JP6028326B2 - Colored curable resin composition - Google Patents

Description

  The present invention relates to a 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 dye obtained by sulfonamidating a compound represented by the formula (A2-1a) and a compound represented by the formula (A2-1b) with 2-ethylhexylamine as a colorant And C.I. I. A colored curable resin composition containing Pigment Blue is known (Patent Document 1).

JP 2010-211198 A

  Conventionally known colored curable resin compositions described above have not always been sufficiently satisfactory in the brightness of the color filter obtained from the colored curable resin composition.

［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のアルキル基又は炭素数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以上の整数である場合、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、それぞれ独立に、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、それぞれ独立に、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。］
で表される化合物を含む着色剤である着色硬化性樹脂組成物。 The present invention includes the following inventions.
[1] including a colorant, a resin, a polymerizable compound, and a polymerization initiator,
The colorant 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 an integer greater than or equal to 2, several R < ⁵ > may mutually be same or different.
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 each 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 curable resin composition which is a coloring agent containing the compound represented by these.

[2] The colored curable resin composition according to [1], wherein the colorant further includes a pigment.
[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].

［式（１’）中、Ｒ¹及びＲ²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。
Ｒ⁴³及びＲ⁴⁴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ハロゲン原子で置換されていてもよく、該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Ｒ⁴³は、一緒になって窒素原子を含む環を形成してもよく、Ｒ²及びＲ⁴⁴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以上の整数である場合、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、それぞれ独立に、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、それぞれ独立に、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。］
で表される化合物を含む着色剤である着色硬化性樹脂組成物。 Furthermore, the present invention includes the following inventions.
[5] including a colorant, a resin, a polymerizable compound, and a polymerization initiator,
The colorant is represented by the formula (1 ′):

[In Formula (1 ′), R ¹ and R ² each independently represent a phenyl group which may have a substituent.
R ⁴³ and R ⁴⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, —CH ₂ — contained in the hydrocarbon group may be replaced by —O—, —CO— or —NR ¹¹ —.
R ¹ and R ⁴³ may be combined to form a ring containing a nitrogen atom, and R ² and R ⁴⁴ 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 an integer greater than or equal to 2, several R < ⁵ > may mutually be same or different.
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 each 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 curable resin composition which is a coloring agent containing the compound represented by these.

  According to the colored curable resin composition of the present invention, a color filter with high brightness can be formed.

The colored curable resin composition of the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and the colorant (A) is represented by the formula (1). A compound represented by the following (hereinafter sometimes referred to as “compound (1)”).
The colorant (A) preferably further contains a pigment (A1).
The colored curable resin composition of the present invention preferably further contains a solvent (E).
In addition, the colored curable resin composition of the present invention includes, if necessary, a dye different from the compound (1) (hereinafter sometimes referred to as “dye (A2)”), a polymerization initiator (D1), and a surfactant. It may contain at least one selected from the group consisting of (F).

［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のアルキル基又は炭素数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以上の整数である場合、複数のＲ⁵は同一であるか相異なる。
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、それぞれ独立に、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、それぞれ独立に、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。］ <Compound (1)>
The colored curable resin composition of the present invention can produce a color filter with high brightness by including the compound (1) as a colorant. The compound (1) may be a tautomer thereof.

[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 an integer of 2 or more, the plurality of R ⁵ are the same or different.
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 each 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 representing 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 heptyl. Straight chain alkyl group having 1 to 20 carbon atoms such as octyl group, nonyl 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 a group, neopentyl group and 2-ethylhexyl group; 3 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group ˜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.

The monovalent saturated hydrocarbon group having 1 to 10 carbon atoms representing R ³ and R ^4, are those having 1 to 10 carbon atoms among those given as the saturated hydrocarbon group 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, an isopropoxy group is 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. Monovalent saturated hydrocarbon groups are more preferred, and methyl and ethyl groups are particularly preferred.

Examples of the alkyl group having 1 to 6 carbon atoms representing 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 representing 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.
As R < ⁶ > and R < ⁷ >, a hydrogen atom, a methyl group, and an ethyl group are preferable, and a hydrogen atom is more preferable.
m is preferably an integer of 0 to 2, and more preferably 1 or 2.

