KR20160024976A - Colored curable resin composition - Google Patents

Abstract

（식 중, Ｌ은 술포닐기 등을, Ｘ는 산소원자 등을 나타내고, Ｒ^７~Ｒ^１３은 각각 독립하여 수소원자 등을 나타내고,
Ｚ는 식（Ｚ１）：

（식 중, Ｒ^１은 탄소수１~２０의 알킬기를 나타내고, 상기 알킬기를 구성하는 －ＣＨ_２－는 산소원자로 치환되어도 되고, Ｒ^２~Ｒ^６은 각각 독립하여 수소원자 등을, ＊는 결합손을 나타낸다.）
로 표시되는 기 또는 식（Ｚ２）：

（식 중, Ａｒ^１은, 오르토위치, 메타위치 또는 그 양쪽에 탄소수１~８의 알킬기를 가지는 페닐기를 나타내고, ＊는 결합손을 나타낸다.）
로 표시되는 기를 나타낸다.）A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator and a solvent, wherein the colorant comprises a compound represented by formula (I).

(Wherein L represents a sulfonyl group or the like, X represents an oxygen atom or the like, R ⁷ to R ¹³ each independently represent a hydrogen atom or the like,
Z is represented by the formula (Z1):

(Wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms, -CH ₂ - constituting the alkyl group may be substituted with an oxygen atom, R ² to R ⁶ each independently represent a hydrogen atom or the like, Lt; / RTI >
Or a group represented by the formula (Z2):

(Wherein Ar ¹ represents a phenyl group having an alkyl group having 1 to 8 carbon atoms at an ortho-position, a meta-position, or both thereof, and * indicates a bond).
Represents a group represented by the formula:

Description

COLORED CURABLE RESIN COMPOSITION [0002]

The present invention relates to a colored curable resin composition.

Dyes are used for color display by using reflected light or transmitted light in the fields of, for example, textile materials, liquid crystal display, inkjet, and the like. Patent Document 1 describes coumarin 6 represented by the following formula as such a dye.

Japanese Patent Application Laid-Open No. 2006-154740 (Example 8)

The present invention relates to providing a colored curable resin composition.

A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator and a solvent comprising a compound represented by the following formula (I).

.

(Wherein L represents a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group (-SO ₂ -),

X represents an oxygen atom or a sulfur atom,

R ⁷ to R ¹³ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group (-CONH ₂ ), a sulfamoyl group (-SO ₂ NH ₂ ), -SO ₃ M, -CO ₂ M , A hydroxyl group, a formyl group, an amino group or a monovalent hydrocarbon group having 1 to 20 carbon atoms,

-CH ₂ - constituting the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ¹⁴ ) -, a sulfonyl group or a carbonyl group,

The hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group,

R ¹⁴ represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms, and when a plurality of R ^{14 s} exist, they may be the same or different,

M represents a hydrogen atom or an alkali metal atom, and when a plurality of M exist, they may be the same or different,

Z is represented by the formula (Z1):

(Wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms, -CH ₂ - constituting the alkyl group may be substituted with an oxygen atom,

R ² to R ⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group, A monovalent hydrocarbon group,

The -CH ₂ - constituting the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ³⁰ ) -, a sulfonyl group or a carbonyl group,

The hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group,

R ³⁰ represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms, and when a plurality of R ^{30 s} exist, they may be the same or different,

M represents a hydrogen atom or an alkali metal atom, and when a plurality of M exist, they may be the same or different, and * represents a bonding hand.)

Or a group represented by the formula (Z2):

(Wherein Ar ¹ represents a phenyl group having an alkyl group having 1 to 8 carbon atoms at an ortho position, a meta position or both of them, and * represents a binding site).

Represents a group represented by the formula:

≪ 2 > The colored curable resin composition according to < 1 >, wherein L is a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms.

≪ 3 > The colored curable resin composition according to < 1 >, wherein L is a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group.

≪ 4 > The colored curable resin composition according to any one of < 1 > to < 3 >, wherein Z is a group represented by the formula (Z1).

<5> The colored curable resin composition according to any one of <1> to <4>, wherein R ¹ is an alkyl group having 1 to 16 carbon atoms, and -CH ₂ - constituting the alkyl group may be substituted with an oxygen atom.

<6> The colored curable resin composition according to <2>, wherein Z is a group represented by the formula (Z1) and R ¹ is an alkyl group having 1 to 8 carbon atoms.

<7> The colored curable resin composition according to <3>, wherein Z is a group represented by the formula (Z1) and R ¹ is an alkyl group having 6 to 10 carbon atoms.

<8> The colored curable resin composition according to any one of <1> to <3>, wherein Z is a group represented by the formula (Z2).

<9> A compound according to any one of <1>, <2>, <3> and <8>, wherein Ar ¹ is a phenyl group having an alkyl group having 1 to 8 carbon atoms at the ortho position or a phenyl group having an alkyl group having 1 to 8 carbon atoms at an ortho- &Lt; / RTI &gt; wherein the coloring curable resin composition according to any one of &lt; 1 &gt;

<10> The colored curable resin composition according to <9>, wherein the alkyl group having 1 to 8 carbon atoms is a methyl group, an ethyl group or an isopropyl group.

<11> The colored curable resin composition according to any one of <1> to <10>, wherein the coloring agent further comprises a pigment.

<12> The colored curable resin composition according to <11>, wherein the pigment is at least one selected from the group consisting of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment.

<13> The colored curable resin composition according to <11>, wherein the pigment is at least one selected from the group consisting of a chlorinated copper phthalocyanine pigment, a copper phthalocyanine pigment, and a zinc bromide phthalocyanine pigment.

