JP5938895B2 - 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 and further containing bis (dibutyldithiocarbamate) zinc is known (Patent Document 1).

JP 2011-118365 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、炭素数１〜３のアルコキシ基で置換されていてもよく、前記飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^１１−で置き換わっていてもよい。
Ｒ¹及びＲ^３は、一緒になって窒素原子を含む環を形成してもよく、Ｒ^２及びＲ^４は、一緒になって窒素原子を含む環を形成してもよい。
Ｒ⁵は、−ＯＨ、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ⁺、−ＣＯ₂Ｈ、−ＣＯ₂ ^-Ｚ⁺、−ＣＯ₂Ｒ⁸、−ＳＯ₃Ｒ⁸又は−ＳＯ₂ＮＲ⁹Ｒ¹⁰を表す。
Ｒ⁶及びＲ⁷は、互いに独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｍは、０〜４の整数を表す。ｍが２以上のとき、複数のＲ⁵は同一でも異なってもよい。
Ｒ⁸は、炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｚ⁺は、⁺Ｎ（Ｒ¹¹）₄、Ｎａ⁺又はＫ⁺を表す。
Ｒ⁹及びＲ¹⁰は、互いに独立に、水素原子又は炭素数１〜２０の１価の飽和炭化水素基を表し、Ｒ⁹及びＲ¹⁰は、互いに結合して窒素原子を含んだ３〜１０員環の複素環を形成していてもよい。
Ｒ¹¹は、互いに独立に、水素原子、炭素数１〜２０の１価の飽和炭化水素基又は炭素数７〜１０のアラルキル基を表す。］ The present invention includes the following inventions.
[1] including a colorant, a resin, a polymerizable compound, a polymerization initiator, and an organometallic compound,
The colorant is a colorant containing a compound represented by the formula (1),
A colored curable resin composition in which the maximum value of the molar extinction coefficient in the visible light region of the organometallic compound is smaller than the maximum value of the molar extinction coefficient in the visible light region of the compound represented by formula (1).

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

［式（Ｆ１）中、Ｗ^１及びＷ^２は、互いに独立に、炭素数１〜６の１価の脂肪族炭化水素基又は炭素数６〜１０の１価の芳香族炭化水素基を表し、該脂肪族炭化水素基及び該芳香族炭化水素基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。
Ｍ^１は、金属原子を表す。
ｘは、１〜３の整数を表し、ｘが２以上のとき、複数のＷ^１及びＷ^２は互いに同一でも異なってもよい。］

［式（Ｆ２）中、Ｗ^３及びＷ^４は、互いに独立に、炭素数１〜６の１価の脂肪族炭化水素基を表し、該脂肪族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。
Ｍ^２は、金属原子を表す。
ｙは、１〜３の整数を表し、ｙが２以上のとき、複数のＷ^３及びＷ^４は互いに同一でも異なってもよい。］ [2] The description in [1], wherein the organometallic compound is at least one selected from the group consisting of a compound represented by the formula (F1), a compound represented by the formula (F2), and hydrates thereof. Colored curable resin composition.

[In Formula (F1), W ¹ and W ² each independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, The hydrogen atom contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a hydroxy group.
M ¹ represents a metal atom.
x represents an integer of 1 to 3, and when x is 2 or more, the plurality of W ¹ and W ² may be the same as or different from each other. ]

[In Formula (F2), W ³ and W ⁴ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, and the hydrogen atom contained in the aliphatic hydrocarbon group is a halogen atom May be substituted.
M ² represents a metal atom.
y represents an integer of 1 to ^3, and when y is 2 or more, the plurality of W ³ and W ⁴ may be the same as or different from each other. ]

[3] The colored curable resin composition according to [1] or [2], wherein the colorant further includes a pigment.
[4] A color filter formed from the colored curable resin composition according to any one of [1] to [3].
[5] A display device including the color filter according to [4].

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

It is the schematic explaining the manufacturing method of the color filter of this invention. It is the schematic explaining the manufacturing method of the color filter of this invention. It is the schematic explaining the manufacturing method of the color filter of this invention.

