TWI617882B - Coloring curable resin composition - Google Patents

Abstract

The present invention provides a colored curable resin composition containing a colorant (A), a resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), wherein The colorant (A) is a coloring agent containing at least one selected from the group consisting of (i), (ii), and (iii).

(i) a compound represented by formula (A2)

(ii) a compound represented by formula (A1)

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

Description

Colored curable resin composition

The present invention relates to a colored curable resin composition.

The colored curable resin composition is used for the production of a color filter used in a display device such as a liquid crystal display panel, an electroluminescence (EL) panel, or a plasma display panel. In the colored curable resin composition, a pigment or a dye is known as a colorant (Non-Patent Document 1).

[Previous Technical Literature]

(Non-patent literature)

Non-Patent Document 1: Suzuki is eighty-two, " liquid crystal (LCD display that can be easily understood), first edition, Nikkan Kogyo Shimbun, March 2005, 112 pages

An object of the present invention is to provide a colored curable resin composition which is capable of obtaining a colored cured product having superior brightness and contrast and a color filter containing the same.

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

[1] A colored curable resin composition containing a colorant (A), a resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), and a colorant (A) Is a coloring agent containing at least one selected from the group consisting of (i), (ii), and (iii).

(i) a compound represented by 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, in the aliphatic hydrocarbon group. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a hydroxyl group, -OR 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 ethyl 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.

The n system represents an integer of 1 to 4. When n is an integer of 2 or more, the plural R ²⁷ may be the same or different from each other. ]

(ii) a compound represented by formula (A1) In the 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 -SO ₂ R ²⁹ .

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

R ³⁰ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R ³¹ -OR ³² , -R ³¹ -CO- OR ³² , -R ³¹ -O-CO-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 amine group.

M ¹ represents Cr or Co.

Y represents Na or K. ]

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

[2] The colored curable resin composition as described in [1], wherein The toner (A) is a coloring agent containing (i), (ii), and (iii).

[3] The colored curable resin composition according to [1], wherein the colorant (A) is a coloring agent containing (i) and (ii).

[4] The colored curable resin composition according to [1], wherein the colorant (A) is a coloring agent containing (i) and (iii).

[5] The colored curable resin composition according to any one of [1] to [4] wherein the pigment is selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Red 177, At least one of the group consisting of CI Pigment Red 242 and CI Pigment Red 254.

[6] The colored curable resin composition according to any one of [1] to [5], which further comprises a boron complex (F) or a zinc complex (G).

[7] of [1] to [6] the colored curable resin composition according to any one, wherein, M ¹ based Cr.

[8] A color filter comprising the colored curable resin composition according to any one of [1] to [7].

[9] A display device comprising the color filter according to [8].

According to the colored curable resin composition of the present invention, a color filter excellent in brightness and contrast can be obtained.

[Best Mode for Carrying Out the Invention]

The colored curable resin composition of the present invention contains a toner (A), a resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), and the color former (A) contains a component selected from the group consisting of (i) and (ii) And (iii) at least one of the groups formed.

(i) a compound represented by the formula (A2) (hereinafter sometimes referred to as "compound (A2)")

In the 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, in the aliphatic group. The hydrocarbon group and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted by a hydroxyl group, -OR 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 ethyl 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.

The n system represents an integer of 1 to 4. When n is an integer of 2 or more, the plural R ²⁷ systems may be the same or different from each other. ]

(ii) a compound represented by the formula (A1) (hereinafter sometimes referred to as "compound (A1)")

In the 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 -SO ₂ R ²⁹ .

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

R ³⁰ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms, -R ³¹ -OR ³² , -R ³¹ -CO- OR ³² , -R ³¹ -O-CO-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 amine group.

M ¹ represents Cr or Co.

Y represents Na or K. ]

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

<Compound (A1)>

In the examples of R ¹ to R ¹⁸ , R ³⁰ and R ³² in the formula (A1), the monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms may, for example, be a methyl group, an ethyl group, an n-propyl group or an isopropyl group. , n-butyl, di-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, decyl, 1-methylbutyl, 1,1 , 3,3-tetramethylbutyl, 1,5-dimethylhexyl, 1,6-dimethylheptyl, 2-ethylhexyl and 1,1,5,5-tetramethylhexyl, and the like.

In the formula (A1), the alkyl group having 1 to 4 carbon atoms may, for example, be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a secondary-butyl group or a tertiary-butyl group. Wait.

In the formula (A1), the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms may, for example, be a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group or a butane. -1,4-diyl, butane-1,3-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane -1,8-diyl, etc.

In the formula (A1), a cyclohexyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms may, for example, be 2-methylcyclohexyl, 2-ethylcyclohexyl, 2-propylcyclohexyl or 2-iso Propylcyclohexyl, 2-butylcyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 4-propylcyclohexyl, 4-isopropylcyclohexyl, 4-butylcyclohexyl, and the like.

In the formula (A1), -R ³¹ -OR ³² may, for example, be a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group or a propoxy group B. Base, methoxypropyl, ethoxypropyl, propoxypropyl, 2-oxo-4-methoxybutyl, octyloxypropyl, 3-ethoxypropyl, 3-(2 -ethylhexyloxy)propyl and the like.

In the formula (A1), -R ³¹ -CO-OR ³² may, for example, be a methoxycarbonylmethyl group, a methoxycarbonylethyl group, an ethoxycarbonylmethyl group, an ethoxycarbonylethyl group or a propoxycarbonyl group. Methyl, propoxycarbonylethyl, butoxycarbonylmethyl, butoxycarbonylethyl and the like.

In the formula (A1), -R ³¹ -O-CO-R ³² may, for example, be an ethyloxymethyl group, an ethyl ethoxyethyl group, an ethylcarbonyloxymethyl group, an ethylcarbonyloxyethyl group or a propyl group. A carbonyloxymethyl group, a propylcarbonyloxyethyl group, a butylcarbonyloxymethyl group, a butylcarbonyloxyethyl group or the like.

