JP2013190733A - Colored curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored curable resin composition allowing formation of a color composition layer with less occurrence of crater-shaped defects.SOLUTION: A colored curable resin composition comprises a coloring agent, a resin, a polymerizable compound, a polymerization initiator and a solvent, where the coloring agent is a coloring agent comprising a compound represented by the formula (1) and a pigment, the solvent is a solvent comprising a diacetone alcohol, and the content ratio of the diacetone alcohol is 0.5 mass% or more and 50 mass% or less relative to the total amount of the solvent. In the formula (1), Rand Rrepresent phenyl groups which may have a substituent; Rand Rrepresent monovalent saturated hydrocarbon groups having a carbon number of 1 to 10; Rrepresents -OH or the like; Rand Rare hydrogen atoms or alkyl groups having a carbon number of 1 to 6; and m is an integer of 0 to 4.

Description

  The present invention relates to a colored curable resin composition, a colored pattern, and a color filter, and more particularly, a colored curable resin composition suitable for forming a colored image constituting a color filter used in a liquid crystal display element or a solid-state imaging element. And a colored pattern and a color filter using the colored curable resin composition.

  Colored curable resin compositions are used in the manufacture of color filters used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels. As such a colored curable resin composition, a colored curable resin composition containing ethyl lactate, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate as a solvent is known (Patent Document 1).

JP 2010-211198 A

  In the conventionally known colored curable resin composition, when the colored curable resin composition is applied to a substrate and then dried under reduced pressure to prepare a colored composition layer, the colored curable resin composition is included in the colored curable resin composition. In some cases, the generated solvent bumped and a crater-like defect occurred.

［式（１）中、Ｒ¹及びＲ^２は、互いに独立に、置換基を有していてもよいフェニル基を表す。
Ｒ^３及びＲ^４は、互いに独立に、炭素数１〜１０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、炭素数６〜１０の芳香族炭化水素基又はハロゲン原子で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基で置換されていてもよく、前記飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^１１−で置き換わっていてもよい。
Ｒ¹及びＲ^３は、一緒になって窒素原子を含む環を形成してもよく、Ｒ^２及びＲ^４は、一緒になって窒素原子を含む環を形成してもよい。
Ｒ⁵は、−ＯＨ、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ⁺、−ＣＯ₂Ｈ、−ＣＯ₂ ^-Ｚ⁺、−ＣＯ₂Ｒ⁸、−ＳＯ₃Ｒ⁸又は−ＳＯ₂ＮＲ⁹Ｒ¹⁰を表す。
Ｒ⁶及びＲ⁷は、互いに独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｍは、０〜４の整数を表す。ｍが２以上のとき、複数のＲ⁵は互いに同一でも異なってもよい。
Ｒ⁸は、炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｚ⁺は、⁺Ｎ（Ｒ¹¹）₄、Ｎａ⁺又はＫ⁺を表す。
Ｒ⁹及びＲ¹⁰は、互いに独立に、水素原子又は炭素数１〜２０の１価の飽和炭化水素基を表し、Ｒ⁹及びＲ¹⁰は、互いに結合して窒素原子を含んだ３〜１０員環の複素環を形成していてもよい。
Ｒ¹¹は、互いに独立に、水素原子、炭素数１〜２０の１価の飽和炭化水素基又は炭素数７〜１０のアラルキル基を表す。］ The present invention includes the following inventions.
[1] including a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent,
The colorant is a colorant comprising a compound represented by formula (1) and a pigment,
The solvent is a solvent containing diacetone alcohol,
A colored curable resin composition in which the content of diacetone alcohol is 0.5% by mass or more and 50% by mass or less based on the total amount of the solvent.

[In Formula (1), R < ¹ > and R < ² > represents the phenyl group which may have a substituent mutually independently.
R ³ and R ⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is an aromatic hydrocarbon group having 6 to 10 carbon atoms. Or a hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —O—, —CO— or —NR ¹¹ —.
R ¹ and R ³ may be combined to form a ring containing a nitrogen atom, and R ² and R ⁴ may be combined to form a ring containing a nitrogen atom.
R ⁵ _{is, -OH, -SO 3 H, -SO} 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ Represents.
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 4. When m is 2 or more, the plurality of R ⁵ may be the same as or different from each other.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ and R ¹⁰ are bonded to each other to contain a nitrogen atom and a 3 to 10 member A heterocyclic ring may be formed.
R ¹¹ independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]

[2] The solvent further includes at least one selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, cyclohexanone and ethyl 3-ethoxypropionate [1] The colored curable resin composition as described.

[3] A color filter formed from the colored curable resin composition according to [1] or [2].
[4] A display device including the color filter according to [3].

  According to the colored curable resin composition of the present invention, there is little occurrence of crater-like defects even when a colored composition layer is produced by drying under reduced pressure after coating on a substrate.