［式（１’）中、Ｒ⁴³及びＲ⁴⁴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ハロゲン原子で置換されていてもよく、該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Ｒ⁴³は、一緒になって窒素原子を含む環を形成してもよく、Ｒ²及びＲ⁴⁴は、一緒になって窒素原子を含む環を形成してもよい。
Ｒ¹、Ｒ²、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ^1０、Ｒ^１１、ｍ及びＺ⁺は、前記と同義である。］
炭素数１〜１０の１価の飽和炭化水素基としては、Ｒ^３及びＲ^４におけるものと同様の基が挙げられ、好ましい基も同じである。
Ｒ¹及びＲ⁴³が一緒になって形成する環、及びＲ²及びＲ⁴⁴が一緒になって形成する環としては、Ｒ¹及びＲ³が一緒になって形成する環と同様の環が挙げられる。 The compound (1) is preferably a compound represented by the formula (1 ′).

[In the formula (1 ′), R ⁴³ and R ⁴⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group is substituted with a halogen atom. And —CH ₂ — contained in the saturated hydrocarbon group may be replaced by —O—, —CO— or —NR ¹¹ —.
R ¹ and R ⁴³ may be combined to form a ring containing a nitrogen atom, and R ² and R ⁴⁴ may be combined to form a ring containing a nitrogen atom.
R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , m and Z ⁺ are as defined above. ]
Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms include the same groups as those in R ³ and R ⁴ , and preferred groups are also the same.
Examples of the ring formed by combining R ¹ and R ⁴³ and the ring formed by combining R ² and R ⁴⁴ include the same ring as the ring formed by combining R ¹ and R ^3. It is done.

［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。
ｒ及びｓは、互いに独立に、０〜５の整数を表す。ｒが２以上である場合、複数のＲ²³は同一でも異なってもよく、ｓが２以上である場合、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 represent an alkyl group having 1 to 4 carbon atoms.
r and s each independently represent an integer of 0 to 5. When r is 2 or more, the plurality of R ²³ may be the same or different, and when s is 2 or more, the plurality of R ²⁴ may be the same or different. ]

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 each independently preferably a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. R ²³ and R ²⁴ are preferably methyl groups.
r and s are preferably integers of 0 to 2, and are 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が好ましく、メチル基及びエチル基がより好ましい。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 each independently preferably a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. 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.

The content of the compound (1) is preferably 0.025% by mass or more and 48% by mass or less, more preferably 0.08% by mass or more and 42% by mass or less, and more preferably 0.1% by mass or more with respect to the total solid content. 30 mass% or less is more preferable. 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.
When the colorant (A) contains the pigment (A1) and / or the dye (A2) together with the compound (1), the content of the compound (1) is 0. 0% relative to the total amount of the colorant (A). 5 mass% or more and 80 mass% or less are preferable, 1 mass% or more and 70 mass% or less are more preferable, and 1 mass% or more and 50 mass% or less are more preferable.

<Pigment (A1)>
The pigment (A1) is not particularly limited, and a known pigment can be used. Examples thereof include compounds classified as pigments according to the color index (published by The Society of Dyers and Colorists).
Examples of the pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 175, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. Pigments;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60, 80; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as CI Pigment Green 7, 36, 58;
C. I. Brown pigments such as CI Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.
These pigments may be used alone or in combination of two or more.

  Examples of the pigment include C.I. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and the like, and C.I. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38 are preferred. I. Pigment blue 15: 3, 15: 6 and C.I. I. Pigment Violet 23 is more preferable, and C.I. I. Pigment Blue 15: 6 is more preferable. By including the above-mentioned pigment, it is easy to optimize the transmission spectrum, particularly when the colored curable resin composition of the present invention is prepared as a blue colored curable resin composition, and the light resistance and chemical resistance of the color filter. Good.

The pigment (A1) is optionally treated with rosin, surface treatment using a pigment derivative having an acidic group or basic group introduced, grafting onto the pigment surface with a polymer compound, sulfuric acid atomization method, etc. May be subjected to the atomization treatment by, cleaning treatment with an organic solvent or water for removing impurities, removal treatment of ionic impurities by an ion exchange method, or the like.
The pigment (A1) 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.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by CIBA), and Ajispur (Ajinomoto Fine). (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.
When the pigment dispersant is used, the amount used is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less with respect to the pigment (A1). When the amount of the pigment dispersant used is within the above range, a pigment dispersion having a uniform dispersion state tends to be obtained.

  When the colorant (A) contains the pigment (A1), the content of the pigment (A1) is preferably 20% by mass or more and 99.5% by mass or less, and 30% by mass with respect to the total amount of the colorant (A). More preferred is 99% by mass or less.