In the formula (A1), -SO ₂ R ²⁹ may, for example, be a sulfo group; an aminosulfonyl group; an N-methylaminosulfonyl group, an N-ethylaminosulfonyl group, or an N-propylaminosulfonate. Sulfhydryl, N-isopropylaminosulfonyl, N-butylaminosulfonyl, N-isobutylaminosulfonyl, N-di-butylaminosulfonyl, N- Tertiary-butylaminosulfonyl, N-pentylaminosulfonyl, N-(1-ethylpropyl)aminosulfonyl, N-(1,1-dimethylpropyl) Aminosulfonyl, N-(1,2-dimethylpropyl)aminosulfonyl, N-(2,2-dimethylpropyl)aminosulfonyl, N-(1-A Butyl)aminosulfonyl, N-(2-methylbutyl)aminosulfonyl, N-(3-methylbutyl)aminosulfonyl, N-cyclopentylaminosulfonate Anthracenyl, N-hexylaminosulfonyl, N-(1,3-dimethylbutyl)aminosulfonyl, N-(3,3-dimethylbutyl)aminosulfonyl, N-heptylaminosulfonyl, N-(1-methylhexyl)aminosulfonyl, N-(1,4-dimethylpentyl)aminosulfonyl, N-octylamino Sulfonyl, N-(2-ethylhexyl)aminosulfonyl, N-(1,5-dimethyl)hexylaminosulfonyl, N-(1,1,2,2-tetra Alkyl butyl sulfonyl, N-propenyl sulfonyl Aminosulfonyl group substituted by an aliphatic hydrocarbon group; N-(2-methoxyethyl)aminosulfonyl, N-(2-ethoxyethyl)aminosulfonyl, N- (1-methoxypropyl)aminosulfonyl, N-(3-methoxypropyl)aminosulfonyl, N-(3-ethoxypropyl)aminosulfonyl, N -(3-propoxypropyl)aminosulfonyl, N-(3-isopropoxypropyl)aminosulfonyl, N-(3-hexyloxypropyl)aminosulfonyl , N-(2-ethylhexyloxypropyl)aminosulfonyl, N-(3-tert-butoxypropyl)aminosulfonyl, N-(4-octyloxybutyl) An aminosulfonyl group substituted with -R ³¹ -OR ³² such as an aminosulfonyl group; N-(methoxycarbonylmethyl)aminosulfonyl, N-(methoxycarbonylethyl)amine Sulfosyl, N-(ethoxycarbonylmethyl)aminosulfonyl, N-(ethoxycarbonylethyl)aminosulfonyl, N-(propoxycarbonylmethyl)amine sulfonate Mercapto, N-(propoxycarbonylethyl)aminosulfonyl, N-(butoxycarbonylmethyl)aminosulfonyl, N-(butoxycarbonylethyl)aminosulfonyl etc. -R ³¹ -CO-OR ³² group of the sulfo-substituted acyl; N-(acetyl yloxymethyl) sulfo acyl group, N- (acetyl methoxyethyl) amine Sulfonyl, N-(ethylcarbonyloxymethyl)aminosulfonyl, N-(ethylcarbonyloxyethyl)aminosulfonyl, N-(propylcarbonyloxymethyl)aminosulfonate , N-(propylcarbonyloxyethyl)aminosulfonyl, N-(butylcarbonyloxymethyl)aminosulfonyl, N-(butylcarbonyloxyethyl)aminosulfonyl, etc. Aminosulfonyl substituted with -R ³¹ -O-CO-R ³² ; N-cyclohexylaminosulfonyl, N-(2-methylcyclohexyl)aminosulfonyl, N-( a ring having a substituent such as a 3-methylcyclohexyl)aminosulfonyl group, an N-(4-methylcyclohexyl)aminosulfonyl group, or an N-(4-butylcyclohexyl)aminosulfonyl group Aminosulfonyl substituted by hexyl; N-benzylaminosulfonyl, N-(1-phenylethyl)aminosulfonyl, N-(2-phenylethyl)aminesulfonate Mercapto, N-(3-phenylpropyl)aminosulfonyl, N-(4-phenylbutyl)aminosulfonyl, N-[2-(2-naphthyl)ethyl]amine Sulfosyl, N-[2-(4-methylphenyl)ethyl]aminosulfonyl, N-(3-phenyl-1-propyl)aminosulfonyl, N-(3 An aminosulfonyl group substituted with an aralkyl group such as a -phenyl-1-methylpropyl)aminosulfonyl group.

In the formula (A1), -SO ₂ R ³² may, for example, be methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, or the like - Butylsulfonyl, tert-butylsulfonyl, pentylsulfonyl, hexylsulfonyl, heptylsulfonyl, octylsulfonyl, 1-methylbutylsulfonyl, 1, 1,3,3-tetramethylbutylsulfonyl, 1,5-dimethylhexylsulfonyl, 1,6-dimethylheptylsulfonyl, 2-ethylhexylsulfonyl and 1 1,5,5-tetramethylhexylsulfonyl and the like. Among them, a methylsulfonyl group and an ethylsulfonyl group are preferred, and a methylsulfonyl group is more preferred.

It is preferable that at least one of R ¹ to R ¹⁸ is a nitro group because a pattern having a more excellent heat resistance is formed.

Further, at least one of R ¹ to R ⁵ and at least one of R ⁶ to R ¹⁰ are preferably -SO ₂ R ²⁹ . When there are a plurality of -SO ₂ R ²⁹ , the plural R ²⁹ systems may be the same or different from each other.

-SO ₂ R ²⁹ is -SO ₃ H, -SO ₂ NHR ³⁰ or -SO ₂ R ³² , preferably -SO ₂ R ³² . Among them, preferred is -SO ₂ CH ₃ .

When the compound of the present invention has -SO ₂ R ³² , at least one of R ¹¹ to R ¹⁴ and at least one of R ¹⁵ to R ¹⁸ are preferably -SO ₂ R ³² . When there are a plurality of -SO ₂ R ³² , the plural R ³² systems may be the same or different.

Preferable examples of the anion portion of the compound (A1) include an anion represented by the formula (1-b1) to the formula (1-b60).

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

The organic solvent to be used in the above reaction may, for example, be dichloromethane, chloroform, tetrahydrofuran, toluene or acetonitrile, and the amount thereof used is not limited. The reaction temperature is usually from 70 to 100 °C. The compound (1d) is used in an amount of usually 2 to 4 moles per mole of the chromium compound or the cobalt compound.

Preferable examples of the compound (1d) include compounds represented by the formula (1-a1) to the formula (1-a64).

The compound (1d) may be a diazonium salt represented by the formula (1b) (hereinafter sometimes referred to as "diazonium salt (1b)") and a pyrazole compound represented by the formula (1c) (hereinafter sometimes referred to as It is produced by a method of reacting "pyrazole compound (1c)"). The diazonium salt (1b) can be diazotized with nitrous acid, nitrite or nitrite by, for example, an amine represented by the formula (1a) (hereinafter sometimes referred to as "amine (1a)"). And get it.

In the formulae (1a) and (1b), R ¹¹ to R ¹⁴ represent the same meanings as described above. The A ^1- line represents an inorganic or organic anion. ]

Examples of the inorganic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchloric acid ion, and hypochlorite ion. Examples of the organic anion include CH ₃ COO ^- , C ₆ H ₅ COO ^- and the like. Preferred examples thereof include chloride ions, bromide ions, CH ₃ COO ^- and the like.

The reaction of the diazonium salt (1d) with the pyrazole compound (1c) is generally carried out in an aqueous solvent, and examples of the aqueous solvent include N-methylpyrrolidone. The reaction temperature is preferably -5 ° C to 60 ° C, more preferably 0 ° C to 30 ° C. The reaction time is preferably from 1 hour to 12 hours, more preferably from 1 hour to 4 hours.

In the formula (1c), R ¹ to R ⁵ and R ¹⁹ represent the same meanings as described above. ]

When the compound (1d) has -SO ₂ R ²⁹ and -SO ₂ R ²⁹ is -SO ₂ NHR ³⁰ , it can also be produced by using the amine (1a) having -SO ₂ NHR ³⁰ , but using a sulfo group. After the reaction with the amine (1a), it is preferred to produce the sulfo group by sulfoximation. For example, after synthesizing an azo compound having a sulfo group (hereinafter referred to as "compound (1s)") in the compound (1d), the sulfo group (-SO ₃ H) can be subjected to sulfonium halogenation by halogenating a sulfinous compound. (-SO ₂ X; X-based halogen atom) to obtain a sulfonium halide compound, and secondly, by reacting a sulfonium halide compound with an amine (R ³⁰ NH ₂ ) to sulfonate a sulfo group to produce a compound (1s).

Examples of the sulfinium halide compound include sulfinium fluoride, sulfinium chloride, sulfinium bromide, and sulfinium iodide. Preferred examples thereof include sulfinium chloride and sulfinium bromide. Good sulphur hexafluoride. The amount of sulfoxide halogen used is 1 to 10 moles relative to the compound (1s) 1 mole. It is better. Further, in the reaction system, when water is added, it is preferred to use a sulfite halogen compound which has been used in the reaction.

The sulfonium halogenation is carried out in a solvent. As the solvent, for example, an ether such as 1,4-dioxane (particularly preferably a cyclic ether); chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, dichloro can be used. Halogenated hydrocarbons such as ethylene, trichloroethylene, perchloroethylene, dichloropropane, pentane chloride, 1,2-dibromoethane, and the like. The amount of the solvent to be used is, for example, 3 parts by mass or more (preferably 5 parts by mass or more) and 10 parts by mass or less (preferably 8 parts by mass or less) based on 1 part by mass of the compound (1 s).

Further, the sulfonium halide is preferably a combination of N,N-dialkylformamide (for example, N,N-dimethylformamide, N,N-diethylformamide or the like). When N,N-dialkylformamide is used, it is used in an amount of from 0.05 to 1 mol per mol of the sulfonium halide compound. When the compound (1s) and N,N-dialkylformamide are preliminarily mixed in a solvent, when a sulfoxide halogen compound is added, heat generation can be suppressed.

The reaction temperature in the halogenation of the sulfonium 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 longer, preferably 3 hours or longer and 8 hours or shorter, more preferably 3 hours or longer and 5 hours or shorter.