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and an organometallic compound (M).
The colorant (A) includes a compound represented by the formula (1) (hereinafter may be referred to as “compound (1)”), and further preferably includes 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 initiation assistant (D1), and a surfactant. You may contain at least 1 sort (s) chosen from the group which consists of an agent (F).
In addition, in this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

［式（１）中、Ｒ¹及びＲ^２は、互いに独立に、置換基を有していてもよいフェニル基を表す。
Ｒ^３及びＲ^４は、互いに独立に、炭素数１〜１０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、炭素数６〜１０の芳香族炭化水素基又はハロゲン原子で置換されていてもよく、該芳香族炭化水素基に含まれる水素原子は、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基で置換されていてもよく、前記飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^１１−で置き換わっていてもよい。
Ｒ¹及びＲ^３は、一緒になって窒素原子を含む環を形成してもよく、Ｒ^２及びＲ^４は、一緒になって窒素原子を含む環を形成してもよい。
Ｒ⁵は、−ＯＨ、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ⁺、−ＣＯ₂Ｈ、−ＣＯ₂ ^-Ｚ⁺、−ＣＯ₂Ｒ⁸、−ＳＯ₃Ｒ⁸又は−ＳＯ₂ＮＲ⁹Ｒ¹⁰を表す。
Ｒ⁶及びＲ⁷は、互いに独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｍは、０〜４の整数を表す。ｍが２以上のとき、複数のＲ⁵は同一でも異なってもよい。
Ｒ⁸は、炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｚ⁺は、⁺Ｎ（Ｒ¹¹）₄、Ｎａ⁺又はＫ⁺を表す。
Ｒ⁹及びＲ¹⁰は、互いに独立に、水素原子又は炭素数１〜２０の１価の飽和炭化水素基を表し、Ｒ⁹及びＲ¹⁰は、互いに結合して窒素原子を含んだ３〜１０員環の複素環を形成していてもよい。
Ｒ¹¹は、互いに独立に、水素原子、炭素数１〜２０の１価の飽和炭化水素基又は炭素数７〜１０のアラルキル基を表す。］ <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 2 or more, the plurality of R ⁵ may be 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 independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The _{^{R 5, -SO 3 H, -SO}} 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ are preferred.
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（２）中、Ｒ²¹、Ｒ²²、Ｒ²³及びＲ²⁴は、互いに独立に、炭素数１〜４のアルキル基を表す。
ｐ及びｑは、互いに独立に、０〜５の整数を表す。ｐが２以上である場合、複数のＲ²³は同一でも異なってもよく、ｑが２以上である場合、複数のＲ²⁴は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.
p and q represent the integer of 0-5 mutually independently. When p is 2 or more, the plurality of R ²³ may be the same or different, and when q 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 preferably each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms. R ²³ and R ²⁴ are preferably methyl groups.
p and q are preferably an integer of 0 to 2, and preferably 1 or 2.

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

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

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

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

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

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

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

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

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

The content of the compound (1) in the colored curable resin composition of the present invention is preferably 0.025% by mass or more and 48% by mass or less, and 0.08% by mass or more and 42% by mass or less with respect to the total amount of solids. Is more preferable, and 0.1 mass% or more and 30 mass% or less is still 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.

  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.

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

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. As the pigment dispersant, 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), 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 with a uniform dispersion 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)>
The dye (A2) is not particularly limited as long as it is different from the compound (1), and known pigments can be used. Oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, acid dyes And dyes such as sulfonamide derivatives of acid dyes such as compounds classified as dyes (other than pigments and having hues) by the Color Index (published by The Society 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. Examples include vat dyes.

  These dyes may be appropriately selected according to the desired spectral spectrum of the color filter. Of these, blue dyes, violet dyes and red dyes are preferred.

  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 Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by Formula (I), and Formula (II) The compound etc. which are represented by these are mentioned.

[In Formula (I) and Formula (II), R 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.

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

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

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

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, it is called “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) There is a bird) Black (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters of
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2.2 1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5 -Hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [ 2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5 , 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, 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 storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the color filter tend to be excellent. 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 unit 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.

  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 (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example.