The colored curable resin composition of the present invention contains a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).
The colorant (A) includes a compound represented by the formula (1) (hereinafter sometimes referred to as “compound (1)”) and a pigment (A2).
The colored curable resin composition of the present invention preferably further contains a leveling agent (F).
The colored curable resin composition of the present invention may contain a polymerization initiation assistant (D1).
In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

［式（１）中、Ｒ¹及びＲ^２は、互いに独立に、置換基を有していてもよいフェニル基を表す。
Ｒ^３及びＲ^４は、互いに独立に、炭素数１〜１０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、炭素数６〜１０の芳香族炭化水素基又はハロゲン原子で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基で置換されていてもよく、前記飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^１１−で置き換わっていてもよい。
Ｒ¹及びＲ^３は、一緒になって窒素原子を含む環を形成してもよく、Ｒ^２及びＲ^４は、一緒になって窒素原子を含む環を形成してもよい。
Ｒ⁵は、−ＯＨ、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ⁺、−ＣＯ₂Ｈ、−ＣＯ₂ ^-Ｚ⁺、−ＣＯ₂Ｒ⁸、−ＳＯ₃Ｒ⁸又は−ＳＯ₂ＮＲ⁹Ｒ¹⁰を表す。
Ｒ⁶及びＲ⁷は、互いに独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｍは、０〜４の整数を表す。ｍが２以上のとき、複数のＲ⁵は互いに同一でも異なってもよい。
Ｒ⁸は、炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｚ⁺は、⁺Ｎ（Ｒ¹¹）₄、Ｎａ⁺又はＫ⁺を表す。
Ｒ⁹及びＲ¹⁰は、互いに独立に、水素原子又は炭素数１〜２０の１価の飽和炭化水素基を表し、Ｒ⁹及びＲ¹⁰は、互いに結合して窒素原子を含んだ３〜１０員環の複素環を形成していてもよい。
Ｒ¹¹は、互いに独立に、水素原子、炭素数１〜２０の１価の飽和炭化水素基又は炭素数７〜１０のアラルキル基を表す。］ <Colorant (A)>
Compound (1) is represented by Formula (1).

[In Formula (1), R < ¹ > and R < ² > represents the phenyl group which may have a substituent mutually independently.
R ³ and R ⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is an aromatic hydrocarbon group having 6 to 10 carbon atoms. Or a hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —O—, —CO— or —NR ¹¹ —.
R ¹ and R ³ may be combined to form a ring containing a nitrogen atom, and R ² and R ⁴ may be combined to form a ring containing a nitrogen atom.
R ⁵ _{is, -OH, -SO 3 H, -SO} 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ Represents.
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 4. When m is 2 or more, the plurality of R ⁵ may be the same as or different from each other.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ and R ¹⁰ are bonded to each other to contain a nitrogen atom and a 3 to 10 member A heterocyclic ring may be formed.
R ¹¹ independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group. A linear alkyl group having 1 to 20 carbon atoms such as octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and icosyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group A branched alkyl group having 3 to 20 carbon atoms such as neopentyl group and 2-ethylhexyl group; 3 to 3 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group. There are 20 alicyclic saturated hydrocarbon groups.

Examples of —OR ⁸ include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and icosyloxy group.

Examples of —CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

Examples of —SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
Examples of —SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.
Examples of —SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

—SO ₂ NR ⁹ R ¹⁰ includes, for example, a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl 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 N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1 , 4-Dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2, , 2-tetramethylbutyl) sulfamoyl group and the like N-1 substituted sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl And N, N-2-substituted sulfamoyl groups such as a group.

R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom. Examples of the heterocyclic ring include the following.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ³ and R ⁴ include those having 1 to 10 carbon atoms among those listed as the saturated hydrocarbon group for R ⁸ .

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group. Among the groups in which the hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted, the alkyl group having 1 to 3 carbon atoms includes a methyl group, an ethyl group, an n-propyl group, An isopropyl group is mentioned, As a C1-C3 alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, and an isopropoxy group are mentioned.
Examples of the saturated hydrocarbon group substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms include benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, toluoylmethyl group, toluoylethyl group, and toluoylpropyl group. , Toluylbutyl group, methoxyphenylmethyl group, methoxyphenylethyl group, methoxyphenylpropyl group, methoxyphenylbutyl group and the like.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.
Examples of the saturated hydrocarbon group substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, and a chlorobutyl group.

R ³ and R ⁴ are preferably unsubstituted monovalent saturated hydrocarbon groups having 1 to 10 carbon atoms, more preferably monovalent saturated hydrocarbon groups having 1 to 4 carbon atoms, and 1 to 3 carbon atoms. A monovalent saturated hydrocarbon group is more preferred.

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, sec-butyl group, tert- A butyl group, an isopentyl group, a neopentyl group, etc. are mentioned.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Z ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ .
As the ⁺ N (R ¹¹ ) ₄ , at least two of the four R ¹¹ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ¹¹ is preferably 20 to 80, 20 to 60 is more preferable.