As described above, the prepared sulfonium halide compound can also be reacted with an amine (R ³⁰ NH ₂ ) after isolation, and the reaction mixture can be directly reacted with an amine (R ³⁰ NH ₂ ). Further, in the case of isolation, for example, if the reaction mixture is mixed with water, the precipitated crystals may be collected by filtration. The crystal of the obtained sulfonium halide compound may be washed with water and dried as needed before the reaction with the amine (R ³⁰ NH ₂ ).

The amine (R ³⁰ NH ₂ ) contains: n-propylamine, n-butylamine, n-hexylamine, dimethylhexylamine (1,5-dimethylhexylamine, etc.), tetramethylbutyl Amine (1,1,3,3-tetramethylbutylamine, etc.), ethylhexylamine (2-ethylhexylamine, etc.), aminophenylbutane (3-amino-1-phenylbutyrate) Alkane, etc.), isopropoxypropylamine, and the like. The amount of the amine (R ³⁰ NH ₂ ) used is 2 mol or more and 10 mol or less, preferably 2 mol or more and 7 mol or less, based on 1 mol of the sulfonium halide compound.

Although the order of addition of the sulfonium halide compound and the amine (R ³⁰ NH ₂ ) is not particularly limited, it is preferred to add (drop) an amine (R ³⁰ NH ₂ ) to the sulfonium halide compound. Further, the reaction of the sulfonium halide compound with the amine (R ³⁰ NH ₂ ) is preferably carried out in a solvent. As the solvent, the same solvent as that used in the preparation of the sulfonium halide compound can be used.

Further, the reaction of the sulfonium halide compound with an amine (R ³⁰ NH ₂ ) is preferably carried out in the presence of a basic catalyst. Examples of the basic catalyst include a tertiary amine (an aliphatic tertiary amine such as triethylamine or triethanolamine; an aromatic tertiary amine such as pyridine), and a secondary amine (diethylamine or the like). An aliphatic secondary amine; a cyclic aliphatic secondary amine such as piperidine or the like. Among these, a tertiary amine, particularly an aliphatic tertiary amine such as triethylamine is preferred. 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, relative to the amine (R ³⁰ NH ₂ ) 1 mol.

When an amine (R ³⁰ NH ₂ ) and a basic catalyst are added to the sulfonium halide compound, the timing of addition of the basic catalyst is not particularly limited, and may be before and after the addition of the amine (R ³⁰ NH ₂ ). At any point in time, it can also be added at the same timing as the amine (R ³⁰ NH ₂ ). Alternatively, it may be added after mixing with a reactive amine, or may be added separately with an amine (R ³⁰ NH ₂ ).

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

The method for obtaining the compound (1d) of the objective compound 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. It is preferred that the acid is added to the aqueous solution after the acid solution is prepared in advance. The temperature at the time of adding the reaction mixture is preferably 10 ° C or more and 50 ° C or less, preferably 20 ° C or more and 50 ° C or less, more 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 further stirred at the above temperature for about 0.5 to 2 hours. The crystals to be filtered are washed with water or the like, and then preferably dried. Further, if necessary, it may be further purified by a known method such as recrystallization.

<compound (A2)>

In the formula (A2), the aliphatic hydrocarbon group having 1 to 8 carbon atoms may, for example, be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a secondary-butyl group or a tertiary group. Butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and the like.

The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in the formula (A2) may, for example, be a phenyl group, a tolyl group, a xylyl group, a trimethylphenyl group, a propylphenyl group or a butylphenyl group.

R ³³ is preferably an alkyl group having 1 to 4 carbon atoms, preferably a methyl group and an ethyl group, more preferably a methyl group.

Since the color density becomes high, R ²¹ to R ²⁴ are preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms having a substituent, and more preferably a hydrogen atom or an ethyl group.

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

R ²⁷ is preferably a vinyl group and a propane-1,2-di group, and more preferably a vinyl group.

R ²⁸ is preferably a hydrogen atom.

n is an integer of 1 to 4, preferably an integer of 2 to 4, more preferably 3 or 4.

-(R ²⁷ -O)nR ²⁸ is a tendency to improve the solubility of the organic solvent of the compound (A2), so 2-(2-hydroxyethoxy)ethyl and 2-[2-(2- More preferably, hydroxyethoxy)ethoxy]ethyl is 2-[2-(2-hydroxyethoxy)ethoxy]ethyl.

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

Among the compounds (A2), preferred examples of the cation derived from the xanthene compound include a cation represented by the formula (1-c1) to the formula (1-c48).

The compound (A2) can be synthesized by using a commercially available dibenzopyran dye (for example, "Rhodamin 6G" manufactured by Tajika Chemical Industry Co., Ltd.).

The total content of the compound (A1) and the compound (A2) is in the In the toner (A), it is preferably 1% by mass or more and 99% by mass or less, more preferably 1% by mass or more and 80% by mass or less, and still more preferably 3% by mass or more and 70% by mass or less.

The mass ratio of the compound (A1) to the compound (A2) is preferably from 1:9 to 9:1, more preferably from 3:7 to 7:3.

<pigment>

The colorant (A) is a compound which (ii) substitutes the compound (A1) or, together with the compound (A1), (iii) contains at least one selected from the group consisting of a yellow pigment, an orange pigment, and a red pigment.

Examples of the yellow pigments include CI Pigment Yellow 1 (hereinafter, the description of CI Pigment Yellow is omitted, and only numbers are shown), 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.

The orange pigment is exemplified by CI Pigment Orange 13 (hereinafter, the description of CI Pigment Orange is omitted, and only the number is shown), 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71 , 73, etc.

The red pigment may be CI Pigment Red 9 (hereinafter, the description of CI Pigment Red is omitted, and only the number is shown), 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209 , 215, 216, 224, 242, 254, 255, 264, 265, and the like.

Wherein, it preferably comprises a pigment yellow 138 selected from C.I. 139, 150, C.I. at least one of Pigment Red 177, 242, 254. When the pigment described above is contained, the optimization of the transmission spectrum is facilitated, and the chemical resistance is improved.

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

The coloring agent (A) may contain an organic pigment other than the yellow pigment, the orange pigment, and the red pigment. Examples of the other pigments include CI Pigment Violet 1 (hereinafter, the description of CI Pigment Violet is omitted, and only the number is described). , purple pigments of 19, 23, 29, 32, 36, 38, etc.

If necessary, the pigment may be subjected to a resin treatment, a surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment of a pigment surface by a polymer compound or the like, and a particle by a sulfuric acid micronization method or the like. The treatment, the washing treatment of an organic solvent or water for removing impurities, the removal treatment by an ion exchange method such as ionic impurities, or the like.

It is preferred that the pigment has a uniform particle size.

When the colored curable resin composition of the present invention contains a pigment as the colorant (A), a pigment dispersant may be contained. The pigment dispersion liquid in a state in which the pigment is uniformly dispersed in the solution can be obtained by dispersing the pigment dispersant.

Examples of the pigment dispersant include a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric, a polyester-based, a polyamine-based, and a propylene-based surfactant. These pigment dispersants may be used singly or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoei Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), and EFKA (BASF). Company system), AJISPER (Ajinomoto FineTechno Co., Ltd.), Disperbyk (manufactured by BYK Chemical Co., Ltd.), etc.

When the pigment dispersant is used, the amount thereof is preferably 100 parts by mass, more preferably 5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the pigment. The amount of the pigment dispersant used is within the above range, and there is a tendency that a pigment dispersion liquid in a uniformly dispersed state can be obtained.

The content of the colorant (A) is preferably from 5 to 60% by mass, preferably from 8 to 55% by mass, more preferably from 10 to 50% by mass, based on the solid content in the colored curable resin composition. Here, the solid fraction refers to the total amount of components in which the solvent is removed in the colored curable resin composition. When the content of the colorant (A) is within the above range, the color density as a color filter is sufficient, and a necessary amount of the adhesive polymer can be contained in the composition, so that a pattern having sufficient mechanical strength can be formed.