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

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

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, (4-acetoxyphenyl) dimethylsulfonium p-toluenesulfonate, benzyl (4-acetoxy). Phenyl) methylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate and other onium salts, 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.

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

  Examples of 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.

  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.

<Organic metal compound (M)>
The organometallic compound (M) is an organic compound having a maximum molar extinction coefficient ε (hereinafter sometimes referred to as “ε _M ”) in the visible light region (wavelength 380 nm to 780 nm) smaller than ε _{M of the} compound (1). It is a metal compound. The organometallic compound is an organometallic complex in which a negative, neutral or positive ligand is coordinated around a metal atom or metal ion, or a metal salt of an organic acid. Among these, those that are soluble in an organic solvent are preferable.

Ε _M of the organometallic compound (M) is prepared by diluting 0.1 g of the organometallic compound (M) to 0.250 L with ethyl lactate, and absorbing the solution in the visible light region with an ultraviolet-visible spectrophotometer. It is obtained by measuring the spectrum and calculating using the Lambert-Beer law.
When 2 or more types of compounds (1) are contained in the colored curable resin composition of this invention, it is based on the compound (1) which has the smallest (epsilon) _M.
Epsilon _M of the organometallic compound (M) is smaller than epsilon _M of compound (1), preferably 1,000 or less, more preferably 500 or less, more preferably 100 or less, still more preferably 80 or less, in particular Preferably it is 60 or less. It is preferable that ε _M is within the above range because the brightness of the color filter tends to increase. When the colored curable resin composition of the present invention contains two or more kinds of compounds (1), ε _M of the organometallic compound (M) is larger than ε _{M of the} compound (1) having the smallest ε _M. small. Furthermore, epsilon _M when the colored curable resin composition of the present invention comprises two or more organometallic compound (M), an organometallic compound having the largest epsilon _M (M) are, epsilon _M of compound (1) Smaller than.

Examples of the metal constituting the metal atom or metal ion of the organometallic compound (M) include typical metals and transition metals.
Typical metals include, for example, group 1 elements (alkali metals), group 2 elements (alkaline earth metals), group 12 elements (zinc group), group 13 elements (boron group), and group 14 of the periodic table. Atoms of metal elements included in group elements (carbon group) and group 15 elements (nitrogen group) can be given.
Specifically, beryllium (Be), magnesium (Mg), aluminum (Al), calcium (Ca), zinc (Zn), gallium (Ga), rubidium (Rb), strontium (Sr), cadmium (Cd), Indium (In), tin (Sn), cesium (Cs), barium (Ba), mercury (Hg), thallium (Tl), lead (Pb), bismuth (Bi), francium (Fr), radium (Ra), etc. Can be mentioned.
Among them, magnesium (Mg), aluminum (Al), calcium (Ca), zinc (Zn), gallium (Ga), rubidium (Rb), strontium (Sr), indium (In), cesium (Cs), barium (Ba) ) Are preferable, atoms of aluminum (Al), zinc (Zn), indium (In), and barium (Ba) are more preferable, and atoms of aluminum (Al), zinc (Zn), and indium (In) are more preferable.

Examples of transition metals include group 3 elements (scandium group), group 4 elements (titanium group), group 5 elements (vanadium group), group 6 elements (chromium group), and group 7 elements of the periodic table. (Manganese group), 4th group 8-10 group element (iron group), and 5-6th group 8-10 group element (platinum group) atom of the metal element is mentioned.
Specifically, scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), Yttrium (Y), Zirconium (Zr), Niobium (Nb), Molybdenum (Mo), Technetium (Tc), Ruthenium (Ru), Rhodium (Rh), Palladium (Pd), Silver (Ag), Lanthanum (La), Cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), Erbium (Er), Thulium (Tm), Ytterbium (Yb), Lutetium (Lu), Hafnium (Hf), Tantalum (Ta), Tungsten (W), Rhenium (Re), Osmium (Os), Iridium (Ir), Platinum (Pt), Gold ( u), and the like.
Among them, scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), etc. Those belonging to the series (that is, the fourth period) are preferable, and cobalt (Co) and nickel (Ni) are more preferable.