The phenyl group representing R ¹ and R ² may have a substituent. Examples of the substituent include a halogen ^{atom, -R 8, -OH, -OR 8} , -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 R 8, -SR 8, -SO 2 R ⁸ , —SO ₃ R ⁸ and —SO ₂ NR ⁹ R ¹⁰ may be mentioned. Among these substituents, —R ⁸ is preferable, and a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is more preferable. -SO ₃ in this case ^- Z ^{+ _{The, -SO 3 - + N (R}} 11) 4 are preferred.
Examples of the phenyl group having a substituent include a toluyl group, a dimethylphenyl group, an ethylphenyl group, a propylphenyl group, an isopropylphenyl group, a methylsulfanylphenyl group, and a methylsulfonylphenyl group. Among these, a phenyl group having a substituent in the ortho position with respect to a bond with nitrogen is preferable.
R ¹ and R ² are each independently a phenyl group having a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, more preferably a toluyl group or a dimethylphenyl group, and o-toluyl. More preferably, it is a group or a 2,6-dimethylphenyl group.

R ¹ and R ³ may be combined to form a ring containing a nitrogen atom, and R ² and R ⁴ may be combined to form a ring containing a nitrogen atom. Examples of the ring containing a nitrogen atom include the following.

The _{^{R 5, -SO 3 H, -SO}} 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ are preferred.
R ⁶ and R ⁷ are preferably a hydrogen atom, a methyl group and an ethyl group, and more preferably a hydrogen atom.
m is preferably an integer of 0 to 2, and more preferably 1 or 2.

［式（２）中、Ｒ²¹、Ｒ²²、Ｒ²³及びＲ²⁴は、互いに独立に、炭素数１〜４のアルキル基を表す。
ｐ及びｑは、互いに独立に、０〜５の整数を表す。ｐが２以上のとき、複数のＲ²³は互いに同一でも異なってもよく、ｑが２以上のとき、複数のＲ²⁴は互いに同一でも異なってもよい。］ As the compound (1), a compound represented by the formula (2) is preferable.

Wherein ^{(2), R 21, R} 22, R 23 and R ^24, independently of each other, represent an alkyl group having 1 to 4 carbon atoms.
p and q represent the integer of 0-5 mutually independently. When p is 2 or more, the plurality of R ²³ may be the same or different from each other, and when q is 2 or more, the plurality of R ²⁴ may be the same or different from each other. ]

Examples of the alkyl group having 1 to 4 carbon atoms representing R ²¹ , R ²² , R ²³ and R ²⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Groups and the like.
R ²¹ and R ²² are preferably each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms. R ²³ and R ²⁴ are preferably methyl groups.
p and q are preferably an integer of 0 to 2, and preferably 1 or 2.

［式（３）中、Ｒ³¹及びＲ³²は、互いに独立に、炭素数１〜４のアルキル基を表す。
Ｒ³³、Ｒ³⁴、Ｒ³⁵及びＲ³⁶は、互いに独立に、水素原子又は炭素数１〜４のアルキル基を表す。］
Ｒ³¹〜Ｒ³⁶を表す炭素数１〜４のアルキル基としては、前記と同じものが挙げられる。Ｒ³¹及びＲ³²は、互いに独立に、炭素数１〜３の１価の飽和炭化水素基であることが好ましい。Ｒ³³〜Ｒ³⁶は、互いに独立に、水素原子又はメチル基であることが好ましい。 As the compound (1), a compound represented by the formula (3) is preferable.
Is preferred.

Wherein (3), R ³¹ and R ^32, independently of each other, represent an alkyl group having 1 to 4 carbon atoms.
R ³³ , R ³⁴ , R ³⁵ and R ³⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]
Examples of the alkyl group having 1 to 4 carbon atoms representing R ^{31 to} R ³⁶ include the same ones as described above. R ³¹ and R ³² are preferably each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms. R ^{33 to} R ³⁶ are preferably each independently a hydrogen atom or a methyl group.

  Examples of compound (1) include compounds represented by any one of formulas (1-1) to (1-15). Especially, the compound represented by Formula (1-1), Formula (1-2) or Formula (1-5)-Formula (1-12) is preferable at the point which is excellent in the solubility to an organic solvent.

As a method for producing the compound (1), the compound represented by the formula (1a), the compound represented by the formula (1b) and the compound represented by the formula (1c) are used in the presence or absence of an organic solvent. The method of making it react with a solvent is mentioned. From the viewpoint of yield, it is preferable to carry out the reaction without solvent. The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 80 ° C to 130 ° C. The reaction time is preferably 1 hour to 12 hours, and more preferably 3 hours to 8 hours.