<Other dyes>

The colorant (A) may also contain a dye different from the compound (A1) and the compound (A2). Examples of the dye include dyes such as an oil-soluble dye, an acid dye, an amine salt of an acid dye, or a sulfoximine derivative of an acid dye. For example, a compound classified as a dye in a color rendering index (published by The Society of Dyers and Colourists) or a known dye described in a dyeing document (Dyeing Note).

Specifically, CI solvent yellow 4 (hereinafter, the description of CI solvent yellow is omitted, only the number is shown), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162; CI solvent red 45 (hereinafter, the description of CI solvent red is omitted, only the number is shown), 49, 125, 130; CI solvent orange 2 (hereinafter, the description of CI solvent orange is omitted, only the number is shown), 7, 11, 15, 26, 56; CI solvent dyes such as CI, acid yellow 1 (hereinafter, the description of CI acid yellow is omitted, only numbers are shown), 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; CI acid red 1 (hereinafter, the description of CI acid red is omitted, only the number is described), 4, 8, and 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; CI Acid Orange 6 (hereinafter, the description of the CI Acid Orange is omitted, only the number is described), 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; CI Acid Violet 6B (hereinafter, the description of CI acid purple is omitted, only the number is described), 7, 9, 17, 19; CI acid dye, CI direct yellow 2 (hereinafter, the description of CI direct yellow is omitted, only the number is shown), 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; CI Direct Red 79 (hereinafter, the description of CI direct red is omitted, only the number is 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; CI direct orange 34 (hereinafter, the description of CI direct orange is omitted, only the number is described), 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI direct purple 47 (hereinafter, the description of CI direct purple is omitted, only the number is recorded.), 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 ; CI direct dyes, etc., CI media (Mordant) yellow 5 (hereinafter, the description of the CI medium yellow is omitted, only the number is shown), 8, 10, 16, 20, 26, 30, 31, 33, 42, 43 45, 56, 61, 62, 65; CI medium red 1 (hereinafter, the description of the CI medium red is omitted, only the number is recorded.), 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; CI medium orange 3 (hereinafter, the description of the CI medium orange is omitted, only the number is recorded.), 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI medium purple 1 (hereinafter, the description of the CI medium purple is omitted, only the number is recorded.), 2, 4, 5, 7, 14 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; and other CI medium dyes.

<boron complex (F)>

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

As the boron complex (F), for example, an anion represented by the following formula (4) can be mentioned.

In the formula (4), W ₁ and W ₂ each independently represent a group in which two monovalent proton-donating substituents emit protons. ]

In the formula (4), a monovalent proton-donating substituent is a group in which two protons are released, and preferably a catechol which may have a substituent or a 2,3-dihydroxy group which may have a substituent. Naphthalene, may also 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, and 1-hydroxy group which may have a substituent 2-naphthoic acid, a binaphthol which may have a substituent, a salicylic acid which may have a substituent, a benzoic acid which may have a substituent, or a mandelic acid which may have a substituent.

The above-mentioned salicylic acid which may have a substituent, for example, salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-aminosalicylic acid, 3-chloro Salicylic acid, 4-bromosalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3,5-di-tertiary-butyl water Salicylic acid, 3,5-dibromosalicylic acid, 3,5-dichlorosalicylic acid, 3,5,6-trichlorosalicylic acid, 3-hydroxysalicylic acid (2,3-dihydroxybenzoic acid) ), 4-hydroxysalicylic acid (2,4-dihydroxybenzoic acid), 5-hydroxysalicylic acid (2,5-dihydroxybenzoic acid), 6-hydroxysalicylic acid (2,6-dihydroxybenzoin) Acid) and so on.

The aforementioned benzoic acid which may have a substituent, for example, may be exemplified by: Wait.

The above-mentioned phenylglycolic acid which may have a substituent, for example, may be exemplified by: Wait.

Examples of the anion represented by the formula (4) include an anion represented by the following formula (A) such as an anion (BC-1) to an anion (BC-28) or a formula (BC-25); Anion (BC-25) to anion (BC-28) represented by formula (BC-28). Further, the anions (BC-1) to anions (BC-24) have the substituents shown in Table 1 as R ₆₁ , R ₆₂ , R ₆₃ and R ₆₄ .

In addition, the anion represented by the formula (4) is an anion (BC-1), an anion (BC-2), an anion (BC-3), an anion (BC-25), an anion (BC-26), Anion (BC-27) is preferred, anion (BC-1), anion (BC-2), anion (BC-25) are preferred, and anions (BC-1) and anions (BC-2) are more preferred. good. The anion of the present invention tends to be excellent in solubility in an organic solvent.

The content of the boron complex (F) is preferably 0.1 parts by mass or more and 20 parts by mass or less based on 100 parts by mass of the colorant (A), and more preferably 0.5 parts by mass or more and 10 parts by mass or less.

<Zinc complex (G)>

The colored curable resin composition of the present invention may further contain a zinc complex (G). The zinc complex (G) may, for example, be a zinc complex represented by the formula (5).

In the 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. ]

In R ⁷¹ to R ⁷⁴ of the formula (5), an alkyl group having 1 to 4 carbon atoms may, for example, be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group or a secondary group - Butyl, tertiary-butyl. Specific examples of the zinc complex represented by the formula (5) include the complex compounds having a substituent shown in Table 2. Among them, (5)-18 is preferred from the viewpoint of improving heat resistance.

The content of the zinc complex (G) is preferably 0.1 parts by mass or more and 30 parts by mass or less, and more preferably 0.5 parts by mass or more and 15 parts by mass or less based on 100 parts by mass of the coloring agent (A).

<Resin B>

The colored curable resin composition of the present invention contains a resin (B). The resin (B) is not particularly limited, but an alkali-soluble resin is preferred.

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

[K1] a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (a) (hereinafter sometimes referred to as "(a)"), and selected from unsaturated carboxylic acids and not A copolymer of at least one type (b) (hereinafter sometimes referred to as "(b)") in a group of saturated carboxylic anhydrides.

[K2] (a), (b), and monomer (c) copolymerizable with (a) (however, (a) and (b) are different) (hereinafter sometimes referred to as "(c) Copolymer

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

[K4] A resin obtained by reacting (a) a copolymer of (b) with (c).

The resin (B) is obtained by containing the structural unit derived from (a), and the reliability of the heat resistance and chemical resistance of the obtained colored pattern can be further improved.

(a) means, for example, at least a group having a cyclic ether structure of 2 to 4 carbon atoms (for example, selected from the group consisting of ethylene oxide, oxetane ring, and tetrahydrofuran ring (Oxolane ring)) 1) a polymerizable compound bonded to an ethylenic unsaturated group. (a) is a cyclic ether having 2 to 4 carbon atoms It is preferred to use a monomer of (meth)acryloxyloxy 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)acrylonitrile" and "(meth)acrylate" have the same meaning.

(a), for example, a monomer (a1) having an ethylene oxide group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(a1)"), having an oxetane group and an ethyl group Unsaturated bonded monomer (a2) (hereinafter referred to as "(a2)"), a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond (a3) (hereinafter sometimes referred to as "(a3)") Wait.

(a1), for example, a monomer (a1-1) having a structure in which a chain olefin is epoxidized (hereinafter sometimes referred to as "(a1-1)")), which has an epoxidized ring olefin. The monomer (a1-2) of the structure (hereinafter sometimes referred to as "(a1-2)").

Examples of (a1-1) include epoxypropyl (meth)acrylate, β-methylepoxypropyl (meth)acrylate, and β-ethylepoxypropyl (meth)acrylate. , propylene propyl vinyl ether, o-vinyl tolyl epoxidized propyl ether, m-vinyl tolyl epoxidized propyl ether, p-vinyl tolyl epoxypropyl ether, α-methyl-o -vinyltoluene-epoxypropyl ether, α-methyl-m-vinyltolylepoxypropyl ether, α-methyl-p-vinyltolylepoxypropyl ether, 2,3-double (glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6- Bis(glycidoxymethyl)styrene, 2,3,4-cis (glycidoxymethyl)styrene, 2,3,5-glycol(epoxypropyloxymethyl)styrene , 2,3,6-para (glycidyl Alkyloxymethylstyrene, 3,4,5-glycol (epoxypropyloxymethyl)styrene, 2,4,6-glycol (epoxypropyloxymethyl)styrene, and the like.