The ligand when the organometallic compound (M) is an organometallic complex is not particularly limited, and may be a monodentate ligand or a polydentate ligand. The molecular weight of one ligand is preferably 20 or more and 500 or less.
Examples of the ligand include tetrahydrofuran, ethylene glycol dimethyl ether, acetonitrile, benzonitrile, oxalato, acetate, ethanolate, 1-butanethiolato, thiophenolate, 2,2′-thiobis (4-t-octyl) phenolate, 2,4. -Pentandionato, 2,2,6,6-tetramethyl-3,5-heptanedionate, trifluoro-2,4-pentanedionate, hexafluoro-2,4-pentanedionate, ethylacetoacetate, dimethyl Amine, diethylamine, tetraethylammonium, piperidine, N-methylaniline, pyridine, 2-phenylpyridine, ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, 1,2-diaminocyclohexane, 2,2′-bipyridine 1,10 -Phenanthroline, ethylenediaminetetraacetate, 1,4,8,11-tetraazacyclotetradecane, tris (2-aminoethyl) amine, triethylphosphine, tributylphosphine, tricyclohexylphosphine, dimethylphenylphosphine, triphenylphosphine, diphenylphosphine , Tricyclohexylphosphine, cyclopentadiene, pentamethylcyclopentadiene, cyclooctene, 1,5-cyclooctadiene, bicyclo [2.2.1] hepta-2,5-diene, benzene, naphthalene, allyl and the like.

  As the preferred ligand, those having no aromatic ring in the ligand are preferred, and acetate, acetylacetonate, hexafluoroacetylacetonate, diethyldithiocarbamate, and di-n-butyldithiocarbamate are more preferred. .

  As long as the organometallic complex has at least one ligand derived from an organic compound, it may have another ligand. Examples of such a ligand include fluoro, chloro, bromo, iodo, hydroxo, aqua, oxo, peroxo, carbonyl, carbonato, cyano, amine, sulfato, nitro, nitrito, phosphato, thiocyanato, isothiocyanate and the like. .

When the organometallic compound (M) is a metal salt of an organic acid, the molecular weight of one organic acid is preferably 20 or more and 500 or less.
Examples of the organic acid include dimethyldithiocarbamic acid, diethyldithiocarbamic acid, dibutyldithiocarbamic acid, N, N-bis (2-hydroxyethyl) dithiocarbamic acid, N-ethyl-N-phenyldithiocarbamic acid, N, N-dibenzyldithiocarbamine. Examples include acid, diethyldithiophosphoric acid, diisopropyldithiophosphoric acid, 2-hydroxypropanoic acid, stearic acid, arsenic acid, and oxalic acid.

  Examples of the organometallic compound (M) include tris (2-hydroxypropanoic acid) aluminum, bis (2-ethylhexanoato) hydroxyaluminum, bis (2-sulfanylpyridine-N-oxide) zinc, and bis (2-hydroxy). Propanoic acid) zinc, bis (2-hydroxypropanoic acid) barium, bis (stearic acid) barium, barium arsenate, barium oxalate, described in JP 2011-118365 A and JP 2004-295116 A Compounds and the like.

  Among them, an organometallic compound containing at least one group selected from the group consisting of —C (═O) — and —C (═S) — is preferable, and a compound represented by the formula (F1), which is represented by the formula ( A compound represented by F2) and at least one compound selected from the group consisting of these hydrates are more preferred. It is preferable that the organometallic compound (M) is any of these compounds because the solubility in an organic solvent tends to be improved.

［式（Ｆ１）中、Ｗ^１及びＷ^２は、互いに独立に、炭素数１〜６の１価の脂肪族炭化水素基又は炭素数６〜１０の１価の芳香族炭化水素基を表し、該脂肪族炭化水素基及び該芳香族炭化水素基に含まれる水素原子は、ヒドロキシ基で置換されていてもよい。
Ｍ^１は、金属原子を表す。
ｘは、１〜３の整数を表し、ｘが２以上のとき、複数のＷ^１及びＷ^２は互いに同一でも異なってもよい。］