<Dye (A2)>
Examples of the dye (A2) include oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfonamides of acid dyes. of Dyers and Colorists)) and known dyes described in dyeing notes (Color Dyeing). Also, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline And dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

Specifically, C.I. I. Solvent Yellow 4 (hereinafter, description of CI Solvent Yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 162;
C. I. Solvent Red 45, 49, 125, 130, 218;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent Blue 4, 5, 37, 67, 70, 90;
C. I. Solvent Green 1, 4, 5, 7, 34, 35, etc. I. Solvent dyes,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,289,308,312,315,316,339,341,345,346,349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Violet 6B, 7, 9, 17, 19, 30, 102;
C. I. Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 62, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;
C. I. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. I. Acid dyes,
C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 2 5,246,247,248,249,250,251,252,256,257,259,260,268,274,275,293;
C. I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. I. Direct dyes,
C. I. C. such as Disperse Yellow 54, 76 I. Disperse dyes,
C. I. Basic Red 1, 10;
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;
C. I. C. such as Basic Green 1; I. Basic dyes,
C. I. Reactive Yellow 2, 76, 116;
C. I. Reactive Orange 16;
C. I. Reactive Red 36; I. Reactive dyes,
C. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Red 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
C. I. Modern orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modern Blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61 74, 77, 83, 84;
C. I. Modern Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. I. Modern dyes,
C. I. C. of Bat Green 1 etc. I. Vat dye,
Etc.
Of these, blue dyes, violet dyes and red dyes are preferred.
These dyes may be appropriately selected according to the desired spectral spectrum of the color filter. These dyes may be used alone or in combination of two or more.

［式（４）中、Ｇ^１は炭素数２〜１２のアルカンジイル基を表し、該アルカンジイル基に含まれる水素原子は、炭素数１〜４のアルキル基で置換されていてもよく、該アルカンジイル基に含まれる−ＣＨ_２−は、−Ｏ−で置き換わっていてもよい。
Ｊ^１は、水素原子、−ＮＲ^ａＲ^ｂ又は−ＮＲ^ａＲ^ｂＨ^＋Ｑ⁻を表す。
Ｒ^ａ及びＲ^ｂは、互いに独立に、水素原子又は炭素数１〜８のアルキル基を表す。
Ｑ⁻は、ハロゲン化物イオン、ＢＦ_４ ⁻、ＰＦ_６ ⁻、ＣｌＯ_４ ⁻、Ｘ−ＣＯ_２ ⁻又はＹ−ＳＯ_３ ⁻を表す。
Ｘ及びＹは、それぞれ独立に、１価の有機基を表す。
ｐは１〜４の整数を表す。］
式（４）は、式（４−０）で表される化合物に含まれるｐ個の水素原子が、−ＳＯ_２−ＮＨ−Ｇ^１−Ｊ^１で置換されていることを表す。ｐが２以上である場合、複数の−ＳＯ_２−ＮＨ−Ｇ^１−Ｊ^１は、互いに同一でも異なっていてもよい。

Moreover, in the classification | category by a chemical structure, a phthalocyanine dye is preferable and the compound represented by Formula (4) is more preferable.

[In Formula (4), G ¹ represents an alkanediyl group having 2 to 12 carbon atoms, and a hydrogen atom contained in the alkanediyl group may be substituted with an alkyl group having 1 to 4 carbon atoms, —CH ₂ — contained in the alkanediyl group may be replaced by —O—.
J ¹ is a hydrogen atom, ^-NR a ^{R b} or ^-NR a ^R b ^H + Q ^- represents a.
R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
Q ⁻ represents a halide ion, BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , X—CO ₂ ^— or Y—SO ₃ ^— .
X and Y each independently represent a monovalent organic group.
p represents an integer of 1 to 4. ]
Formula (4) represents that p hydrogen atoms contained in the compound represented by formula (4-0) are substituted with —SO ₂ —NH—G ¹ —J ¹ . When p is 2 or more, the plurality of —SO ₂ —NH—G ¹ —J ¹ may be the same as or different from each other.

［式（Ｇ−１）及び式（Ｇ−２）中、Ｇ^２〜Ｇ^５は、それぞれ独立に、炭素数１〜８のアルカンジイル基を表す。
ｎ^１は、１〜３の整数を表す。
ｎ^２は、０〜３の整数を表す。
ただし、式（Ｇ−１）で表される基に含まれる炭素原子及び酸素原子の合計数は、３〜１２であり、式（Ｇ−２）で表される基に含まれる炭素原子及び酸素原子の合計数は、ぞれぞれ２〜１２である。
＊は、−ＮＨ−との結合手を表す。］ Examples of the alkanediyl group having 2 to 12 carbon atoms include a methylene group, an ethylene group, a propanediyl group, and a butanediyl group.
Examples of the alkanediyl group having 2 to 12 carbon atoms in which —CH ₂ — is replaced by —O— include a group represented by the formula (G-1) and a group represented by the formula (G-2). .