(a1-2): monooxyethylene cyclohexene, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel Chemical Industry Co., Ltd.), 3, 4 Epoxycyclohexylmethyl (meth) acrylate (for example, CYCLOMER A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, CYCLOMER M100; A compound represented by the formula (I), a compound represented by the formula (II), and the like are produced by Daicel Chemical Industry Co., Ltd.

[In the formulae (I) and (II), R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may also be Hydroxyl substitution.

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

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

* indicates the binding object with O. ]

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

The alkyl group in which the hydrogen atom is substituted by a hydroxyl group can be exemplified by a hydroxyl group. Methyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-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.

The alkanediyl group may, for example, be a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group or a pentane-1,5- Dibasic, hexane-1,6-diyl and the like.

X ¹ and X ^{2 are} preferably a single bond, a methylene group, an ethylene group, a *-CH ₂ -O- (* means a bond target with O), and *-CH ₂ CH ₂ -O. -Based, a better series: single bond, *-CH ₂ CH ₂ -O- group.

The compound represented by the formula (I) may, for example, be a compound represented by the formula (I-1) to the formula (I-15). Preferably, the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9), the formula (I-11) to the formula (I) I-15). More preferably, it is a formula (I-1), Formula (I-7), Formula (I-9), Formula (I-11) to Formula (I-15).

The compound represented by the formula (II) may, for example, be a compound represented by the formula (II-1) to the formula (II-15). Preferably, the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9), the formula (II-11) to the formula (II) II-15).

More preferably, it is a formula (II-1), Formula (II-7), Formula (II-9), Formula (II-15).

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

The monomer (a2) having an oxetane group and an ethylenically unsaturated bond is more preferably a monomer having an oxetane group and a (meth) acryloxy group. (a2) can be exemplified by 3-methyl-3-methylpropenyloxy Oxycyclobutane, 3-methyl-3-propenyloxymethyloxetane, 3-ethyl-3-methylpropenyloxymethyloxetane, 3-B 3--3-propenyloxymethyloxetane, 3-methyl-3-methylpropenyloxyethyloxetane, 3-methyl-3-propenyloxyethyl Oxetane, 3-ethyl-3-methylpropenyloxyethyloxetane, 3-ethyl-3-propenyloxyethyloxetane, and the like.

The monomer (a3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond is more preferably a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group.

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

(a) It is preferable to improve (a1) from the viewpoint of further improving the reliability of heat resistance and chemical resistance of the obtained colored pattern. Further, from the viewpoint of excellent storage stability of the colored curable resin composition, (a1-2) is more preferable.

(b) Specifically, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid, fumaric acid, citraconic acid; , mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6- Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexene dicarboxylic acid; methyl-5-norzene-2,3-dicarboxylate Acid, 5-carboxyl linkage [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-B a bicyclic unsaturated compound containing a carboxyl group such as a heptane ring [2.2.1] hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-ethylene Phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, Unsaturated dicarboxylic anhydrides such as 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydrate (Himic anhydride); succinic acid mono[2-(methyl)acryloxyethyl] a divalent or higher polyvalent carboxylic acid unsaturated mono[(meth)acryloxyalkylalkyl]ester such as an ester or a mono[2-(methyl)acryloxyethyl) phthalate; Examples of the α-(hydroxymethyl)acrylic acid include unsaturated acrylates having a hydroxyl group and a carboxyl group in the same molecule.

Among these, acrylic acid, methacrylic acid, maleic anhydride or the like is preferred from the viewpoint of copolymerization reactivity or solubility in an aqueous alkali solution.

(c) Examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and secondary butyl (meth) acrylate. Tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (methyl) Acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8 -Based (meth) acrylate (known in the art as dicyclopentyl (meth) acrylate.), dicyclopentyloxyethyl (meth) acrylate, idyl (Meth) acrylate, adamantyl (meth) acrylate, propylene (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (methyl (meth)acrylates such as acrylate and tolyl (meth) acrylate; hydroxyl group-containing such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate ( Methyl) acrylates; diethyl maleate, blessing a dicarboxylic acid diester such as diethyl acid or diethyl itaconate; bicyclo [2.2.1] hept-2-ene, 5-methyl bicyclo [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]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene , 5,6-bis(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-ethyl bicyclic [2.2.1] Hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tris-butoxycarboxyl linkage [2.2.1] Hept-2-ene, 5-cyclohexyloxycarboxybicyclo[2.2.1]hept-2-ene, 5-phenoxycarboxybicyclo[2.2.1]hept-2-ene, 5,6-double (Tris-butoxycarboxy)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarboxy)bicyclo[2.2.1]hept-2-ene Unsaturated compounds; N-phenyl maleimide, N-cyclohexyl醯iimine, N-benzylmethylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-malaya Aminobutyrate, N-succinimide-6-maleimide caproate, N-succinimide-3-maleimide propionate, N-(9-acridine Dicarbonyl quinone imine derivatives such as maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy Styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, propenylamine, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2, 3-dimethyl-1,3-butadiene and the like.

Among these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmethylmaline Amine, bicyclo [2.2.1] hept-2-ene, etc. are preferred.

In the resin [K1], the ratio derived from the respective structural units is preferably in the following range in the total structural unit constituting the resin [K1].

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

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

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

Resin [K1] can be referred to, for example, in the literature "Experimental Method for Polymer Synthesis" (Otsuno Ryokan, Ltd., Chemical Co., Ltd., 1st Edition) It is manufactured by the method described in the first brush issued on March 1, 1972, and the cited documents described in the document.

Specifically, a method in which the quantitative amount, the polymerization initiator, the solvent, and the like of (a) and (b) are placed in a reaction vessel, and oxygen is replaced by nitrogen, and the mixture is deoxidized, stirred, heated, and kept warm. Further, the polymerization initiator, the solvent and the like used herein are not particularly limited, and any one generally used in the field can be used. For example, the polymerization initiator may be exemplified by an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), or the like) or organic peroxidation. The solvent (such as benzamidine peroxide) may be any solvent as long as it can dissolve each monomer, and a solvent or the like described later may be used as a solvent of the curable resin composition.

Further, the obtained copolymer may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used. In particular, when a solvent (E) to be described later is used as a solvent in the polymerization, the solution after the reaction can be used as it is, and the step of omitting the production can be simplified.

In the resin [K2], the ratio derived from the respective structural units is preferably in the following range in the total structural unit constituting the resin [K2].

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

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

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

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

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

Specifically, the quantitative, polymerization initiator, solvent, and the like of (a), (b), and (c) are placed in a reaction vessel, and oxygen is replaced by nitrogen, and the mixture is stirred and heated under deoxygenation. The method of insulation. As the obtained copolymer, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) may be taken out by a method such as reprecipitation.

In the resin [K3], the ratio derived from the respective structural units is preferably in the range of the following in the entire structural unit constituting the resin [K3].

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

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

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

The resin [K4] is obtained by adding a copolymer of (b) and (c) to a cyclic ether having 2 to 4 carbon atoms (a) and adding (b) a carboxyl group.

First, the copolymer of (b) and (c) is produced in the same manner as the method described in the production method of [K1]. At this time, the ratio derived from the respective structural units is in the entire structural unit of the copolymer constituting (b) and (c), It is preferably within the following range.

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

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

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

In the manufacture of the copolymer of (b) and (c), the environment in the flask is changed from nitrogen to air to make the reaction catalyst of (a) carboxyl group and cyclic ether (for example, dimethylaminomethyl group) The phenol or the like is 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a) to (c), and the polymerization inhibitor (for example, hydroquinone or the like) is added to the total of (a) to (c). The amount of 100 parts by mass of 0.001 to 5 parts by mass is placed in the flask, for example, at 60 to 130 ° C, by reacting for 1 to 10 hours, the resin [K4] can be obtained. The reaction conditions such as the method, the reaction temperature, and the time can be appropriately adjusted depending on the production equipment or the heat generated by the polymerization. Further, similarly to the polymerization conditions, the method of preparation and the reaction temperature can be appropriately adjusted in consideration of the production equipment or the heat generated by the polymerization.