［式（１ｂ）及び式（１ｃ）中、Ｒ^１〜Ｒ^４は、それぞれ上記と同じ意味を表す。］

[In formula (1b) and formula (1c), R ^{1 to} R ⁴ each represent the same meaning as described above. ]

  Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; alcohol solvents such as methanol, ethanol and butanol; nitro hydrocarbon solvents such as nitrobenzene; methyl isobutyl ketone Ketone solvents such as 1; amide solvents such as 1-methyl-2-pyrrolidone; and the like.

The amount of the compound represented by the formula (1b) and the compound represented by the formula (1c) is preferably 1 mol or more and 8 mol or less with respect to 1 mol of the compound represented by the formula (1a). More preferably, it is 1 mol or more and 5 mol or less. You may make it react in steps, respectively, and you may make it react simultaneously.
It is preferable that the compound represented by the formula (1b) and the compound represented by the formula (1c) have the same structure in that the production of the compound (1) is easy.

  The method for obtaining the target compound (1) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the reaction mixture can be mixed with an acid (for example, acetic acid and the like), and the precipitated crystals can be collected by filtration. The acid is preferably prepared by preparing an aqueous solution of the acid in advance, and then adding the reaction mixture to the aqueous solution. The temperature at which the reaction mixture is added is preferably 10 ° C. or higher and 50 ° C. or lower. Thereafter, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

Examples of the pigment (A2) include organic pigments and inorganic pigments, and compounds classified as pigments by the color index (published by The Society of Dyers and Colorists).
Specific examples of the pigment include C.I. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. And green pigments such as CI Pigment Green 7, 36, and 58.

  Among them, C.I. I. Pigment red violet 23, C.I. I. Pigment Blue 15: 3 and 15: 6 are preferable. I. Pigment Blue 15: 6 is more preferable.

  If necessary, the pigment may be rosin treatment, surface treatment using a pigment derivative or pigment dispersant into which an acidic group or basic group is introduced, a graft treatment on the pigment surface with a polymer compound, sulfuric acid fine particles, etc. A pulverization process such as an atomization method, a cleaning process using an organic solvent or water for removing impurities, a removal process using an ion exchange method for ionic impurities, or the like may be performed. The pigment preferably has a uniform particle size. By carrying out a dispersion treatment by containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

  As the pigment dispersant, commercially available surfactants can be used, for example, silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, etc. These surfactants can be used, and each can be used alone or in combination of two or more. Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, and polyethyleneimines. Other trade names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (Mitsubishi Materials Electronic Chemicals Co., Ltd.), MegaFac (manufactured by DIC Corporation), Florard ( Sumitomo 3M Co., Ltd.), Asahi Guard (Asahi Glass Co., Ltd.), Surflon (AGC Seimi Chemical Co., Ltd.), Solsperse (Geneca Co., Ltd.), EFKA (CIBA Co.), Ajispur (Ajinomoto Fine Techno) Dispersbyk (by Big Chemie) And the like.

  When the pigment dispersant is used, the amount used is preferably 1 part by mass or less, more preferably 0.05 part by mass or more and 0.5 part by mass or less per 1 part by mass of the pigment. When the amount of the pigment dispersant used is in the above range, it is preferable because a pigment dispersion in a uniform dispersion state tends to be obtained.

The content of the compound (1) is preferably 0.1% by mass or more and 60% by mass or less, and more preferably 0.1% by mass or more and 30% by mass or less with respect to the total amount of the colorant (A).
The content of the pigment (A2) is preferably 40% by mass or more and 99.9% by mass or less, and more preferably 70% by mass or more and 99.9% by mass or less with respect to the total amount of the colorant (A).

  The colorant (A) may contain a colorant different from the compound (1) and the pigment (A2) as long as the color performance of the colored curable resin composition of the present invention is not impaired.

  The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and further preferably 10 to 50% by mass with respect to the total amount of the solid content. When the content of the colorant (A) is within the above range, the color density when the color filter is obtained is sufficient, and a necessary amount of resin or polymerizable compound can be contained in the composition. A pattern with sufficient mechanical strength can be formed. Here, the “total amount of solid content” in this specification refers to an amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1] At least one (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), and a cyclic ether structure having 2 to 4 carbon atoms And a copolymer of a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”);
Resin [K2] (a) and (b), monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) In some cases)
Resin [K3] Copolymer of (a) and (c);
Resin [K4] A resin obtained by reacting (b) with a copolymer of (a) and (c);
Resin [K5] A resin obtained by reacting (a) with a copolymer of (b) and (c);
Resin [K6] A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting with a carboxylic acid anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] 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 Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

(B) is, for example, a polymerizable compound having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. (B) is preferably a monomer having a C2-C4 cyclic ether structure and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Can be mentioned.

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

  As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) 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- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by Formula (I), and Formula (II) The compound etc. which are represented by these are mentioned.

[In Formula (I) and Formula (II), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. May be.
X ^a and ^{X b} is a single ^{bond, -R c -, * - R} c -O -, * - represents the R c -S- or ^* -R c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond 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 sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Examples include a -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.
R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— and * —CH ₂ CH ₂ —O—, more preferably a single bond, * —CH _2. CH ₂ —O— (* represents a bond with O).