[In Formula (G-1) and Formula (G-2), G ^{2 to} G ⁵ each independently represents an alkanediyl group having 1 to 8 carbon atoms.
n ¹ represents an integer of 1 to 3.
n ² represents an integer of 0 to 3.
However, the total number of carbon atoms and oxygen atoms contained in the group represented by formula (G-1) is 3 to 12, and carbon atoms and oxygen contained in the group represented by formula (G-2). The total number of atoms is 2 to 12, respectively.
* Represents a bond with -NH-. ]

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

Examples of —SO ₂ —NH—G ¹ —J ¹ include groups represented by the following formulas.

When G ¹ is a group represented by the formula (G-1), examples of —SO ₂ —NH—G ¹ -J ¹ include a group represented by the following formula.

When G ¹ is a group represented by the formula (G-2), examples of —SO ₂ —NH—G ¹ -J ¹ include a group represented by the following formula.

When J ¹ is —NR ^a R ^b , examples of —SO ₂ —NH—G ¹ —J ¹ include groups represented by the following formulae.

When J ¹ is —NR ^a R ^b H ⁺ Q ^— , examples of —SO ₂ —NH—G ¹ —NR ^a R ^b H ⁺ include groups represented by the following formulae.

［Ｒ^ｙは、炭素数１〜２０のアルキル基を表す。
ｍは、０〜５の整数を表す。］
Ｑ⁻としては、Ｘ−ＣＯ_２ ⁻及びＹ−ＳＯ_３ ⁻が好ましく、式（Ｑ−４）で表されるアニオンがより好ましい。これらのアニオンであると、式（２）で表される化合物の溶剤への溶解性が高くなる傾向がある。 Q ⁻ represents a halide ion, BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , X—CO ₂ ^— or Y—SO ₃ ^— .
X and Y represent a monovalent organic group. As a monovalent organic group, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, the group which combined these, etc. are mentioned.
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group.
Examples of the cycloalkyl group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclodecyl group.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, and an anthryl group.
X—CO ₂ ^— is an organic anion containing a CO ₂ ^— group, and Y—SO ₃ ^— is an organic anion containing an SO ₃ ^— group. For example, the formula (Q-1) to the formula (Q-4) The anion represented by these is mentioned.

[ ^Ry represents an alkyl group having 1 to 20 carbon atoms.
m represents an integer of 0 to 5. ]
Q ^- The, X-CO ₂ ^- and Y-SO ₃ ^- are preferable, and anions represented by the formula (Q-4) is more preferable. When these anions are used, the solubility of the compound represented by the formula (2) in the solvent tends to increase.

Examples of the compound represented by formula (4) include compounds represented by formula (2-1) to formula (2-92). Formula (2-1) Among the compounds represented by - formula (2-92), if ^{n a} is an integer of 2 or more, a plurality of _-SO 2 ^{-NH-G 1} -J 1 is different each benzene It is preferably bonded to a ring.

For example, specific examples of the compound represented by the formula (2-24) include compounds represented by the formula (2-24-1) and the formula (2-24-2).

  When the colorant (A) contains the dye (A2), the content of the dye (A2) is preferably 0.5% by mass or more and 35% by mass or less, and preferably 1% by mass with respect to the total amount of the colorant (A). More preferred is 30% by mass or less.

As the colorant (A), a colorant composed of the compound (1) and the pigment (A1) and a colorant composed of the compound (1), the pigment (A1) and the dye (A2) are preferable.
When the colorant (A) is a colorant composed of the compound (1) and the pigment (A1), these contents are respectively based on the total amount of the colorant (A).
Compound (1): 0.5 mass% or more and 80 mass% or less Pigment (A1); 20 mass% or more and 99.5 mass% or less is preferable,
Compound (1): 1 mass% or more and 50 mass% or less Pigment (A1); 50 mass% or more and 99 mass% or less are more preferable.

When the colorant (A) is a colorant composed of the compound (1), the pigment (A1) and the dye (A2), the content of each of these is relative to the total amount of the colorant (A).
Compound (1): 0.5 mass% or more and 79.5 mass% or less Pigment (A1); 20 mass% or more and 99 mass% or less Dye (A2); 0.5 mass% or more and 35 mass% or less are preferable,
Compound (1): 1% by mass or more and 50% by mass or less Pigment (A1): 49% by mass or more and 98% by mass or less Dye (A2): 1% by mass or more and 30% by mass or less is more preferable.