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

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate/(meth)acrylic acid copolymer, and 3,4-epoxytricyclo[5.2. .1.0 ^2.6 ] Resin of thiol acrylate/(meth)acrylic copolymer, etc. [K1]; epoxy propyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylate Polymer, epoxypropyl (meth) acrylate / styrene / (meth) acrylate copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] methacrylate / (meth) acrylate a resin such as /N-cyclohexylmaleimide copolymer, 3-methyl-3-(methyl)propenyloxymethyloxetane/(meth)acrylic acid/styrene copolymerization [ K2]; benzyl (meth) acrylate / (meth) acrylate copolymer, styrene / (meth) acrylic copolymer, etc. [K3]; in benzyl (meth) acrylate / Addition of a glycidyl (meth) acrylate resin to a (meth)acrylic copolymer, tricyclodecyl (meth) acrylate / styrene / (meth) acrylate copolymer addition of propylene Base (meth) acrylate resin, tricyclodecyl (meth) acrylate / benzo Resin (meth) acrylate / (meth) acrylic copolymer adduct glycidyl (meth) acrylate resin, etc. [K4] and the like. Among them, the resin [K1] and the resin [K2] are preferred, the resin [K1] is preferred, and the 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate/(meth)acrylic acid copolymer is preferred. Things are better.

The weight average molecular weight of the converted polystyrene of the resin (B) 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, and further preferably 7,000 to 28,000. . When the molecular weight is within the above range, the hardness of the coating film is increased, and the residual film ratio is also increased, and the solubility in the developing liquid of the unexposed portion is good, and the resolution tends to be improved.

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

The acid value of the resin (B) is preferably from 50 to 150 mg-KOH/g, more preferably from 60 to 135 mg-KOH/g, still more preferably from 70 to 135 mg-KOH/g. Here, the acid value is set to a value for measuring the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be obtained, for example, by titration using an aqueous potassium hydroxide solution.

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

<Photopolymerizable Compound (C)>

The colored curable resin composition of the present invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) is a compound which is polymerized by an active radical generated by a photopolymerization initiator (D), oxygen, or the like by irradiation with light, and examples thereof include a polymerizable ethylenically unsaturated bond. The compound or the like is preferably a (meth) acrylate compound.

Among them, the photopolymerizable compound (C) is preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a photopolymerizable compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate. Ester and the like. Photopolymerizable compound (C), can be single It can be used alone or in combination of two or more.

The content of the photopolymerizable compound (C) is preferably 7 to 65 mass%, more preferably 13 to 60 mass%, still more preferably 17 to 55 mass%, based on the solid content of the color curable resin composition. When the content of the photopolymerizable compound (C) is within the above range, it can be sufficiently cured, and the film thickness ratio before and after development can be improved, and the undercut is less likely to occur in the pattern. Good tendency, so good.

<Photopolymerization initiator (D)>

The colored curable resin composition of the present invention contains a photopolymerization initiator (D).

The photopolymerization initiator (D) is produced by the action of light to generate active radicals, oxygen, or the like, and is not particularly limited as long as the compound capable of starting polymerization can be used, and a known polymerization initiator can be used.

The photopolymerization initiator (D) is preferably a compound which generates an active radical by the action of light, and contains a compound selected from the group consisting of an alkylphenone compound, a triazine compound, a mercaptophosphine oxide compound, and an antimony compound. At least one photopolymerization initiator in the group of the biimidazole compound is preferred, and a photopolymerization initiator containing a ruthenium compound is more preferred.

Examples of the alkylphenone compound include diethoxyacetophenone, 2-methyl-2-morpholinyl-1-(4-methylsulfonylphenyl)propan-1-one, and 2-dimethyl Amino-1-(4-morpholinophenyl)-2-benzylidenebutan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2- (4-methylphenylmethyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 An oligomer of [4-(1-methylvinyl)phenyl]propan-1-one or the like is preferably exemplified by 2-methyl-2-morpholino-1-(4-methyl) Sulfohydroxyphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-tolylbutan-1-one, and the like. Commercial products such as IRGACURE 369 and 907 (above, manufactured by BASF Corporation) can also be used.

The triazine compound can be exemplified by 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine and 2,4-bis(trichloromethyl). - 6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine, 2 ,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2- (5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl -1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1, 3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, and the like.

Examples of the mercaptophosphine compound include 2,4,6-trimethylbenzyldiphenylphosphine oxide. Commercial products such as IRGACURE 819 (manufactured by BASF Corporation) can also be used.

The hydrazine compound may be exemplified by N-benzimidyloxy-1-(4-phenylsulfonylphenyl)butan-1-one-2-imine, N-benzylideneoxy-1-(N) 4-phenylsulfonylphenyl)octane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H- Oxazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2) , 4-dioxolylmethyloxy)benzimidyl}-9H-indazol-3-yl]ethane-1-imine and the like. Can also make Commercial products such as IRGACURE OXE-01, OXE-02 (above, manufactured by BASF Corporation), and N-1919 (made by Adeka Co., Ltd.) are used.

As the biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichloro) can be mentioned. Phenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, see JP-A-6-75372, JP-A-6-75373, etc.), 2, 2'-double ( 2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis Oxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-double (2-Chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, Japanese Patent Publication No. Sho 48-38403, JP-A-62-174204) The phenyl group of the 4, 4', 5, 5'-position is an imidazole compound substituted by a carboxyalkoxy group (for example, refer to JP-A-7-10913, etc.). Preferred systems are: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorobenzene -4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl Imidazole.

Examples of the acid generator which generates an acid by light include 4-hydroxyphenyldimethylphenyl p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethyloxyl. Phenyldimethylhydrazine p-tolylsulfonate, 4-acetoxyphenyl/methyl/benzylphosphonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium Anthracene salts such as hexafluoroantimonate, diphenylphosphonium p-toluenesulfonate, diphenylphosphonium hexafluoroantimonate, and nitrobenzyl tosylate, benzoin tosylate Classes, etc.

Photopolymerization initiator (D), for example, such as a triazine compound, A compound which simultaneously generates active radicals and an acid by light.

Further, the photopolymerization initiator (D) may, for example, be a benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzoin isobutyl ether. Compound; benzophenone, methyl o-benzylidene benzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3' a benzophenone compound such as 4,4'-tetrakis (tertiary-butylperoxycarbonyl)benzophenone or 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone An anthraquinone compound such as 2-ethylhydrazine or camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and a titanocene compound. These are preferably used in combination with a photopolymerization initiation aid (D1) (particularly an amine) to be described later.

The content of the photopolymerization initiator (D) is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per 100 parts by mass of the total of the resin (B) and the photopolymerizable compound (C). When the content of the photopolymerization initiator is within the above range, the sensitivity is high, the exposure time is shortened, and the productivity is improved.

<Photopolymerization Starter Aid (D1)>

The coloring-curable resin composition of the present invention may further contain a photopolymerization initiation aid (D1). a photopolymerization initiation aid (D1), which is generally used in combination with a photopolymerization initiator (D), to promote the polymerization of a photopolymerizable compound which starts polymerization by a photopolymerization initiator, or Sensitizer.

The photopolymerization initiation aid (D1) can be exemplified by an amine compound, An alkoxy fluorene compound, a Thioxanthone compound, a carboxylic acid compound or the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamino group. Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'- Bis(dimethylamino)benzophenone (commonly known as Michler's ketone; Michlerone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethyl Methylamino)benzophenone or the like, of which 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

The alkoxy ruthenium 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.

The thioxanthone compound can be exemplified by 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-propoxythioxanthone and the like.

The carboxylic acid compound may, for example, be phenylsulfonylacetic acid, methylphenylsulfonylacetic acid, ethylphenylsulfonylacetic acid, methylethylphenylsulfonylacetic acid or dimethylphenylsulfonyl Acetic acid, methoxyphenylsulfonyl acetic acid, dimethoxyphenylsulfonyl acetic acid, chlorophenylsulfonyl acetic acid, dichlorophenylsulfonyl acetic acid, N-phenylglycine, phenoxy Acetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

The photopolymerization initiation aid (D1) may be used singly or in combination of two or more.