[In Formula (F1), W ¹ and W ² each independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, The hydrogen atom contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a hydroxy group.
M ¹ represents a metal atom.
x represents an integer of 1 to 3, and when x is 2 or more, the plurality of W ¹ and W ² may be the same as or different from each other. ]

［式（Ｆ２）中、Ｗ^３及びＷ^４は、互いに独立に、炭素数１〜６の１価の脂肪族炭化水素基を表し、該脂肪族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。
Ｍ^２は、金属原子を表す。
ｙは、１〜３の整数を表し、ｙが２以上のとき、複数のＷ^３及びＷ^４は互いに同一でも異なってもよい。］

[In Formula (F2), W ³ and W ⁴ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, and the hydrogen atom contained in the aliphatic hydrocarbon group is a halogen atom May be substituted.
M ² represents a metal atom.
y represents an integer of 1 to ^3, and when y is 2 or more, the plurality of W ³ and W ⁴ may be the same as or different from each other. ]

Examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms in W ¹ and W ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, A pentyl group, a hexyl group, etc. are mentioned. Examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms in which a hydrogen atom is substituted with a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, and a 1-hydroxypropyl group. 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group , 4-hydroxybutyl group and the like. Among them, preferred is an ethyl group, a butyl group or a 2-hydroxyethyl group.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in W ¹ and W ² include aryl groups such as phenyl group, toluyl group, xylyl group, propylphenyl group and butylphenyl group; Aralkyl group and the like can be mentioned. Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in which a hydrogen atom is substituted with a hydroxy group include a hydroxyphenyl group and a hydroxymethylphenyl group. Among them, preferred is a phenyl group or a benzyl group.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms in W ³ and W ⁴ include the same groups as those in W ¹ and W ² .
As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Preferably it is a fluorine atom.
Examples of the monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms in which a hydrogen atom is substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a trifluoroethyl group, and a chloromethyl group. Chloroethyl group, dichloroethyl group, chloropropyl group, chlorobutyl group, bromobutyl group, iodobutyl group and the like. Among these, a methyl group, a tert-butyl group, or a trifluoromethyl group is preferable.

  Examples of the compound represented by the formula (F1) include bis [N, N-bis (2-hydroxyethyl) dithiocarbamate] zinc, bis (N, N-dimethyldithiocarbamate) zinc, and bis (N, N- Diethyldithiocarbamate) zinc, bis (N, N-dibutyldithiocarbamate) zinc, bis (N-ethyl-N-phenyldithiocarbamate) zinc, bis (N, N-dibenzyldithiocarbamate) zinc and the like. .

  Examples of the compound represented by the formula (F2) include tris (2,4-pentanedionato) aluminum (III), tris (trifluoro-2,4-pentanedionato) aluminum (III), tris (2 , 4-pentanedionato) indium (III), tris (2,2,6,6-tetramethyl-3,5-heptaneedionato) indium (III), tris (trifluoro-2,4-pentanedionato) indium (III), bis (2,4-pentanedionato) barium, bis (hexafluoro-2,4-pentanedionato) barium, bis (2,2,6,6-tetramethyl-3,5-heptaneedionato) Barium, bis (2,4-pentanedionato) nickel (II), bis (N, N-dibutyldithiocarbamate) nickel (II) Bis (2,4-pentanedionato) cobalt (II), bis (hexafluoro-2,4-pentanedionato) cobalt (II), and the like.

  As the organometallic compound (M), bis (2,4-pentanedionato) nickel (II), bis (2,4-pentandionato) cobalt (II), tris (2,4-pentandionato) indium (III), tris (2,4-pentanedionato) aluminum (III), bis (hexafluoro-2,4-pentanedionato) cobalt (II), bis (N, N-dibutyldithiocarbamate) zinc, bis [N, N-bis (2-hydroxyethyl) dithiocarbamate] zinc and hydrates thereof are preferred. These compounds are preferable because a high-contrast color filter can be obtained and the compound tends to have high solubility in an organic solvent, so that a color filter with less generation of foreign matter tends to be obtained.

  The content of the organometallic compound (M) is preferably 0.1 parts by mass or more and 20 parts by mass or less, and 0.5 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). The amount is more preferably 15 parts by mass or less, and further preferably 1 part by mass or more and 10 parts by mass or less. When the content of the organometallic compound (M) is within the above range, a color filter having high brightness and contrast can be obtained.