  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 it is used as a color filter is sufficient, and the resin (B) and the polymerizable compound (C) are contained in a necessary amount in the composition. Therefore, a pattern with sufficient mechanical strength can be formed.

<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 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 (a1) 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.

  (B1) is, for example, a monomer (b1-1) having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”) And a monomer (b1-2) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter may be 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 Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate ( For example, Cyclomer A400 (manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), represented by formula (I) Examples thereof include compounds and compounds represented by formula (II).

[In Formula (I) and Formula (II), R ⁵¹ and R ⁵² 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 ⁵¹ and X ⁵² represents a single ^{bond, -R 53 -, * - R} 53 -O -, * - R 53 -S- or * -R ⁵³ represents a -NH-.
R ⁵³ 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 ⁵¹ and R ⁵² 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 ⁵¹ and X ⁵² are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O— and * —CH ₂ CH ₂ —O—, and 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 any one of the formulas (I-1) to (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 any one of the formulas (II-1) to (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) can be used alone. They can also be mixed in any ratio. When mixing, the mixing ratio is a molar ratio, preferably 5:95 to 95: 5, more preferably 10:90 to 90:10, and still more preferably 20:80 in the formula (I): formula (II). ~ 80: 20.

  As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. (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.

  As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (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.
Of these, styrene, 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.

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 colored curable resin composition tends to have excellent storage stability, developability when forming a pattern, and solvent resistance of the resulting pattern. is there.

  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.) Any solvent may be used as long as it dissolves each monomer. Examples of the solvent (E) for the colored curable resin composition include the solvents described below.

  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 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 the pattern, and the solvent resistance and heat resistance of the resulting pattern are obtained. In addition, the mechanical strength tends to be excellent.

  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 it within this range, the storage stability of the colored curable resin composition, the developability when forming the pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting pattern are improved. Tend. 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 preferably in the following range with respect to the total number of moles of all 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 (highmic acid anhydride) and the like. It is done. 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 Resin such as resin obtained by adding glycidyl (meth) acrylate to acid copolymer [K4]; resin obtained by reacting (meth) acrylic acid with tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer , Tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resin such as a resin obtained by reacting (meth) acrylic acid with the polymer [K5]; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid and tetrahydro Examples thereof include a resin [K6] such as a resin reacted with phthalic anhydride.
These resins may be used alone or in combination of two or more.

  Especially, as resin (B), resin [K1], resin [K2], and resin [K4] 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 within the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed portion in the developer is good, and the resolution tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

  The acid value of the resin (B) is 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, and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

  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 pattern can be formed, and the resolution and the remaining film ratio of the pattern tend to be improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by heat or an active radical and / or acid generated from the polymerization initiator (D). For example, a compound having a polymerizable ethylenically unsaturated bond is used. Preferably, it 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. The polymerizable compounds may be used alone or in combination of two or more.
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 pattern formation and the chemical resistance of the pattern 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. More preferred is a polymerization initiator containing a sulfur compound.

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（登録商標）ＯＸＥ０１、ＯＸＥ０２（以上、ＢＡＳＦ社製）、Ｎ−１９１９（ＡＤＥＫＡ社製）等の市販品を用いてもよい。 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, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-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 (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used.

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 (registered trademark) 369, 907 and 379 (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-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-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) 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) -Methylphenyl) Thenyl] -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 and 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 (trialkoxy) Phenyl) 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, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- 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, dimethyl (4-acetoxyphenyl) sulfonium p-toluenesulfonate, benzyl (4-acetoxy). Phenyl) methylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, onium salts such as diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And 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 that productivity is improved.

In addition to the polymerization initiator (D), a polymerization initiation assistant (D1) may further be included. The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the photopolymerizable compound that has been polymerized by the polymerization initiator.
Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

  Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylaminobenzoate, N, N-dimethyl-p-toluidine, 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, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

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

Carboxylic acid compounds include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.
The polymerization initiation assistant (D1) may be used alone or in combination of two or more.

  When these polymerization initiation assistants (D1) are used, the amount used 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, the pattern can be formed with higher sensitivity, and the productivity of the pattern tends to be improved.

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent, aromatic hydrocarbon solvent, amide solvent, dimethyl sulfoxide, etc. Can be selected and used.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate and γ-butyrolactone.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, and the like phenetol and methyl anisole.

