovalent proton-donating substituents releasing protons.] According to claim 1,
The said coloring agent (A) is a coloring agent containing (a), (a), and (a) A colored curable resin composition. According to claim 1,
The said coloring agent (A) is a coloring agent containing (a) and (a), The colored curable resin composition. According to claim 1,
The said coloring agent (A) is a coloring agent containing (a) and (a) A colored curable resin composition. According to claim 1,
The pigments include C.I. Pigment Yellow 138, C. I. Pigment Yellow 139, C. I. Pigment Yellow 150, C. I. Pigment Red 177, C. I. Pigment Red 242 and C. I. The colored curable resin composition which is at least 1 sort(s) chosen from the group which consists of pigment red 254. delete According to claim 1,
Wherein M is colored curable resin composition ¹ is Cr. A color filter formed of the colored curable resin composition according to any one of claims 1 to 5 and 7. A display device comprising the color filter of claim 8 .