<14> The colored curable resin composition according to any one of <11> to <13>, wherein the pigment is a green pigment.

<15> The pigment according to any one of <11> to <14>, wherein the pigment is at least one selected from the group consisting of C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. By weight based on the total weight of the curable resin composition.

<16> A color filter formed from the colored curable resin composition according to any one of <1> to <15>.

&Lt; 17 &gt; A liquid crystal display device comprising a color filter according to &lt; 16 &gt;.

<18> The compound represented by the formula (Ia-1).

(Wherein L ^a represents ^a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group (-SO ₂ -), X represents an oxygen atom or a sulfur atom, R ⁷ to R ¹³ each independently represent a hydrogen atom , A halogen atom, a cyano group, a nitro group, a carbamoyl group (-CONH ₂ ), a sulfamoyl group (-SO ₂ NH ₂ ), -SO ₃ M, -CO ₂ M, a hydroxy group, a formyl group, -CH ₂ - which constitute the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ¹⁴ ) -, a sulfonyl group or a carbonyl group, and the hydrogen contained in the hydrocarbon group atoms are optionally substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl _{group, -SO 3 M, -CO 2 M} , a hydroxy group, a formyl group or an amino group, ^{R 14} is And when a plurality of R ^{14 s} exist, they may be the same or different, and M represents a hydrogen atom or an alkali metal atom, and when a plurality of Ms exist, they may be the same or different, May be the same or different,

Z ^a represents a group represented by the formula (Z1).

(Wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms, -CH ₂ - constituting the alkyl group may be substituted with an oxygen atom, R ² to R ⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, A nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxy group, a formyl group, an amino group or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the -CH ₂ - May be substituted with an oxygen atom, a sulfur atom, -N (R ³⁰ ) -, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, -SO ₃ M, and may be substituted with -CO ₂ M, a hydroxy group, a formyl group or an amino group, ^{R 30} represents a monovalent hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom , If R ³⁰ is a plurality are present, they be the same, are different, and if a plurality M are present, they be the same, are different, and * represents a bonding hand.))

<19> The compound according to <18>, wherein R ¹ is an alkyl group having 1 to 16 carbon atoms, and -CH ₂ - constituting the alkyl group may be substituted with an oxygen atom.

<20> The compound according to <18>, wherein R ¹ is an alkyl group having 6 to 10 carbon atoms.

<21> The compound represented by the formula (Ia-2).

(Wherein L ^a represents ^a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group (-SO ₂ -), X represents an oxygen atom or a sulfur atom, R ⁷ to R ¹³ each independently represent a hydrogen atom, A halogen atom, a cyano group, a nitro group, a carbamoyl group (-CONH ₂ ), a sulfamoyl group (-SO ₂ NH ₂ ), -SO ₃ M, -CO ₂ M, a hydroxy group, a formyl group, -CH ₂ - constituting the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ¹⁴ ) -, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the hydrocarbon group is optionally substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl _{group, -SO 3 M, -CO 2 M} , a hydroxy group, a formyl group or an amino group, ^{R 14} is When represents a predetermined atom or a monovalent hydrocarbon with a carbon number of 1 ~ 20, R ¹⁴ are a plurality are present, they be the same, are different, M is a hydrogen atom or an alkali metal atom, if M a plurality are present, they May be the same or different,

Z ^b represents a group represented by the formula (Z2).

(Wherein Ar ¹ represents a phenyl group having an alkyl group having 1 to 8 carbon atoms at an ortho position, a meta position, or both of them, and * indicates a bond))

<22> The compound according to <21>, wherein Ar ¹ is a phenyl group having an alkyl group having 1 to 8 carbon atoms at the ortho position, or a phenyl group having an alkyl group having 1 to 8 carbon atoms at the ortho position and meta position.

<23> The compound according to <22>, wherein the alkyl group having 1 to 8 carbon atoms is a methyl group, an ethyl group or an isopropyl group.

<24> A colorant comprising a compound according to any one of <18> to <23>.

<25> A colorant according to <24>, further comprising a pigment.

&Lt; 26 &gt; A compound represented by the formula (IIa).

(Wherein L ^a represents ^a divalent hydrocarbon group or a sulfonyl group having 1 to 20 carbon atoms, X represents an oxygen atom or a sulfur atom, R ¹¹ to R ¹³ each independently represent a hydrogen atom, a halogen atom, -SO ₃ M, -CO ₂ M, a hydroxy group, a formyl group, an amino group or a monovalent hydrocarbon group of 1 to 20 carbon atoms, and the -CH 3 constituting the hydrocarbon group ₂ - may be substituted by an oxygen atom, a sulfur atom, -N (R ¹⁴ ) -, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, -SO ₃ M, -CO ₂ M, a hydroxy group, a formyl group or an amino group, and R ¹⁴ represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms, If you pay, ^{R 14} is a plurality exist other, all of which are be the same, are different, M is a hydrogen atom or an alkali metal atom, if M a plurality are present, they be the same, are different, ^{R 15} and R ¹⁶ Each independently represent an alkyl group having 1 to 20 carbon atoms.)

&Lt; 27 &gt; A compound represented by the formula (III).