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

  Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. Etc.

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

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

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

These solvents may be used alone or in combination of two or more.
Among the above-mentioned solvents, an organic solvent having a boiling point at 1 atm of 120 ° C. or higher and 180 ° C. or lower is preferable from the viewpoints of coating properties and drying properties. As the solvent (E), propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl- 2-Pentanone and N, N-dimethylformamide are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and ethyl 3-ethoxypropionate are more preferred.

  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 total amount of 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. .

<Surfactant (F)>
Examples of the surfactant (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) Can be mentioned.

  Examples of the fluorosurfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals), Surflon (registered trademark) S381, S382, SC101, SC105 (Asahi Glass Co., Ltd.) and E5844 (Daikin Fine Chemical Laboratory Co., Ltd.).

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

These surfactants may be used alone or in combination of two or more.
The content of the surfactant (F) is preferably 0.001% by mass or more and 0.2% by mass or less, and preferably 0.002% by mass or more and 0.00% by mass or less with respect to the total amount of the colored curable resin composition. It is 1 mass% or less, More preferably, it is 0.01 mass% or more and 0.05 mass% or less. This content does not include the content of the pigment dispersant. When the content of the surfactant (F) is within the above range, the flatness of the coating film can be improved.

<Other ingredients>
The colored curable resin composition of the present invention may contain various additives such as a filler, other polymer compound, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent, if necessary. .

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, the compound (1), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and the pigment (A1) and dye used as necessary. (A2) It can be prepared by mixing the polymerization initiation assistant (D1), the surfactant (F), the solvent (E) and other components.
When the pigment (A1) is included, the pigment (A1) is previously mixed with a 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. Is preferred. At this time, part or all of the resin (B) and the pigment dispersant may be blended as necessary. In the obtained pigment dispersion, compound (1), the remainder of resin (B), polymerizable compound (C) and polymerization initiator (D), and the remainder of solvent (E) used as necessary, The objective colored curable resin composition can be prepared by mixing the surfactant (F) and other components so as to have a predetermined concentration.
The compound (1) and the dye (A2) in the case of containing the dye (A2) may be prepared in advance by dissolving them 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 0.01 to 10 μm.

<Color filter manufacturing method>
Examples of a method for producing a color filter 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 and dried to form a composition layer, and the composition layer is exposed through a photomask and developed. In the photolithographic method, a coating film that is a cured product of the composition layer can be formed by not using a photomask and / or not developing during exposure.
The film thickness of the pattern to be produced is not particularly limited, and can be appropriately adjusted according to the purpose and application. 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 film thickness of the composition layer is not particularly limited, and can be appropriately adjusted depending on the material used, application, and the like.

Next, the composition layer is exposed through a photomask for forming a target 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.
It is preferable to use an exposure apparatus such as a mask aligner and a stepper because the entire exposed surface can be irradiated with parallel light rays uniformly and the photomask and the composition layer can be accurately aligned.

By developing the exposed composition layer in contact with a developer, a pattern is formed on the substrate. By the development, the unexposed portion of the composition layer is dissolved and removed in the developer. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium 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 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.

The pattern and coating film thus obtained are useful as a color filter.
According to the colored curable resin composition of the present invention, a color filter having particularly excellent brightness can be produced. The color filter is useful as a color filter used for a display device (for example, a liquid crystal display device, an organic EL device, etc.), electronic paper, a solid-state image sensor, and the like.

  Next, the present invention will be described more specifically with reference to examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

[Synthesis Example 1]
20 parts of the compound represented by the formula (1a) 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 suction filtration residue and dried to obtain 24 parts of a compound represented by the formula (1-1). The yield was 80%.

The structure of the compound represented by the formula (1-1) was confirmed by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 603.4
Exact Mass: 602.2

（質量分析）イオン化モード＝ＥＳＩ＋： ｍ／ｚ＝[Ｍ＋Ｈ]^＋６３０．３
Ｅｘａｃｔ Ｍａｓｓ： ６３０．３ [Synthesis Example 2]
A compound represented by the formula (1-5) was obtained in the same manner as in Synthesis Example 1 except that N-isopropyl-o-toluidine was used instead of N-ethyl-o-toluidine.
Identification of compound represented by formula (1-5)