<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 (containing OH in the molecule, -O-,- Solvents not containing CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like can be 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.

  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 Co., Ltd.), 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 includes additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., if necessary. May be included.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention is used, for example, as a compound (1), a resin (B), a polymerizable compound (C), a polymerization initiator (D), an organometallic compound (M), and as necessary. The pigment (A1), the dye (A2), the polymerization initiation assistant (D1), the surfactant (F), the solvent (E), and other components can be mixed.
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. The desired colored curable resin composition can be prepared by mixing the remaining components and the like in the obtained pigment dispersion 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.

<Manufacturing method of color filter and liquid crystal display device>
Examples of the method for producing the color pattern of the color filter from the colored curable resin composition of the present invention include a photolithographic method, an ink jet method, and a printing method. Of these, the photolithographic method is preferable. In the photolithographic method, the colored curable resin composition of the present invention is applied to a substrate and dried by removing volatile components such as a solvent to form a composition layer. Next, the composition layer is exposed and developed through a photomask. After development, a colored pattern can be formed by heating as necessary. In the colored pattern forming method, a colored 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 colored pattern and the colored coating film thus obtained can be used as a color filter.
The film thickness of the color filter to be produced is not particularly limited, and can be adjusted as appropriate according to the purpose and application, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5. ~ 6 μm.
As a 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, an aluminum, silver, silver / copper / palladium alloy thin film or the like is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

Next, a method for forming a pattern on a glass substrate on which a thin film transistor (hereinafter referred to as “TFT”) is formed will be described.
Specifically, a plurality of TFTs 22 are formed for each pixel on the glass substrate 21 by a known method such as a photolithography technique (see FIG. 1). The TFT 22 is formed of, for example, molybdenum (Mo) on the glass substrate 21 and constitutes part of the gate line, and, for example, a nitride film (SiN _x ) and an oxide film formed on the gate electrode 22a. A gate insulating film 22b made of a laminated film of (SiO ₂ ), a polycrystalline silicon film 22c formed on the gate insulating film 22b, and a laminated film of an oxide film (SiO ₂ ) and a nitride film (SiN _x ), for example. The protective film 22d is formed of a film. A region facing the gate electrode 22a of the polycrystalline silicon film 22c is a channel region of the TFT 22, and regions on both sides of the channel region are a source region or a drain region. The source region of the polycrystalline silicon film 22c is electrically connected to a signal line 27 made of, for example, aluminum (Al) through a connection hole (contact hole) provided in the protective film 22d. The drain region of the polycrystalline silicon film 22c is electrically connected to the pixel electrode 24 through a connection hole (contact hole) 201 as will be described later.

  When forming a plurality of TFTs 22 on the glass substrate 21 for each pixel, an alignment mark (not shown) is formed on the glass substrate 21 simultaneously with the TFTs 22. As will be described later, this alignment mark serves as a reference for alignment in the formation process of the color filter layer 23. These alignment marks can also be used as marks serving as a reference for bonding the drive substrate and the counter substrate. The alignment mark can be formed in the same process using at least one layer when forming a metal layer such as wiring or a polycrystalline silicon layer in the manufacturing process of the TFT 22.

Next, the colored curable resin composition of the present invention is applied on the glass substrate 21 on which the TFT 22 and the alignment mark are formed, and volatile components such as a solvent are removed by drying by heating (prebaking) and / or drying under reduced pressure. And dried to form a composition layer having a thickness of 0.5 to 5.0 μm, for example, 1.0 μm.
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.

Next, the composition layer is irradiated with ultraviolet rays through a photomask (not shown), and unnecessary portions (unexposed portions) are selectively removed with a developing solution, whereby the polycrystalline silicon film 22c is removed. After obtaining the composition layer formed in the pixel in which the connection hole (contact hole) 201 reaching the drain region is formed, it is washed with water.
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.