When the photopolymerization initiator (D1) is used, the amount thereof is preferably 0.01 to 50 parts by mass, more preferably 100 parts by mass, based on the total amount of the resin (B) and the polymerizable compound (C). 0.1 to 40 parts by mass. Further, it is preferably 0.01 to 10 moles, more preferably 0.01 to 5 moles, per mole of the photopolymerization initiator (D). When the amount of the polymerization initiation aid (D1) is within this range, a pattern can be formed with high sensitivity, and the productivity of the pattern tends to be improved.

<Solvent (E)>

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

The solvent (E) is not particularly limited, and a solvent generally used in the field can be used. For example, it may be selected from the group consisting of an ester solvent (a solvent containing -COO-), a hydrazine solvent other than an ester solvent (a solvent containing -O-), an ether ester solvent (a solvent containing -COO- and -O-), and an ester solvent. It is used among other ketone solvents (solvent containing -CO-), an alcohol solvent, an aromatic hydrocarbon solvent, a guanamine solvent, dimethyl hydrazine, and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl acid acetate, and isoamyl acetate. Ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclohexanol Acetate, γ-butyrolactone, and the like.

Ether solvents can be listed as: ethylene glycol monomethyl ether, ethylene two Alcohol 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, four Hydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, two Ethylene glycol dibutyl ether, anisole, phenethyl ether, methyl anisole, and the like.

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

The ketone solvent may, for example, be 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone or 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.

The aromatic hydrocarbon solvent can be exemplified by benzene, toluene and dimethyl Benzene, mesitylene, and the like.

The guanamine solvent may, for example, be N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone.

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

Among the above-mentioned solvents, from the viewpoint of coatability and drying property, an organic solvent having a boiling point of from 120 ° C to 180 ° C at 1 atm is preferred. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, two Glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc., preferably propylene glycol monomethyl ether, propylene glycol single More preferably, methyl ether acetate, ethyl lactate, ethyl 3-ethoxypropionate or the like. When such a solvent is contained, the flatness at the time of coating is excellent.

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

<Interacting Agent (H)>

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

Examples of the surfactant (H) 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 polyoxygenated surfactants include surfactants having a siloxane coupling. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, polyether modified polyoxyl SH8400 (trade name: Toray Dow Corning), KP321 , KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (Momentive Performance Materials Japan contract company) .

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Specifically, FLUORAD (trade name) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (trade name) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC R30, MEGAFAC RS-718-K (made by DIC), EFTOP (trade name) EF301, EFTOP EF 303, EFTOP EF351, EFTOP EF352 (Mitsubishi Materials Electronics Co., Ltd.), SURFLON (trade name) S381, SURFLON S382, SURFLON SC101, SURFLON SC105 (made by Asahi Glass Co., Ltd.), E5844 (Dakjin Institute of Fine Chemicals (shares) System) and so on.

The polyfluorene-based surfactant having the fluorine atom may, for example, be a surfactant having a siloxane coupling or a fluorocarbon chain. Specifically, MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, MEGAFAC F443 (manufactured by DIC) can be cited.

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

The content of the surfactant (H) is preferably 0.001% by mass or more and 0.2% by mass or less based on the coloring curable resin composition, and is preferably 0.002% by mass or more and 0.1% by mass or less, more preferably 0.01% by mass or more and 0.05%. Below mass%. When the content of the surfactant (H) is within the above range, the flatness of the coating film can be improved.

The colored curable resin composition of the present invention is a coloring agent (A), an alkali-soluble resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), a solvent (E), and an interface activity. The composition of the agent (H) can provide a coloring pattern which is excellent in coatability and excellent in solvent resistance and spectral separation.

The colored curable resin composition of the present invention may further contain a filler, another polymer compound, an adhesion promoter, an antioxidant, an ultraviolet absorber, a light stabilizer, a chain transfer agent, etc., as needed. Various additives.

A method of forming a colored pattern by using the colored curable resin composition of the present invention, for example, a coloring curable resin composition of the present invention is applied to a substrate or another resin layer (for example, on a substrate) On the other colored curing resin composition layer formed above, etc., a volatile layer such as a solvent is removed/dried to form a colored layer, and the colored layer is exposed through a photomask, and the development method does not require photo etching. Photo lithography method of printing machine, etc.

The thickness of the coating film at this time is not particularly limited, and may be appropriately adjusted depending on the material to be used, the use, and the like, and is, for example, 0.1 to 30 μm, preferably 1 to 20 μm, more preferably 1 to 6 μm.

Examples of the method of applying the colored hardening resin composition include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method, and a die coating method. Further, a dip coater, a bar coater, a spin coater, a slit and a spin coater, and a slit coater (referred to as a die coater, a curtain coater, a spin coater, etc.) may be used. Coating machine to coat.

Examples of the solvent removal/drying include natural drying, air drying, reduced pressure drying, and heat drying. The specific drying temperature is preferably from 10 to 120 ° C, more preferably from 25 to 100 ° C.

The drying time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.

The drying under reduced pressure is preferably carried out at a pressure of 50 to 150 Pa in the range of 20 to 25 °C.

The dried coating film is exposed by a photomask for forming a desired pattern.

The pattern shape on the photomask at this time is not particularly limited, and a pattern shape corresponding to the intended use can be used.

The light source used for the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. Specifically, a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, or the like may be cited, or may be intercepted by using a filter that cuts a specific wavelength range, or a band-passing filter that intercepts a specific wavelength domain may also be used (Band- Pass filter) and selectively taken out for exposure.

It is preferable to uniformly illuminate the parallel light rays on the entire exposed surface or to properly align the positions of the reticle and the substrate with a reticle aligner, a stepper, or the like.

After the exposure, the photosensitive liquid is contacted to dissolve a predetermined portion, for example, an unexposed portion, and development is performed to obtain a pattern. Examples of the developing liquid system include an aqueous solution of a basic compound (potassium hydroxide, sodium carbonate, tetramethylammonium hydroxide or the like). The developing solution may also contain a surfactant.

As the development method, any one of a paddle method, a dipping method, a spray method, and the like can be used. It is also possible to tilt the substrate at an arbitrary angle during development. After the development, it is better to wash with water.

Post-baking can also be carried out as needed. The post-baking is preferably carried out, for example, at 150 to 230 ° C for a range of 10 to 240 minutes.

According to the colored curable resin composition of the present invention, a coating film, a pattern, and a high-quality color filter excellent in heat resistance and light resistance can be obtained. In addition, a display device including such a color filter or a pattern as a part of the components is, for example, a device related to various colored images such as a known liquid crystal display device, an organic EL device, or a solid-state imaging device. It can be used in a well-known manner.

Next, the examples are listed to explain the hair more specifically. Bright. In the examples, the content and the % and the amount of the use amount are used, and when it is not particularly limited, it means a mass basis.

Hereinafter, the structure of the compound was confirmed by mass analysis (LC; Model 1200, manufactured by Agilent, MASS; LC/MSD model manufactured by Agilent).

[Synthesis Example 1]

After adding 65 parts of water to 7.5 parts of 2-amino-4-methylsulfonyl-6-nitrophenol (CAS No. 101861-04-5), 1.3 parts of sodium hydroxide was added and dissolved. Under ice cooling, 6.1 parts of an aqueous solution of 35% sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and then 19.4 parts of 35% hydrochloric acid was added little by little to dissolve and stir for 2 hours to obtain a diazonium salt. Suspension. Next, 5.6 parts of decylamine sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 26 parts of water, and this aqueous solution was slowly added to make the excess sodium nitrite inactive.