(Wherein R ⁷ to R ⁹ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, Or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and -CH ₂ - constituting the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ¹⁴ ) -, a sulfonyl group or a carbonyl group, The hydrogen atom contained in the group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group or an amino group. R ¹⁴ represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms, and when a plurality of R ¹⁴ exist, they may be the same or different. M represents a hydrogen atom or an alkali metal atom, and when a plurality of M exist, they may be the same or different,

Z is represented by the formula (Z1):

(Wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms, -CH ₂ - constituting the alkyl group may be substituted with an oxygen atom, R ² to R ⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, A nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxy group, a formyl group, an amino group or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the -CH ₂ - May be substituted with an oxygen atom, a sulfur atom, -N (R ³⁰ ) -, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, -SO ₃ M, -CO ₂ M, and may be substituted by, hydroxy, formyl or amino groups, ^{R 30} is a monovalent group represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms , If R ³⁰ is a plurality are present, they be the same, are different, and M represents a hydrogen atom or an alkali metal atom, if M a plurality are present, it is the same, are different, and * represents a bonding hand. )

Or a group represented by the formula (Z2):

(Wherein Ar ¹ represents a phenyl group having an alkyl group having 1 to 8 carbon atoms at an ortho-position, a meta-position, or both, and * represents a bond).

Represents a group represented by R &lt; 1 &gt;

And the like.

According to the present invention, the color filter can be formed without sublimation of the coloring agent. The color filter formed from the colored curable resin composition of the present invention is useful as a color filter used in a display device (e.g., a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image pickup device.

The colored curable resin composition of the present invention comprises a colorant, a resin, a polymerizable compound, a polymerization initiator and a solvent containing a compound represented by formula (I) (hereinafter referred to as compound (I)).

The compound (I) also includes tautomers or salts thereof.

&Lt; Compound (I) &gt;

In formula (I), L represents a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, a divalent hydrocarbon group having 1 to 20 carbon atoms, or a sulfonyl group (-SO ₂ -).

Examples of the divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms include groups represented by the formulas (L1) to (L12), and from the viewpoint of the availability of the raw materials, the formulas (L1), (L7) Is preferably a group represented by formula (L10) or formula (L11), more preferably a group represented by formula (L1), formula (L7), formula (L8) or formula (L11) It is particularly preferable that the group is a displayed group. In the following formulas (L1) to (L12),? Represents a binding hand.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include methylene, dimethylene, trimethylene, tetramethylene, 1,1-ethylene, 2,2-propylene, fluorene- , And a bivalent hydrocarbon group having 1 to 16 carbon atoms is preferable.

From the viewpoint of the thermal stability of the compound (I), it is preferable that L is a divalent hydrocarbon group having 1 to 16 carbon atoms or a sulfonyl group, and from the viewpoint of obtaining the starting material, any one of the following formulas (L21) to Is more preferably a group to be displayed, more preferably a group represented by any one of formulas (L21) to (L23), and particularly preferably a group represented by formula (L21) or (L22). In the following formula,? Represents a binding hand.

In the formula (I), X represents an oxygen atom or a sulfur atom, preferably an oxygen atom. A color filter formed of a colored curable resin composition comprising a colorant containing a compound (I) wherein X is an oxygen atom tends to have a high brightness.

In the formula (I), each of R ⁷ to R ¹³ independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, , An amino group or a monovalent hydrocarbon group of 1 to 20 carbon atoms, and -CH ₂ - constituting the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ¹⁴ ) -, a sulfonyl group or a carbonyl group, The hydrogen atom to be included may be a halogen atom, a cyano group, a nitro group, a carbamoyl group (-CONH ₂ ), a sulfamoyl group (-SO ₂ NH ₂ ), -SO ₃ M, -CO ₂ M, a hydroxy group, And R ¹⁴ represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms. When a plurality of R ^{14 s} exist, they may be the same or different.

M represents a hydrogen atom or an alkali metal atom, and when a plurality of M exist, they may be the same or different. Examples of the alkali metal atom include a sodium atom and a potassium atom. M is preferably a hydrogen atom.

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

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropenyl group, a 1-propenyl group, a 2-propenyl group, a butyl group, an isobutyl group, Butenyl group, a pentyl group, an isopentyl group, a 3-pentyl group, a neopentyl group, a tert-pentyl group, a 1-methyl- Methyl-1-pentyl group, 2-ethyl-1-pentyl group, hexyl group, isohexyl group, Aliphatic hydrocarbon groups such as a hexyl group, a heptyl group, a 3-ethyl-1-heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group and an octadecyl group;

A cyclohexyl group, a cyclohexyl group, a cycloheptyl group, a 1-methylcyclohexyl group, a 2-methylcyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, Dimethyl cyclohexyl group, 2,3-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2, 3-dimethylcyclohexyl group, 1, Dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, A 4,4-dimethylcyclohexyl group, a 2,4,6-trimethylcyclohexyl group, a 2,2,6,6-tetramethylcyclohexyl group, a 3,3,5,5-tetramethylcyclohexyl group, etc. Alicyclic hydrocarbon group;

A phenyl group, an o-tolyl group, a m-tolyl group, a p-tolyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, (2-propyl) phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-naphthyl group, a 2-naphthyl group, An aromatic hydrocarbon group such as a phenyl group,

A cyclohexylmethyl group, a benzyl group, a phenethyl group, and the like.