  Thereafter, in order to reflow (reflow) and / or cure the composition layer in which the connection hole (contact hole) 201 is formed, for example, at a temperature in the range of 150 to 250 ° C., preferably in the range of 160 to 235 ° C., It is preferably 1 to 120 minutes, and heated for 10 to 60 minutes. Thus, the colored curable resin composition layer 23A is formed. This colored curable resin composition layer 23A corresponds to the color filter of the present invention.

  By repeating this operation, the colored curable resin composition layer 23A is formed from the red colored curable resin composition, the green colored curable resin composition, and the blue colored curable resin composition, respectively, thereby corresponding to each pixel column. Thus, the color filter layer 23 including the red filter 23a, the green filter 23b, and the blue filter 23c is formed (see FIG. 2). A region between the filters of the color filter layer 23 is a mixed region of adjacent colors. Since this region is a light-shielding region facing the signal line 27, there is no particular problem in quality. Note that the region between the filters may not be colored.

  Subsequently, a photosensitive resin film 29 as a protective film having a film thickness of 0.3 to 2.0 μm, for example, is formed so as to cover the color filter layer 23 by, for example, a spin coating method. Next, the photosensitive resin film 29 is irradiated with ultraviolet rays through a photomask (not shown), and the regions corresponding to the connection holes 201 and unnecessary portions are selectively removed with a developer, thereby polycrystal After a connection hole (contact hole) 202 reaching the drain region of the silicon film 22c is formed, it is washed with water. Thereafter, in order to reflow (reflow) the photosensitive resin film 29, heating is performed at a temperature in the range of 100 to 300 ° C., for example, 200 ° C. Next, in order to remove residues such as dyes and organic substances deposited in the contact hole 202, etching with oxygen plasma is performed, and further, for example, etching with dilute hydrofluoric acid is performed to remove the oxide film formed by oxygen plasma. To do.

  Next, a transparent conductive material, for example, ITO (Indium-Tin Oxide) is formed on the photosensitive resin film 29 by sputtering, for example, and this ITO film is formed by photolithography and etching. Patterning is performed to form a transparent pixel electrode 24 (see FIG. 3). The pixel electrode 24 may be formed of a metal such as aluminum (Al) or silver (Ag) depending on a device to be manufactured. After that, after forming an alignment film by a known method, a liquid crystal display device can be manufactured by bonding the drive substrate and the counter substrate.

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

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.
In the following synthesis examples, the compounds were identified by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).

[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%.

Identification of compound represented by formula (1-1) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 603.4
Exact Mass: 602.2

式（１−６）で表される化合物の同定
（質量分析）イオン化モード＝ＥＳＩ＋： ｍ／ｚ＝ [Ｍ＋H]^＋ ６５９．４
Ｅｘａｃｔ Ｍａｓｓ： ６５８．３ [Synthesis Example 2]
A compound represented by the formula (1-6) was obtained in the same manner as in Synthesis Example 1 except that N-isopropyl-2,6-dimethylaniline was used instead of N-ethyl-o-toluidine.

Identification of compound represented by formula (1-6) (mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 659.4
Exact Mass: 658.3

[Synthesis Example 3]
A mixture of a compound represented by the formula (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 the dye (A2-1) (formula (A2-1-1) to formula (A2-1-8) 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部を乳酸エチル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３５．４％、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 4]
In a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, nitrogen was flowed at 0.02 L / min to form a nitrogen atmosphere, 305 parts of ethyl lactate was added, and the mixture was heated to 70 ° C. with stirring. 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 at a molar ratio of 50:50.) A solution is prepared by dissolving in 240 parts and 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 obtained by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 225 parts of ethyl lactate was dropped into the flask using another dropping funnel over 4 hours. After completion of the dropwise addition of the polymerization initiator solution, the temperature was maintained at 70 ° C. for 4 hours, and then cooled to room temperature. 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 35.4% and an acid value in terms of solid content of 103 mgKOH / g was obtained. Resin B1 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 1 to 6 and Comparative Example 1
Each component was mixed so that it might become a composition shown in Table 1, and the colored curable resin composition was obtained.