Then, 5.6 parts of 3-methyl-1-phenyl-5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 70 parts of water, and the pH was adjusted to 8.0 using sodium hydroxide. Here, the suspension containing the diazonium salt takes 15 minutes, and a 10% sodium hydroxide solution is appropriately added while the pH is controlled in the range of 7 to 7.5, and the mixture is dropped. After the dropwise addition was terminated, stirring was continued for another 30 minutes to obtain a yellow suspension. Stir for 1 hour. The yellow solid obtained by filtration was dried under reduced pressure at 60 ° C to obtain 11.7 parts (yield: 87%) of the compound of formula (p-2).

10 parts of the compound of the formula (p-2) was added to 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) to dissolve, and ammonium sulfate (III) 12 hydrate was added (Wako Pure Chemical Industries, Ltd.) 3.1 parts, 3.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.), and then heated under reflux for 4 hours and a half. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline solution, and the red-orange solid obtained after filtration was dried at 60 ° C to obtain 13.6 parts of the compound represented by formula (z-2) (yield 63) %).

[Synthesis Example 2]

In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen gas was introduced at a flow rate of 0.02 L/min to prepare a nitrogen atmosphere, and 305 parts of propylene glycol monomethyl ether acetate was placed, and the mixture was heated to 70 ° C while stirring. Next, 60 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl acrylate (the compound represented by formula (I-1) and the formula represented by formula (II-1) The compound was mixed with a molar ratio of 50:50. 440 parts, dissolved in 140 parts of propylene glycol monomethyl ether acetate, and prepared into a solution. The solution was taken for 4 hours using a dropping funnel, and dropped to keep warm. In a 70 ° C flask.

On the other hand, 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 225 parts of propylene glycol monomethyl ether acetate, and the other solution was used. The funnel was dropped and it took 4 hours to drip into the flask. After the solution of the polymerization initiator was terminated, it was kept at 70 ° C for 4 hours, and then cooled to room temperature to obtain a weight average molecular weight (Mw) of 9.1 × 10 ³ , a molecular weight distribution of 2.16, and a solid content of 34.8%. The acid value of the fraction was 81 mg-KOH/g of the resin B1 solution. The resin B1 has the structural unit shown below.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained by the synthesis example were measured by the GPC method under the following conditions.

Device; K2479 (Shimadzu Corporation (stock) system)

Pipe string; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ° C

Solvent; THF (tetrahydrofuran)

Flow rate; 1.0mL/min

Detector; standard material for RI calibration; TSK Standard Poly- Styrene F-40, F-4, F-288, A-2500, A-500 (made by Tosoh Co., Ltd.)

The weight average molecular weight and the number average molecular weight ratio (Mw/Mn) in terms of polystyrene obtained above were used as the molecular weight distribution.

Example

The composition shown in Table 3 was mixed, and each component was mixed to obtain a colored curable resin composition.

¹⁾ Pigment: mixed pigment dispersant and propylene glycol monomethyl ether acetate in the amount of B-1 ²⁾ , previously dispersed.

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

In addition, in Table 3, each component is represented by the following. Further, the resin (B) is a part by mass converted into a solid content.

Compound (A2): a compound represented by formula (1-c23)

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

Compound (A3):

Pigment: C.I. Pigment Red 254

Resin (B): Resin (B1)

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

Photopolymerization initiator (D): 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one (IRGACURE 369; manufactured by BASF Corporation)

Polymerization initiation aid (D1): 2,4-diethylthioxanthone (KAYACURE (registered trademark) DETX-s; manufactured by Nippon Kayaku Co., Ltd.)

Polymerization initiator (D2): OXE 01 (manufactured by BASF Corporation)

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 coloring patterns]

The composition of the colored curable resin composition was applied by a spin coating method on a 2 square-square glass substrate (Eagle XG; manufactured by Corning Incorporated), and then prebaked at 100 ° C for 3 minutes to form a composition layer. After cooling, the interval between the composition layer on the substrate and the patterned quartz glass mask was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used at 150 mJ/ under atmospheric pressure. The exposure amount of cm ² (365 nm reference) was irradiated with light. Further, the mask used a mask formed with a line and space pattern of 100 μm. After the light irradiation, the coating film was immersed in a water-based developing solution containing 0.12% of a nonionic surfactant and 2% of sodium carbonate, and immersed for development at 23 ° C for 80 seconds, and then washed in an oven at 230 ° C. After 20 minutes of post-baking, a colored pattern can be obtained.

[Measurement of film thickness]

The film thickness of the obtained coloring pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 3.

[Colorimetric evaluation]

The coloring pattern on the obtained glass substrate was measured for spectroscopic using a color measuring machine (OSP-SP-200; manufactured by Olympus Co., Ltd.), and the XYZ coloring system of CIE was measured using the isochromatic function of the C light source. The XY chromaticity coordinate (X, Y) and the tristimulus value Y. The larger the value of Y, the higher the brightness. The results are shown in Table 3.

[Contrast evaluation]

Exposure was carried out without using a photomask, and the same coloring process as that of forming a colored pattern was performed except that development was not performed, and a colored coating film on a glass substrate was produced. For the colored coating film on the obtained glass substrate, a contrast color measuring machine (CT-1; Detector, BM-5A, light source; F-10) was used, and the blank value was set to 30,000. , measure the contrast value. A colored coating film on a glass substrate was used as a measurement sample by a polarizing film (POLAX-38S; manufactured by Luceo Corporation). The results are shown in Table 4.

[Industry use possibility]

According to the colored curable resin composition of the present invention, a color filter excellent in brightness and contrast can be produced.

Claims (8)

A colored curable resin composition containing a colorant (A), a resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), and further contains the following (iv) a boron complex (F) or a zinc complex (G) of the following (v), wherein the coloring agent (A) contains (i) and further contains (ii) and (iii) At least one of the group formed, (i) a cation represented by 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, the aliphatic hydrocarbon group and the aromatic group. The hydrogen atom contained in the group hydrocarbon group may be substituted by a hydroxyl group, -OR ³³ or a halogen atom; R ³³ represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms; and R ²⁵ and R ²⁶ each independently represent hydrogen; An atom or a methyl group; R ²⁷ represents an ethyl group, a propane-1,3-diyl group or a propane-1,2-diyl group; and R ²⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; An integer represented by 1 to 4, and when n is an integer of 2 or more, the plural R ²⁷ groups may be the same or different from each other; (ii) the compound represented by the formula (A1) In the 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 -SO ₂ R ²⁹ ; and R ²⁹ means -OH. , -NHR ³⁰ or -R ³² ; R ³⁰ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a cyclohexyl group which may be substituted by an alkyl group having 1 to 4 carbon atoms, -R ³¹ - OR ³² , -R ³¹ -CO-OR ³² , -R ³¹ -O-CO-R ³² , or an aralkyl group having 7 to 10 carbon atoms; R ³¹ represents a divalent aliphatic group having 1 to 8 carbon atoms a hydrocarbon group; 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 amine group; and M ¹ represents a Cr or a Co; Is a Na or K; (iii) a pigment (iv) selected from the group consisting of a yellow pigment, an orange pigment, and a red pigment, and a boron complex represented by the formula (4), In the formula (4), W ₁ and W ₂ each independently represent a catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, or 2 which may have a substituent. 2'-biphenyldiol, 3-hydroxy-2-naphthoic acid which may have a substituent, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2- which may have a substituent Naphthoic acid, a binaphthol which may have a substituent, a salicylic acid which may have a substituent, a benzoic acid which may have a substituent or a mandelic acid which may have a substituent; (v) a zinc complex represented by formula (5), In the 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. The colored curable resin composition according to claim 1, wherein the colorant (A) is a coloring agent containing (i), (ii), and (iii). The colored curable resin composition according to claim 1, wherein the colorant (A) is a coloring agent containing (i) and (ii). The colored curable resin composition according to claim 1, wherein the colorant (A) is a coloring agent containing (i) and (iii). The colored curable resin composition according to any one of claims 1 to 4, wherein the pigment is selected from the group consisting of CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, and CI Pigment Red 177. At least one of the group consisting of CI Pigment Red 242 and CI Pigment Red 254. The colored curable resin composition according to any one of claims 1 to 4, wherein M ¹ is Cr. A color filter formed of the colored curable resin composition according to any one of claims 1 to 6. A display device comprising the color filter of claim 7 of the patent application.