  Examples of the compound represented by the formula (I) include compounds represented by the formula (I-1) to the formula (I-15). Preferably Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9) or Formula (I-11) to Formula (I-15) The compound represented by these is mentioned. More preferably, the compound represented by Formula (I-1), Formula (I-7), Formula (I-9) or Formula (I-15) is mentioned.

  Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to the formula (II-15). Preferably Formula (II-1), Formula (II-3), Formula (II-5), Formula (II-7), Formula (II-9) or Formula (II-11) to Formula (II-15) The compound represented by these is mentioned. More preferably, the compound represented by Formula (II-1), Formula (II-7), Formula (II-9), or Formula (II-15) is mentioned.

  The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the content ratio thereof [the compound represented by the formula (I): the compound represented by the formula (II)] is: On a molar basis, it is preferably 5:95 to 95: 5, more preferably 20:80 to 80:20.

  (B2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. (B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane , 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

  (B3) is more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

  (B) is preferably (b1) in that the color filter obtained can have higher reliability such as heat resistance and chemical resistance. Furthermore, (b1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 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, it is called “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) There is a bird) Black (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters of
Hydroxy 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, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] 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-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance. preferable.

In the resin [K1], the ratio of the structural unit derived from each is the total structural unit constituting the resin [K1]
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (b); 40-98 mol%
It is preferable that
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (b); 50-90 mol%
It is more preferable that
When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter are excellent. Tend.

  The resin [K1] is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, by substituting oxygen with nitrogen to create a deoxygenated atmosphere, with stirring, The method of heating and heat retention is mentioned. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) As the solvent, any solvent that dissolves each monomer may be used. Examples of the solvent (E) for the colored curable resin composition of the present invention include a solvent described later.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction is used as it is for the preparation of the colored curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of the present invention can be simplified.

In the resin [K2], the ratio of the structural units derived from each of the structural units in the resin [K2]
Structural unit derived from (a); 2-45 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (c); 1 to 65 mol%
It is preferable that
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (c); 5 to 60 mol%
It is more preferable that
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter, There is a tendency to be excellent in heat resistance and mechanical strength.

  Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].

In the resin [K3], the proportion of structural units derived from each of the structural units constituting the resin [K3]
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (c); 40 to 98 mol%
It is preferable that
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (c); 50-90 mol%
It is more preferable that
Resin [K3] can be produced, for example, in the same manner as described for the production method of resin [K1].

Resin [K4] obtains a copolymer of (a) and (c), and (a) has a carboxylic acid and / or carboxylic acid anhydride having (a) a cyclic ether having 2 to 4 carbon atoms that (b) has It can manufacture by adding to.
First, a copolymer of (a) and (c) is produced in the same manner as described in the method for producing resin [K1]. In this case, it is preferable that the ratio of the structural units derived from each is the same as that described for the resin [K3].

Next, the C2-C4 cyclic ether which (b) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer.
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( Dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (eg, hydroquinone, etc.) are placed in a flask and reacted, for example, at 60-130 ° C. for 1-10 hours to produce resin [K4]. it can.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By making this range, the storage stability of the colored curable resin composition, the developability when forming the colored pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting colored pattern are good. Tend to be. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

Resin [K5] obtains a copolymer of (b) and (c) as a first step in the same manner as in the method for producing resin [K1] described above. Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of the structural units derived from (b) and (c) is respectively based on the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol%
Structural unit derived from (c); 5-95 mol%
It is preferable that
Structural unit derived from (b); 10-90 mol%
Structural unit derived from (c); 10 to 90 mol%
It is more preferable that

Further, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) of the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic acid anhydride of (a). Resin [K5] can be obtained by reacting the product.
As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K5], and (b1-1) is more preferable.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5]. Carboxylic anhydride is reacted with a hydroxy group generated by reaction of cyclic ether with carboxylic acid or carboxylic anhydride.
Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride, and the like. As for the usage-amount of carboxylic acid anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6. ] Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meta ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- ( Resin [K2] such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / Glycidyl (meth) acrylate was added to resin [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer such as (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer Resin, tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer added with glycidyl (meth) acrylate, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic Resins such as resins obtained by adding glycidyl (meth) acrylate to an acid copolymer [K4]; resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid , Tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resin [K5] such as a resin obtained by reacting a copolymer with (meth) acrylic acid; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid Furthermore, resin [K6] such as a resin obtained by reacting tetrahydrophthalic anhydride may be used.
Especially, as resin (B), resin [K1] and resin [K2] are preferable.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. . When the molecular weight is in the above range, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and a high resolution and high hardness colored pattern tends to be obtained.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

  The acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150, and still more preferably 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example.