A group in which -CH ₂ - constituting this monovalent hydrocarbon group is substituted with an oxygen atom, a sulfur atom, -N (R ¹⁴ ) -, a sulfonyl group or a carbonyl group, and a hydrogen atom contained in such a monovalent hydrocarbon group, , A cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxy group, a formyl group, or an amino group is exemplified by methoxy group, ethoxy group, propoxy group, Alkoxy groups such as a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group and a (2-ethyl-1-hexyl) oxy group;

An aryloxy group such as a phenoxy group;

An aralkyloxy group such as a benzyloxy group;

Propylcarbonyl group, 1-propenylcarbonyl group, butylcarbonyl group, isobutylcarbonyl group, sec-butylcarbonyl group, tert-butylcarbonyl group, (2-ethyl-1-butyl) carbonyl group, a 2-butenylcarbonyl group, a 1,3-butadienylcarbonyl group, a pentylcarbonyl group, an isopentylcarbonyl group, a 3-pentylcarbonyl group, a neopentylcarbonyl group, (1-ethyl-1-pentyl) carbonyl group, (3-ethyl-1-pentyl) carbonyl group, (Pentyl) carbonyl group, hexylcarbonyl group, isohexylcarbonyl group, (5-methyl-1-hexyl) carbonyl group, Heptylcarbonyl group, octylcarbonyl group, nonylcarbonyl group, decylcarbonyl group, undecylcarbonyl group, dodecylcarbonyl group, cyclohexylmethylcarbonyl group, cyclopropylcarbonyl group, cyclobutylcarbonyl group, cyclohexylcarbonyl group, An acyl group such as a cyclopentylcarbonyl group and a cyclohexylcarbonyl group;

An acyloxy group such as an acetoxy group or a benzoyloxy group;

Alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group and propoxycarbonyl group;

A group represented by the following formulas (GL-1) to (GL-8) (wherein, in the following formulas,?

N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-isopropylcarbamoyl group, N-butylcarbamoyl group, N-isobutylcarbamoyl group, N-sec- N-tert-butylcarbamoyl group, N-pentylcarbamoyl group, N- (1-ethyl-1-propyl) carbamoyl group, N- (1,1- (1-methyl-1-propyl) carbamoyl group, N- (2,2-dimethyl- (1-butyl) carbamoyl group, an N-cyclopentylcarbamoyl group, an N-hexylcarbamoyl group, N- (1-methyl- Dimethyl-1-butyl) carbamoyl group, N- (3,3-dimethyl-1-butyl) carbamoyl group, N- (1-methyl-1-hexyl) carbamoyl group, N- (1,4-dimethylpentyl) carbamoyl group, N-octylcarbamoyl group, N- Substituted carbamoyl groups such as N- (1,5-dimethyl-1-hexyl) carbamoyl group, N- (1,5- diary;

An N, N-diethylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-dimethylcarbamoyl group, (1-methyl-1-propyl) carbamoyl group, an N, N-heptylmethylcarbamoyl group, an N, N-heptylmethylcarbamoyl group, A disubstituted carbamoyl group such as N, N-bis (2-ethyl-1-hexyl) carbamoyl group;

N-isopropylsulfamoyl group, N-methylsulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethyl-1-propyl) sulfamoyl group, N- (1,1-dimethyl-1-propyl) sulfamoyl group , N- (1, 2-dimethyl-1-propyl) sulfamoyl group, N- (2,2- (3-methyl-1-butyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethyl (3-dimethyl-1-butyl) sulfamoyl group, N- heptylsulfamoyl group, N- (1-methyl-1-hexyl) sulfamide (1, 2-dimethyl-1-pentyl) sulfamoyl group, N- 1-hexyl) sulfamoyl group, and N- (1,1,2,2-tetramethyl-1-butyl) sulfamoyl group;

N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-bis (1-methyl-1-propyl) sulfamoyl group, N, N-heptylmethylsulfamoyl group, Disubstituted sulfamoyl groups such as N, N-bis (2-ethyl-1-hexyl) sulfamoyl group;

N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-isobutylamino group, N-sec-butylamino group, Propyl) amino group, N- (1, 2-dimethyl-1-propyl) amino group, N- (1-methyl-1-butyl) amino group, N- (2-methyl- (3-dimethyl-1-butyl) amino group, N-heptylamino group, N- (1-methyl 1-hexyl) amino group, N- (1,4-dimethyl-1-pentyl Amino group, N- (1, 2, 2-tetramethyl-1-hexyl) amino group, N- -Butyl) amino group;

N, N-diethylamino group, N, N-dimethylamino group, N, N-ethylmethylamino group, N, N-diethylamino group, (1-methyl-1-propyl) amino group, N, N-heptylmethylamino group and N, N-bis , N-dialkylamino group;

N-tert-butylaminomethyl group, N-tert-butylaminomethyl group, N-tert-butylaminomethyl group, N-isopropylaminomethyl group, Propylaminomethyl group, N- (1, 2-dimethyl-1-propyl) aminomethyl group, N- Propyl) aminomethyl group, N- (2-methyl-1-butyl) aminomethyl group, N- (3,3-dimethyl-1-butyl) aminomethyl group, N- (3,3-dimethylbutyl) aminomethyl group, N- Dimethyl-1-butyl) aminomethyl group, N- (1-methyl-1-pentyl) aminomethyl group, N- (1, ) N-alkylaminomethyl groups such as an aminomethyl group, N- (1,5-dimethyl-1-hexyl) aminomethyl group, and N- (1,1,2,2-tetramethyl-1-butyl) aminomethyl group;

An N, N-dimethylaminomethyl group, an N, N-ethylmethylaminomethyl group, an N, N-diethylaminomethyl group, (1-methyl-1-propyl) aminomethyl group, N, N-heptylmethylaminomethyl group, N, N-di -1-hexyl) aminomethyl group, and the like;