(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 630.3
Exact Mass: 630.3

（質量分析）イオン化モード＝ＥＳＩ＋： ｍ／ｚ＝[Ｍ＋Ｈ]^＋６５９．９
Ｅｘａｃｔ Ｍａｓｓ： ６５８．９ [Synthesis Example 3]
A compound represented by the formula (1-8) was obtained in the same manner as in Synthesis Example 1 except that N-propyl-2,6-dimethylaniline was used instead of N-ethyl-o-toluidine.
Identification of compound represented by formula (1-8)

(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 659.9
Exact Mass: 658.9

（質量分析）イオン化モード＝ＥＳＩ＋： ｍ／ｚ＝[Ｍ＋Ｈ]^＋７５５．３
Ｅｘａｃｔ Ｍａｓｓ： ７５４．２ [Synthesis Example 4]
A compound represented by the formula (1-12) was obtained in the same manner as in Synthesis Example 1 except that N-benzyl-2,6-dimethylaniline was used instead of N-ethyl-o-toluidine.
Identification of compound represented by formula (1-12)

(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 755.3
Exact Mass: 754.2

[Synthesis Example 5]
A mixture of a compound represented by the formula (A2-1a) and a compound represented by the formula (A2-1b) (trade name Chugai Aminol Fast Pink R; manufactured by Chugai Kasei Co., Ltd.) 15 in a flask equipped with a condenser and a stirrer. 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 exchange water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60 ° C., and represented by dye (A2-2) (formula (A2-2-1) to formula (A2-2-8). 11.3 parts of a mixture of compounds to be obtained.

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部をプロピレングリコールモノメチルエーテルアセテート２２５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、重量平均分子量Ｍｗは、１．３×１０^４、分子量分布が２．５、固形分３３％、溶液酸価が３４ｍｇＫＯＨ／ｇ（固形分換算の酸価は１０３ｍｇＫＯＨ／ｇ）の樹脂Ｂ１溶液を得た。樹脂Ｂ１は下記に示す構造単位を有する。

[Synthesis Example 6]
Nitrogen was flowed at 0.02 L / min into a flask equipped with a stirrer, thermometer, reflux condenser and dropping funnel to form a nitrogen atmosphere, 305 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 70 ° C. with stirring. did. Next, 60 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) The compound is mixed in a molar ratio of 50:50.) A solution is prepared by dissolving 240 parts and 140 parts of propylene glycol monomethyl ether acetate, and the resulting solution is added using a dropping funnel over 4 hours. The solution was dropped into a flask kept at 70 ° C.

On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts of propylene glycol monomethyl ether acetate was placed in a flask using another dropping funnel over 4 hours. It was dripped. 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. The weight average molecular weight Mw was 1.3 × 10 ⁴ , the molecular weight distribution was 2.5, the solid content A resin B1 solution having 33% and a solution acid value of 34 mg KOH / g (acid value in terms of solid content is 103 mg KOH / g) was obtained. Resin B1 has the structural units shown below.

[Synthesis Example 7]
After introducing 182 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 ° C., 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, monomethacrylate of tricyclodecane skeleton (tricyclo [5.2.1.0 ^2,6 ] decan-8-yl 3.6 g of 2,2′-azobisisobutyronitrile was added to a mixture consisting of 22.0 g (0.10 mol) of methacrylate; FA-513M manufactured by Hitachi Chemical Co., Ltd. and 136 g of propylene glycol monomethyl ether acetate. The solution was added dropwise and stirring was continued at 100 ° C. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxy group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. The resin B2 had a weight average molecular weight Mw of 3.0 × 10 ⁴ , a solid content of 37% by mass, and a solid content acid value of 79 mgKOH / g. A solution was obtained. Resin B2 has the structural units shown below.

[Synthesis Example 8]
Into 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. Next, 38 parts of acrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) 282 parts is dissolved in 150 parts of propylene glycol monomethyl ether acetate to prepare a solution using a dropping funnel over 4 hours. The solution was dropped into a flask kept at a temperature of ° C. On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 230 parts of propylene glycol monomethyl ether acetate was placed in a flask using another dropping funnel over 4 hours. It was dripped. After dropping of the solution of the polymerization initiator is completed, the temperature is kept at 70 ° C. for 4 hours, and then cooled to room temperature, the weight average molecular weight Mw is 8.6 × 10 ³ , the molecular weight distribution is 2.2, A resin B3 solution having an acid value of 35% and solid content conversion of 81 mgKOH / g was obtained. Resin B3 has the structural units shown below.