  Content of resin (B) becomes like this. Preferably it is 7-65 mass% with respect to the total amount of solid content, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the remaining film rate tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond. Is a (meth) acrylic acid ester compound.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) ) Isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol Hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Is mentioned.
Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

  The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of the solid content. is there. When the content of the polymerizable compound (C) is within the above range, the remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, and O-acyloxy compounds. More preferred is a polymerization initiator containing a sulfur compound.

前記Ｏ−アシルオキシム化合物としては、例えば、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−｛２−メチル−４−（３，３−ジメチル−２，４−ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−イミン、Ｎ−ベンゾイルオキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−オン−２−イミン等が挙げられる。イルガキュアＯＸＥ０１、ＯＸＥ０２（以上、ＢＡＳＦ社製）、Ｎ−１９１９（ＡＤＥＫＡ社製）等の市販品を用いてもよい。中でも、Ｏ−アシルオキシム化合物は、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン及びＮ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミンからなる群から選ばれる少なくとも１種が好ましく、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミンがより好ましい。これらのＯ−アシルオキシム化合物であると、高明度なカラーフィルタが得られる傾向にある。 The O-acyl oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-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- {2-methyl-4- (3,3-dimethyl-2, 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (ADEKA) may be used. Among these, O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1 At least one selected from the group consisting of -on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred. When these O-acyloxime compounds are used, a color filter with high brightness tends to be obtained.

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

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4 -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one Etc. Commercial products such as Irgacure 369, 907, 379 (above, manufactured by BASF) may be used.
Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxy Examples include acetophenone and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

  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) -6- (4-methoxy Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -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-methylpheny ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

  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 (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4 , 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 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 (trial Xylphenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (for example, see JP-A-7-10913).

  Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, Examples thereof include benzoin tosylate.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so the productivity of the color filter is improved.

<Polymerization initiation aid (D1)>
The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is included, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

  Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4 2-dimethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (Ethylmethylamino) benzophenone and the like can be mentioned, among which 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (Hodogaya Chemical Co., Ltd.) may be used.

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

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

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

  When using these polymerization initiation assistants (D1), the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Preferably it is 1-20 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, a colored pattern can be formed with higher sensitivity and the productivity of the color filter tends to be improved.

<Solvent (E)>
The solvent (E) contains diacetone alcohol (that is, 4-hydroxy-4-methylpentan-2-one), and the content of diacetone alcohol is 0.5% by mass or more and 50% by mass or more based on the total amount of the solvent. It is 1 mass% or less, Preferably it is 1 mass% or more and 30 mass% or less.
The solvent combined with diacetone alcohol is preferably at least one selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, cyclohexanone and ethyl 3-ethoxypropionate, More preferably, it is at least one selected from the group consisting of propylene glycol monomethyl ether acetate and ethyl lactate.

  The content of the solvent (E) is preferably 70 to 95% by mass and more preferably 75 to 92% by mass with respect to the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good. Therefore, it is preferable.

<Leveling agent (F)>
Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms.
Examples of the silicone surfactant include surfactants having a siloxane bond. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH29PA, SH30PA, polyether-modified silicone oil SH8400 (trade name: Toray Silicone; manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (Momentive Performance Materials Japan) Manufactured).

  Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Florard (trade name) FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFuck (trade name) F142D, F171, F172, F173, F177, F183, F183, R30, F554 (manufactured by DIC Corporation), Ftop (trade name) EF301, EF303, EF351, EF351 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (tradename) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100 (all trade names: manufactured by BM Chemie) and the like.

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, MegaFuck (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned.

  The content of the leveling agent (F) is preferably 0.001% by mass to 0.2% by mass, more preferably 0.002% by mass to 0.1% by mass, and still more preferably 0.005% by mass. % Or more and 0.05% by mass or less.

<Other ingredients>
The colored curable resin composition of the present invention includes additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., if necessary. May be included.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention is used, for example, as a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and as necessary. It can be prepared by mixing the leveling agent (F), the polymerization initiation assistant (D1) and other components.
The pigment (A2) is preferably mixed in advance with part or all of the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The desired colored curable resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
Compound (1) may be prepared in advance by dissolving in part or all of the solvent (E) in advance. The solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.1 to 10 μm.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited, and can be adjusted as appropriate according to the purpose and application, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5. ~ 6 μm.

  As the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate In addition, aluminum, silver, or a silver / copper / palladium alloy thin film is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

Formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored curable resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth composition layer is obtained.
Examples of the coating method include spin coating, slit coating, and slit and spin coating.
30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa. The colored curable resin composition of the present invention has an effect that there are few occurrences of crater-like defects even when drying under reduced pressure under such conditions.
The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
Use an exposure device such as a mask aligner or a stepper because the entire exposure surface can be illuminated with parallel rays uniformly, or the photomask can be accurately aligned with the substrate on which the colored composition layer is formed. Is preferred.