(1-propenyl) group, perfluoro (2-propenyl) group, perfluorobutyl group, perfluorobutyl group, perfluorobutyl group, perfluorobutyl group, perfluorobutyl group, perfluorobutyl group, perfluorobutyl group, perfluorobutyl group, perfluorobutyl group, perfluorobutyl group, (Perfluorohexyl) group, perfluoro (sec-butyl) group, perfluoro (tert-butyl) group, perfluor (1-methylpentyl) group, a perfluoro (1-methylpentyl) group, a perfluoro (isopentyl) group, a perfluoro (3-pentyl) group, a perfluoro neopentyl group, (1-pentyl) group, perfluoro (2-pentenyl) group, perfluorohexyl group, perfluoroisopentyl group, perfluoro Hexyl) group, perfluoroheptyl group, perfluoro An aliphatic hydrocarbon group having a fluorine atom such as a perfluorooctyl group, a perfluorooctyl group, a perfluorodecyl group, a perfluorodecyl group, a perfluorododecyl group, and a perfluorooctadecyl group;

Perfluorocyclopentyl group, perfluorocyclopentyl group, perfluorocyclohexyl group, perfluorocyclohexenyl group, perfluorocycloheptyl group, perfluoro (1-methylcyclohexyl) group, perfluorocyclohexyl group, perfluorocyclohexyl group, perfluorocyclohexyl group, perfluorocyclohexyl group, perfluorocyclohexyl group, (2-methylcyclohexyl) group, a perfluoro (3-methylcyclohexyl) group, a perfluoro (4-methylcyclohexyl) (Dimethylcyclohexyl) group, a perfluoro (1,4-dimethylcyclohexyl) group, a perfluoro (2,3-dimethylcyclohexyl) (5-dimethylcyclohexyl) group, a perfluoro (2,6-dimethylcyclohexyl) group, a perfluoro (3,4-dimethylcyclohexyl) (2,2-dimethylcyclohexyl) group, a perfluoro (3,3-dimethylcyclohexyl) group, a perfluoro (4,4-dimethylcyclohexyl) group, a perfluoro (2,4,6-trimethylcyclohexyl) An alicyclic hydrocarbon group having a fluorine atom such as perfluoro (2,2,6,6-tetramethylcyclohexyl) group and perfluoro (3,3,5,5-tetramethylcyclohexyl) group;

Perfluoroalkyl group, perfluoro (o-trilyl) group, perfluoro (m-tril) group, perfluoro (p- A perfluoro (1-naphthyl) group, a perfluoro (p-cumylthio) group, a perfluoro An aromatic hydrocarbon group having a fluorine atom such as a perfluoro (2-naphthyl) group, a 1-trifluoromethylphenyl group, a 2-trifluoromethylphenyl group, a 3-trifluoromethylphenyl group or a 4-trifluoromethylphenyl group;

Perfluoroalkoxy group, perfluoroalkoxy group, perfluoroethoxy group, perfluoro propoxy group, perfluoro (isopropoxy) group, perfluoro butoxy group, perfluoro (isobutoxy) (Perfluoro) methoxy group, perfluoro (methoxy) group, perfluoroalkoxy group, perfluoroalkoxy group, perfluorobutoxy group, perfluorobutoxy group, Propyl) methoxy group, (perfluoro (isopropyl)) methoxy group, perfluoro (isopropenyl) methoxy group, perfluoro (Perfluoro (butyl)) methoxy, (perfluorobutyl) methoxy, perfluoro (isobutyl) methoxy, perfluoro ( (Perfluoro (isopentyl)) methoxy group, (perfluoro (3-pentadienyl)) methoxy group, perfluoro (Perfluoro (neopentyl)) methoxy group, (perfluoro (tert-pentyl)) methoxy group, perfluoro Methylpentyl)) methoxy group, (perfluoro (2-pentenyl)) methoxy group, perfluorohexyl methoxy group, perfluoro (isohexyl) (Perfluorohexyl) methoxy group, (perfluorooctyl) methoxy group, (perfluorooctyl) methoxy group, (perfluorodecyl ) Methoxy group, (perfluoroundecyl) methoxy group, (perfluoro Dodecyl) methoxy group, (perfluoro-octadecyl), a substituted oxy group having a fluorine atom such as a methoxy group;

(Trifluoromethyl) phenylmethyl group, 2,5-bis (trifluoromethyl) phenylmethyl group, 2,6-bis (trifluoromethyl) phenylmethyl group, A methyl group, a 3,4-bis (trifluoromethyl) phenylmethyl group, and a 3,5-bis (trifluoromethyl) phenylmethyl group.

R ⁷ to R ¹¹ and R ¹³ are preferably a hydrogen atom.

R ¹² is preferably a hydrogen atom, -SO ₃ M or -CO ₂ M, more preferably a hydrogen atom or -SO ₃ M, and particularly preferably a hydrogen atom.

In the formula (I), Z represents a group represented by the following formula (Z1) or a group represented by the following formula (Z2). In the following formula, * indicates a binding hand.

In the formula (Z1), R ¹ represents an alkyl group having 1 to 20 carbon atoms, and -CH ₂ - constituting the alkyl group may be substituted with an oxygen atom. Examples of such alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, Pentyl group, 3-ethyl-1-pentyl group, hexyl group, isohexyl group, 5-methyl Ethyl-1-heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, octadecyl group and the like can be given , And an alkyl group having 1 to 16 carbon atoms is preferable.

-CH ₂ constituting the alkyl group thereof - is can be a group of oxygen atoms, a group represented by the formula (GL-1) ~ expression (GL-8).

When L is a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms and Z is a group represented by the formula (Z1), R ¹ in the formula (Z1) is preferably in terms of solubility in a solvent of the compound (I) An alkyl group having 1 to 16 carbon atoms or a group represented by any one of the formulas (GL-1) to (GL-8), more preferably an alkyl group having 1 to 8 carbon atoms or a group represented by any one of formulas More preferably an alkyl group having 2 to 8 carbon atoms (e.g., an ethyl group, a butyl group, a 2-ethyl-1-hexyl group or a 1-octyl group) (GL-1) to (GL-6), particularly preferably an alkyl group having 2 to 4 carbon atoms, or a group represented by any one of formulas (GL-1) to (GL-4).