In Table 1, each component represents the following.
(A) Colorant: 1-1: Compound represented by Formula (1-1) (A) Colorant: 1-6: Compound represented by Formula (1-6) (A) Colorant: A1- 1: C.I. I. Pigment Blue 15: 6 (Pigment)
(A) Colorant: A2-1: Dye (A2-1)
(B) Resin: B-1: Resin B1 solution (C) Polymerizable compound: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd .; KAYARAD (registered trademark) DPHA)
(D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF)
(M) Organometallic compound: M-1: Zinc bis (dibutyldithiocarbamate) (M) Organometallic compound: M-2: Bis [bis (2-hydroxyethyl) dithiocarbamate] zinc (M) Organometallic compound: M -3: Tris (2,4-pentanedionato) indium (M) Organometallic compound: M-4: Tris (2,4-pentanedionato) aluminum (M) Organometallic compound: M-5: Bis (2 , 4-Pentandionato) Nickel (II)
(M) Organometallic compound: M-6: Bis (2,4-pentanedionato) cobalt (II)
(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: Fluorosurfactant (Megafuck (registered trademark) F554; manufactured by DIC Corporation)

[Calculation of molar extinction coefficient]
Each sample was weighed in 0.1 g into a volumetric flask and then diluted to 0.250 L with ethyl lactate. The absorption spectrum of this solution was measured with an ultraviolet-visible spectrophotometer (V-650DS; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm), and the visible light region (Lambert-Beer law) The maximum value [ε _M ] of the molar extinction coefficient ε at 380 nm to 780 nm) was calculated. The results are shown in Table 2.

[Formation of colored pattern]
A colored photosensitive composition was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) by spin coating, and then pre-baked at 100 ° C. for 3 minutes to obtain a colored composition layer. After cooling, the distance between the glass substrate on which the colored 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 in an air atmosphere. Light was irradiated with an exposure amount of ² (based on 365 nm). A photomask having a 100 μm line and space pattern was used. 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-baking for 20 minutes to obtain a colored pattern.

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

[Chromaticity evaluation]
About the coloring pattern on the obtained glass substrate, the spectrum was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the CIE XYZ color system using the color matching function of the 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 colored coating film was formed on the glass substrate by performing the same operation as that for forming the colored pattern 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 colored coating film was formed between polarizing films (POLAX-38S; manufactured by Luceo Co., Ltd.). The results are shown in Table 3.

  From the result of the Example, it was confirmed that the coloring pattern obtained from the colored curable resin composition of the present invention exhibits a high lightness blue color and further has a high contrast. 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.

21 Glass substrate 22 TFT (switching element)
22a Gate electrode 22b Gate insulating film 22c Polycrystalline silicon film 22d Protective film 23 Color filter layer 23A Colored curable resin composition layer (color filter)
23a Red filter 23b Green filter 23c Blue filter 24 Pixel electrode 27 Signal line 29 Photosensitive resin film (protective film)
201, 202 connection hole

Claims (4)

Including a colorant, a resin, a polymerizable compound, a polymerization initiator and an organometallic compound,
The colorant is a colorant containing a compound represented by the formula (1),
The organometallic compound is at least one selected from the group consisting of a compound represented by formula (F1), a compound represented by formula (F2), and a hydrate thereof;
A colored curable resin composition in which the maximum value of the molar extinction coefficient in the visible light region of the organometallic compound is smaller than the maximum value of the molar extinction coefficient in the visible light region of the compound represented by formula (1).

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

[In Formula (F1), W ¹ and W ² each independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, The hydrogen atom contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group may be substituted with a hydroxy group.
M ¹ represents a metal atom.
x represents an integer of 1 to 3, and when x is 2 or more, the plurality of W ¹ and W ² may be the same as or different from each other. ]

[In Formula (F2), W ³ and W ⁴ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, and the hydrogen atom contained in the aliphatic hydrocarbon group is a halogen atom May be substituted.
M ² represents a metal atom.
y represents an integer of 1 to ^3, and when y is 2 or more, the plurality of W ³ and W ⁴ may be the same as or different from each other. ] Colorant, more colorant comprising a pigment according to claim 1 Symbol placement colored curable resin composition. A color filter formed by claims 1 or 2 colored curable resin composition. A display device comprising the color filter according to claim 3 .

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