A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.
The developing method may be any of paddle method, dipping method, spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

  Furthermore, it is preferable to post-bake the obtained colored pattern. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

  According to the colored curable resin composition of the present invention, a color filter having particularly few defects can be produced. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

Hereinafter, the colored curable resin composition of the present invention will be described in more detail by way of examples.
Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

式（１−１）で表される化合物の同定；
（質量分析）イオン化モード＝ＥＳＩ＋： ｍ／ｚ＝[Ｍ＋Ｈ]^＋６０３．４
Ｅｘａｃｔ Ｍａｓｓ： ６０２．２ [Synthesis Example 1]
20 parts of the compound represented by the formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under shading conditions, and the resulting solution was stirred at 110 ° C. for 6 hours. did. The obtained reaction solution was cooled to room temperature, then added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour, whereby crystals were precipitated. The precipitated crystals were obtained as a residue of suction filtration and then dried to obtain 24 parts of a compound represented by the formula (1-1). The yield was 80%.

Identification of the compound represented by formula (1-1);
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 603.4
Exact Mass: 602.2

式（１−６）で表される化合物の同定
（質量分析）イオン化モード＝ＥＳＩ＋： ｍ／ｚ＝ [Ｍ＋H]^＋ ６５９．４
Ｅｘａｃｔ Ｍａｓｓ： ６５８．３
〔合成例３〕
冷却管及び攪拌装置を備えたフラスコに、式（Ｘ０−１）で表される化合物及び式（Ｘ０−２）表される化合物の混合物（商品名Chugai Aminol Fast Pink R；中外化成製）を１５部、クロロホルム１５０部及びＮ，Ｎ−ジメチルホルムアミド８．９部を投入し、攪拌下２０℃以下を維持しながら、塩化チオニル１０．９部を滴下して加えた。滴下終了後、５０℃に昇温し、同温度で５時間維持して反応させ、その後２０℃に冷却した。冷却後の反応溶液を、攪拌下２０℃以下に維持しながら、２−エチルヘキシルアミン１２．５部及びトリエチルアミン２２．１部の混合液を滴下して加えた。その後、同温度で５時間攪拌して反応させた。次いで得られた反応混合物をロータリーエバポレーターで溶媒留去した後、メタノールを少量加えて激しく攪拌した。この混合物を、イオン交換水３７５部の混合液中に攪拌しながら加えて、結晶を析出させた。析出した結晶を濾別し、イオン交換水でよく洗浄し、６０℃で減圧乾燥して、キサンテン染料Ｘ１（式（Ｘ−１−１）〜式（Ｘ−１−８）で表される化合物の混合物）１１．３部を得た。 [Synthesis Example 2]
A compound represented by the formula (1-6) was obtained in the same manner as in Synthesis Example 1 except that N-isopropyl-2,6-dimethylaniline was used instead of N-ethyl-o-toluidine.

Identification of compound represented by formula (1-6) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 659.4
Exact Mass: 658.3
[Synthesis Example 3]
A mixture of a compound represented by the formula (X0-1) and a compound represented by the formula (X0-2) (trade name Chugai Aminol Fast Pink R; manufactured by Chugai Kasei Co., Ltd.) 15 Part, 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide were added dropwise and 10.9 parts of thionyl chloride was added dropwise while maintaining at 20 ° C. or lower with stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixture of 375 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals are separated by filtration, washed thoroughly with ion-exchanged water, dried under reduced pressure at 60 ° C., and compounds represented by xanthene dye X1 (formula (X-1-1) to formula (X-1-8)) Of 11.3 parts).

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）３０部を乳酸エチル９５部に溶解した溶液を、別の滴下ロートを用いて４時間かけてフラスコ内に滴下した。重合開始剤の溶液の滴下が終了した後、４時間、７０℃に保持し、その後室温まで冷却して、固形分が４８％の樹脂Ｂ１溶液を得た。樹脂Ｂ１は、重量平均分子量が８．０×１０^３、分子量分布（Ｍｗ／Ｍｎ）が２．５、固形分換算の酸価が１０４ｍｇ−ＫＯＨ／ｇであった。樹脂Ｂ１は下記に示す構造単位を有する。

[Synthesis Example 4]
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, 220 parts of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. Next, 84 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) A solution is prepared by dissolving 336 parts of a mixture of compounds (content ratio (molar ratio) is 50:50) in 140 parts of ethyl lactate, and the solution is heated to 70 ° C. over 4 hours using a dropping funnel. It was dripped in the flask kept warm.

On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 95 parts of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. After completion of the dropwise addition of the polymerization initiator solution, the temperature was maintained at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a resin B1 solution having a solid content of 48%. Resin B1 had a weight average molecular weight of 8.0 × 10 ³ , a molecular weight distribution (Mw / Mn) of 2.5, and an acid value in terms of solid content of 104 mg-KOH / g. Resin B1 has the structural units shown below.