When L is a divalent hydrocarbon group or sulfonyl group having 1 to 20 carbon atoms and Z is a group represented by the formula (Z1), from the viewpoint of solubility in the solvent of the compound (I), R ¹ in the formula (Z1) Is preferably an alkyl group having 1 to 16 carbon atoms or a group represented by any one of formulas (GL-1) to (GL-8), more preferably an alkyl group having 4 to 12 carbon atoms, (GL-8), more preferably an alkyl group having 6 to 10 carbon atoms (e.g., 2-ethyl-1-hexyl group or 1-octyl group) (GL-8), particularly preferably an alkyl group having 6 to 10 carbon atoms or a group represented by any one of the formulas (GL-3) to (GL-6).

In formula (Z1), R ² to R ⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxy group, , An amino group or a monovalent hydrocarbon group of 1 to 20 carbon atoms, and -CH ₂ - constituting the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ³⁰ ) -, a sulfonyl group or a carbonyl group, The hydrogen atom contained in the group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group or an amino group. R ³⁰ represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms, and when a plurality of R ^{30 s} exist, they may be the same or different, M represents a hydrogen atom or an alkali metal atom, They may be the same or different.

Examples of R ² to R ⁶ include the same ones as those of R ⁷ to R ¹³ . R ³⁰ may be the same as R ¹⁴ .

When L is a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms and Z is a group represented by the formula (Z1), R ² in the formula (Z1) is preferably in terms of solubility in the solvent of the compound (I) Is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and still more preferably a hydrogen atom, a methyl group, an ethyl group, a 2-propyl group or a tert- And particularly preferably a hydrogen atom or a methyl group. A color filter formed of a colored curable resin composition containing a colorant containing a compound (I) wherein R ² is a group thereof tends to have a high brightness.

When L is a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms and Z is a group represented by the formula (Z1), R ⁴ in the formula (Z1) is preferably in terms of solubility in a solvent of the compound (I) -SO ₃ M, -CO ₂ M or an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, 1-hexyl group, 1-hexyl group, 1-octyl group and the like), more preferably a hydrogen atom, -SO ₃ M, -CO ₂ M or an alkyl group having 1 to 4 carbon atoms, Is a hydrogen atom or a methyl group.

L is C 1 -C 20 fluorinated hydrocarbon divalent group of, when the date Z is represented by formula (Z1), ^{R 6} is preferably an aliphatic hydrocarbon group, a hydrogen atom or 1 to 10 carbon atoms, more preferably hydrogen More preferably a hydrogen atom, a methyl group, an ethyl group, a 2-propyl group or a tert-butyl group, and particularly preferably a hydrogen atom or a methyl group. A color filter formed of a colored curable resin composition containing a colorant containing the compound (I) wherein R &lt; ⁶ &gt; is a group thereof tends to have high brightness.

When L is a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms and Z is a group represented by the formula (Z1), R ³ and R ⁵ are preferably hydrogen atoms.

When L is a divalent hydrocarbon group or a sulfonyl group having 1 to 20 carbon atoms and Z is a group represented by the formula (Z1), from the viewpoint of solubility in the solvent of the compound (I), R ² is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group or a 2-propyl group, Is a methyl group. A color filter formed of a colored curable resin composition containing a colorant containing a compound (I) wherein R ² is a group thereof tends to have a high brightness.

When L is a divalent hydrocarbon group or sulfonyl group having 1 to 20 carbon atoms and Z is a group represented by the formula (Z1), R ⁴ in the formula (Z1) in view of solubility in the solvent of the compound (I) Is preferably a hydrogen atom, -SO ₃ M, -CO ₂ M or an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, More preferably a hydrogen atom, -SO ₃ M, -CO ₂ M or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, Preferably a hydrogen atom or a methyl group.

L is a divalent hydrocarbon group or an alkylsulfonyl group of 1 to 20 carbon atoms, when Z is a date represented by formula (Z1), ^{R 6} is preferably a hydrogen atom, an aliphatic hydrocarbon group, -SO ₃ M of 1 to 10 carbon atoms Or -CO ₂ M, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or -SO ₃ M, and particularly preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

When L is a divalent hydrocarbon group or sulfonyl group having 1 to 20 carbon atoms and Z is a group represented by the formula (Z1), R ³ and R ⁵ are preferably hydrogen atoms.

In the formula (Z1)

(PHK-1) to (PHK-31) may be mentioned as specific examples of the groups represented by the formulas (PHK-1) to (PHK-31). In the formula, &amp;thetas; represents a bonding hand.

In the formula (Z2), Ar ¹ represents a phenyl group having an alkyl group having 1 to 8 carbon atoms at an ortho position, a meta position, or both. Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, Methyl-1-pentyl group, 3-ethyl-1-pentyl group, hexyl group, isohexyl group, isopentyl group, isopentyl group, Methyl-1-hexyl group, 2-ethyl-1-hexyl group, heptyl group and octyl group, preferably an alkyl group having 1 to 6 carbon atoms and more preferably an alkyl group having 1 to 4 carbon atoms.

A phenyl group having an alkyl group having 1 to 8 carbon atoms at the ortho position means a phenyl group having an alkyl group having 1 to 8 carbon atoms in at least one of the two ortho positions. The phenyl group having an alkyl group having 1 to 8 carbon atoms at the meta position means a phenyl group having an alkyl group having 1 to 8 carbon atoms in at least one of two meta positions. A phenyl group having an alkyl group having 1 to 8 carbon atoms at both the ortho and meta positions means a phenyl group having an alkyl group having 1 to 8 carbon atoms in at least one of two ortho positions and at two meta positions.