[Synthesis Example 9]
Into a 1 L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed 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 and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by formula (I-1) and a formula (II-1) The solution is prepared by dissolving 336 parts of the compound to be mixed at a molar ratio of 50:50 in 140 parts of ethyl lactate, and the solution is kept at 70 ° C. for 4 hours using a dropping funnel. The solution was dropped into the flask. 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 dropping of the solution of the polymerization initiator is completed, it is kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw is 8.0 × 10 ³ , the molecular weight distribution is 2.5, the solid content is A resin B4 solution having 48% and a solution acid value of 50 mg-KOH / g (acid value in terms of solid content was 104 mgKOH / g) was obtained. Resin B4 has the structural units shown below.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example 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 and Comparative Examples Colored curable resin compositions were obtained by mixing the components so that the compositions shown in Tables 1 and 2 were obtained.

In Tables 1 and 2, “A1-1 ¹⁾ ” was mixed with an acrylic pigment dispersant and propylene glycol monomethyl ether acetate in an amount described in the “E-1 ³⁾ ” column and dispersed in advance.
The "E-12 ⁾ " column represents the total propylene glycol monomethyl ether acetate content.
In Table 1 and Table 2, each component represents the following. Moreover, resin (B) represents the mass part of solid content conversion.
(A) Colorant: 1-1: Compound represented by Formula (1-1) (A) Colorant: 1-5: Compound represented by Formula (1-5) (A) Colorant: 1- 8: Compound represented by formula (1-8) (A) Colorant: 1-12: Compound represented by formula (1-12) (A) Colorant: A1-1: C.I. I. Pigment Blue 15: 6 (Pigment)
(A) Colorant: A2-1: C.I. I. Salt of direct blue 264 and dodecylbenzenesulfonic acid (manufactured by Orient Chemical Industry Co., Ltd.) (dye)
(A) Colorant: A2-2: Dye (A2-2)
(B) Resin: B-1: Resin B1
(B) Resin: B-2: Resin B2
(B) Resin: B-3: Resin B3
(B) Resin: B-4: Resin B4
(C) Polymerizable compound: C-1: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd .; KAYARAD (registered trademark) DPHA)
(D) Polymerization initiator: D-1: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF)
(E) Solvent: E-1: Propylene glycol monomethyl ether acetate (E) Solvent: E-2: Propylene glycol monomethyl ether (E) Solvent: E-3: Ethyl lactate (F) Surfactant: F-1: Mega Fuck (registered trademark) F554 (manufactured by DIC Corporation)
(F) Surfactant: F-2: Polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

[Formation of pattern]
A colored photosensitive composition was applied by spin coating on a 2 inch square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to obtain a composition layer. After cooling, the distance between the glass substrate on which the composition layer is formed and the photomask made of quartz glass is set to 100 μm, and using an exposure machine (TME-150RSK; manufactured by Topcon Corporation), 150 mJ / cm ^{2 in the} atmosphere. Was irradiated with light at an exposure amount (365 nm reference). A photomask having a 100 μm line and space pattern was used. After light irradiation, the coating film was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 80 seconds, washed with water, and 220 ° C. in an oven. And post-baked for 20 minutes to obtain a pattern.

[Film thickness measurement]
About the obtained pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). The results are shown in Table 3.

[Chromaticity evaluation]
About the pattern on the obtained glass substrate, spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and in the XYZ color system of CIE using the color matching function of C light source. xy chromaticity coordinates (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.

[Contrast evaluation]
A coating film was formed on the glass substrate by performing the same operation as the pattern formation except that the exposure was performed without using a photomask. About the obtained coating film, contrast was measured by using a contrast colorimeter (CT-1; manufactured by Aisaka Electric Co., Ltd .; detector: BM-5A, light source: F-10) with a blank value of 30000. A measurement sample was obtained by sandwiching a glass substrate on which a coating film was formed with a polarizing film (POLAX-38S; manufactured by Luceo Co., Ltd.). The results are shown in Table 3.

  From the results of the examples, it was confirmed that the pattern obtained from the colored curable resin composition of the present invention was blue with high brightness. From this, it can be seen that the pattern obtained from the colored curable resin composition of the present invention is useful as a high-brightness color filter, and that a display device including the color filter is excellent in display characteristics.

  According to the colored curable resin composition of the present invention, a color filter with high brightness can be formed.

Claims (4)

Including a colorant, a resin, a polymerizable compound, a surfactant and a polymerization initiator,
The colorant has the formula ( 3 ):

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 represent a methyl group. ]
A colorant comprising a compound represented by:
A colored curable resin composition, wherein the surfactant is any one of a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom.
  The colored curable resin composition according to claim 1, wherein the colorant further comprises a pigment.   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.