The polystyrene-converted weight average molecular weight (Mw) and number average molecular weight (Mn) of the resins obtained in the synthesis examples were measured using the GPC method under the following conditions.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

Examples 1 to 6 and Comparative Example 1
(Preparation of colored curable resin composition)
Each component was mixed so that it might become a composition shown in Table 1, and the colored curable resin composition was obtained.

In Table 1, “A2-1” was mixed with an acrylic pigment dispersant and propylene glycol monomethyl ether acetate in an amount described in the “E-3 ²⁾ ” column and dispersed in advance.
The column “E-3 ¹⁾ ” represents the total content of propylene glycol monomethyl ether acetate.

In Table 1, each component represents the following. Resin (B) represents the content (parts) of the solution.
Colorant (A): 1-1: Compound represented by Formula (1-1) Colorant (A): 1-6: Compound represented by Formula (1-6) Colorant (A): X- 1: Xanthene dye X1
Colorant (A): A2-1: C.I. I. Pigment Blue 15: 6 (Pigment)
Resin (B): Resin B1 solution Polymerizable compound (C): Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd .; KAYARAD (registered trademark) DPHA)
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF)
Solvent (E): E-1: Diacetone alcohol Solvent (E): E-2: Ethyl lactate Solvent (E): E-3: Propylene glycol monomethyl ether acetate Solvent (E): E-4: Propylene glycol monomethyl ether Leveling agent (F): Fluorosurfactant (Megafac (registered trademark) F554; manufactured by DIC Corporation)

  The content rate of each solvent contained in the prepared colored curable resin composition is as shown in Table 2 with respect to the total amount of the solvent contained.

<Preparation of colored pattern>
A colored curable resin composition was applied by spin coating on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to obtain a colored composition layer. After standing to cool, the distance between the substrate on which the colored composition layer is formed and the quartz glass photomask is set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) is used in an air atmosphere at 150 mJ / cm. Light was irradiated with an exposure amount of ² (based on 365 nm). A photomask having a 100 μm line and space pattern was used. The colored composition layer after the light irradiation is developed by immersion in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds, washed with water, Post-baking was carried out at 30 ° C. for 30 minutes to obtain a colored pattern.

[Film thickness measurement]
About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product).

[Chromaticity evaluation]
About the obtained coloring pattern, spectrum was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE using the characteristic function of C light source (X, y) and tristimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 3.

(Defect evaluation)
On a 2-inch square glass substrate (Eagle 2000; manufactured by Corning), a colored curable resin composition was applied by spin coating so that the film thickness after drying was 2.3 μm, and then a vacuum dryer ( VCD Microtech Co., Ltd.) was used and dried under reduced pressure to an ultimate pressure of 100 Pa to obtain a colored composition layer. About the obtained coloring composition layer, the surface was observed using the surface shape optical microscope (250-times magnification; VF-7510; product made from Keyence Corporation). The case where the number of crater-like defects on the substrate was 3 or less was evaluated as ◯, the case where it was 3 or more and 10 or less, Δ, and the case where the number exceeded 10 were evaluated as x. The results are shown in Table 2.

[Foreign matter evaluation]
In the same manner as the defect evaluation, the surface of the obtained colored composition layer was observed using a surface shape optical microscope (magnification 250 times; VF-7510; manufactured by Keyence Corporation). The case where it was not recognized was set as x. The results are shown in Table 2.

  Even when the colored curable resin composition of the present invention is applied to a substrate and then dried under reduced pressure to produce a colored composition layer, the occurrence of crater-like defects is small.

Claims (4)

Including colorants, resins, polymerizable compounds, polymerization initiators and solvents,
The colorant is a colorant comprising a compound represented by formula (1) and a pigment,
The solvent is a solvent containing diacetone alcohol,
A colored curable resin composition in which the content of diacetone alcohol is 0.5% by mass or more and 50% by mass or less based on the total amount of the solvent.

[In Formula (1), R < ¹ > and R < ² > represents the phenyl group which may have a substituent mutually independently.
R ³ and R ⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group is an aromatic hydrocarbon group having 6 to 10 carbon atoms. Or a hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —O—, —CO— or —NR ¹¹ —.
R ¹ and R ³ may be combined to form a ring containing a nitrogen atom, and R ² and R ⁴ may be combined to form a ring containing a nitrogen atom.
R ⁵ _{is, -OH, -SO 3 H, -SO} 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ Represents.
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 4. When m is 2 or more, the plurality of R ⁵ may be the same as or different from each other.
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ and R ¹⁰ are bonded to each other to contain a nitrogen atom and a 3 to 10 member A heterocyclic ring may be formed.
R ¹¹ independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]   The coloring according to claim 1, wherein the solvent is a solvent further comprising at least one selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, cyclohexanone and ethyl 3-ethoxypropionate. Curable resin composition.   A color filter formed from the colored curable resin composition according to claim 1.   A display device comprising the color filter according to claim 3.