Ar ¹ is preferably a phenyl group having an alkyl group having 1 to 8 carbon atoms at the ortho position or a phenyl group having an alkyl group having 1 to 8 carbon atoms at the ortho position and meta position.

Ar ¹ may have a substituent other than the alkyl group having 1 to 8 carbon atoms. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom and iodine atom), cyano group, nitro group, carbamoyl group, sulfamoyl group, -SO ₃ M, -CO ₂ M, An amino group, and -SO ₃ M and -CO ₂ M are preferable.

Specific examples of Ar ¹ include groups represented by the following formulas (PHK-1) to (PHK-10) and (PHK-13) to (PHK-29). In the formula, &amp;thetas; represents a bonding hand.

Examples of the compound (I) include a compound represented by the formula (IA) shown below in Tables 1 to 3 or an alkali metal salt thereof, a compound represented by the formula (IB) shown in the following Tables 4 to 5 or an alkali metal salt thereof, 6 to the compound represented by the formula (IAA) shown in Table 19 or an alkali metal salt thereof, and a compound represented by the formula (IAB) shown in the following Tables 20 to 28 or an alkali metal salt thereof.

In the following Tables 1 to 5, "L1" represents a group represented by the formula (L1), "O" represents an oxygen atom, "S" represents a sulfur atom, "Me""Et" represents an ethyl group, "Bu" represents a butyl group, "Hex" represents a hexyl group, "EHx" represents a 2-ethyl-1-hexyl group, "Oct" Is a group represented by the formula (GL-1), "GL2" is a group represented by the formula (GL-2), "GL3" Represents a group represented by the formula (GL-5), "H" represents a hydrogen atom, "SA" represents -SO ₃ H, "CA" represents -CO ₂ H, "PHK- PHK-16 &quot; K-1) ~ a group represented by the formula (PHK-16).

X ^A L ^A R ^1A R ^2A R ^4A R ^12A I-1 O L1 Meat H H H I-2 O L1 Meat Me Me H I-3 O L1 Meat H Me H I-4 O L1 Meat Me H H I-5 O L1 This H H H I-6 O L1 This Me Me H I-7 O L1 This H Me H I-8 O L1 This Me H H I-9 O L1 Hex H H H I-10 O L1 Hex Me Me H I-11 O L1 Hex H Me H I-12 O L1 Hex Me H H I-13 O L1 EHx H H H I-14 O L1 EHx Me Me H I-15 O L1 EHx H Me H I-16 O L1 EHx Me H H I-17 O L1 Oct H H H I-18 O L1 Oct Me Me H I-19 O L1 Oct H Me H I-20 O L1 Oct Me H H I-21 O L1 GL1 H H H I-22 O L1 GL1 Me Me H I-23 O L1 GL1 H Me H I-24 O L1 GL1 Me H H I-25 O L1 GL3 H H H I-26 O L1 GL3 Me Me H I-27 O L1 GL3 H Me H I-28 O L1 GL3 Me H H I-29 O L1 GL5 H H H I-30 O L1 GL5 Me Me H I-31 O L1 GL5 H Me H I-32 O L1 GL5 Me H H I-33 S L1 Meat H H H I-34 S L1 Meat Me Me H I-35 S L1 Meat H Me H

X ^A L ^A R ^1A R ^2A R ^4A R ^12A I-36 S L1 Meat Me H H I-37 S L1 This H H H I-38 S L1 This Me Me H I-39 S L1 This H Me H I-40 S L1 This Me H H I-41 S L1 Hex H H H I-42 S L1 Hex Me Me H I-43 S L1 Hex H Me H I-44 S L1 Hex Me H H I-45 S L1 EHx H H H I-46 S L1 EHx Me Me H I-47 S L1 EHx H Me H I-48 S L1 EHx Me H H I-49 S L1 Oct H H H I-50 S L1 Oct Me Me H I-51 S L1 Oct H Me H I-52 S L1 Oct Me H H I-53 S L1 GL1 H H H I-54 S L1 GL1 Me Me H I-55 S L1 GL1 H Me H I-56 S L1 GL1 Me H H I-57 S L1 GL3 H H H I-58 S L1 GL3 Me Me H I-59 S L1 GL3 H Me H I-60 S L1 GL3 Me H H I-61 S L1 GL5 H H H I-62 S L1 GL5 Me Me H I-63 S L1 GL5 H Me H I-64 S L1 GL5 Me H H I-65 O L1 Meat H SA H I-66 O L1 Meat H H SA I-67 O L1 Meat H CA H I-68 O L1 Meat H H CA I-69 O L1 Meat Me SA H I-70 O L1 Meat Me H SA

X ^A L ^A R ^1A R ^2A R ^4A R ^12A I-71 O L1 Meat Me CA H I-72 O L1 Meat Me H CA I-73 O L1 Oct H SA H I-74 O L1 Oct H H SA I-75 O L1 Oct H CA H I-76 O L1 Oct H H CA I-77 O L1 Oct Me SA H I-78 O L1 Oct Me H SA I-79 O L1 Oct Me CA H I-80 O L1 Oct Me H CA I-141 O L1 GL2 H H H I-142 O L1 GL2 Me H H I-143 O L1 GL2 H Me H I-144 O L1 GL2 Me Me H I-171 S L1 GL2 H H H I-172 S L1 GL2 Me H H I-173 S L1 GL2 H Me H I-174 S L1 GL2 Me Me H

X ^B L ^B Ar ^1B R ^12B I-81 O L1 PHK1 H I-82 O L1 PHK2 H I-83 O L1 PHK3 H I-84 O L1 PHK4 H I-85 O L1 PHK5 H I-86 O L1 PHK6 H I-87 O L1 PHK7 H I-88 O L1 PHK8 H I-89 O L1 PHK9 H I-90 O L1 PHK10 H I-91 O L1 PHK1 SA I-92 O L1 PHK2 SA I-93 O L1 PHK3 SA I-94 O L1 PHK4 SA I-95 O L1 PHK5 SA I-96 O L1 PHK6 SA I-97 O L1 PHK7 SA I-98 O L1 PHK8 SA I-99 O L1 PHK9 SA I-100 O L1 PHK10 SA I-101 O L1 PHK1 CA I-102 O L1 PHK2 CA I-103 O L1 PHK3 CA I-104 O L1 PHK4 CA I-105 O L1 PHK5 CA I-106 O L1 PHK6 CA I-107 O L1 PHK7 CA I-108 O L1 PHK8 CA I-109 O L1 PHK9 CA I-110 O L1 PHK10 CA I-163 O L1 PHK13 H I-164 O L1 PHK14 H I-165 O L1 PHK15 H I-166 O L1 PHK16 H

X ^B L ^B Ar ^1B R ^12B I-111 S L1 PHK1 H I-112 S L1 PHK2 H I-113 S L1 PHK3 H I-114 S L1 PHK4 H I-115 S L1 PHK5 H I-116 S L1 PHK6 H I-117 S L1 PHK7 H I-118 S L1 PHK8 H I-119 S L1 PHK9 H I-120 S L1 PHK10 H I-121 S L1 PHK1 SA I-122 S L1 PHK2 SA I-123 S L1 PHK3 SA I-124 S L1 PHK4 SA I-125 S L1 PHK5 SA I-126 S L1 PHK6 SA I-127 S L1 PHK7 SA I-128 S L1 PHK8 SA I-129 S L1 PHK9 SA I-130 S L1 PHK10 SA I-131 S L1 PHK1 CA I-132 S L1 PHK2 CA I-133 S L1 PHK3 CA I-134 S L1 PHK4 CA I-135 S L1 PHK5 CA I-136 S L1 PHK6 CA I-137 S L1 PHK7 CA I-138 S L1 PHK8 CA I-139 S L1 PHK9 CA I-140 S L1 PHK10 CA I-167 S L1 PHK13 H I-168 S L1 PHK14 H I-169 S L1 PHK15 H I-170 S L1 PHK16 H

In the following Tables 6 to 19, "L21" represents a group represented by the formula (L21), "L22" represents a group represented by the formula (L22), "L23""L24" represents a group represented by the formula (L24), "O" represents an oxygen atom, "S" represents a sulfur atom, "Me" represents a methyl group, "Et" EHx "represents a 2-ethyl-1-hexyl group," Oct "represents an octyl group," MB "represents a 3-methyl-1-butyl group GL2 "represents a group represented by the formula (GL-2), and" GL3 "represents a group represented by the formula (GL-1)," DC "represents a dodecyl group," GL1 " Represents a group represented by three), "GL5" represents a group represented by the formula (GL5), "H" represents a hydrogen atom, "SA" represents an -SO ₃ H, "CA" is -CO ₂ H.

X ^A L ^A R ^1A R ^2A R ^4A R ^6A R ^12A IA-1 O L21 Meat Me Me H H IA-2 O L21 Meat Me H H H IA-3 O L21 Meat H H H H IA-4 O L21 Meat H Me H H IA-5 O L21 This Me Me H H IA-6 O L21 This Me H H H IA-7 O L21 This H H H H IA-8 O L21 This H Me H H IA-9 O L21 Hex Me Me H H IA-10 O L21 Hex Me H H H IA-11 O L21 Hex H H H H IA-12 O L21 Hex H Me H H IA-13 O L21 EHx Me Me H H IA-14 O L21 EHx Me H H H IA-15 O L21 EHx H H H H

X ^A L ^A R ^1A R ^2A R ^4A R ^6A R ^12A IA-16 O L21 EHx H Me H H IA-17 O L21 Oct Me Me H H IA-18 O L21 Oct Me H H H IA-19 O L21 Oct H H H H IA-20 O L21 Oct H Me H H IA-21 O L21 GL1 Me Me H H IA-22 O L21 GL1 Me H H H IA-23 O L21 GL1 H H H H IA-24 O L21 GL1 H Me H H IA-25 O L21 GL3 Me Me H H IA-26 O L21 GL3 Me H H H IA-27 O L21 GL3 H H H H IA-28 O L21 GL3 H Me H H IA-29 O L21 GL5 Me Me H H IA-30 O L21 GL5 Me H H H IA-31 O L21 GL5 H H H H IA-32 O L21 GL5 H Me H H IA-33 O L22 Meat Me Me H H IA-34 O L22 Meat Me H H H IA-35 O L22 Meat H H H H IA-36 O L22 Meat H Me H H IA-37 O L22 This Me Me H H IA-38 O L22 This Me H H H IA-39 O L22 This H H H H IA-40 O L22 This H Me H H IA-41 O L22 Hex Me Me H H IA-42 O L22 Hex Me H H H IA-43 O L22 Hex H H H H IA-44 O L22 Hex H Me H H IA-45 O L22 EHx Me Me H H IA-46 O L22 EHx Me H H H IA-47 O L22 EHx H H H H IA-48 O L22 EHx H Me H H IA-49 O L22 Oct Me Me H H IA-50 O L22 Oct Me H H H

X ^A L ^A R ^1A R ^2A R ^4A R ^6A R ^12A IA-51 O L22 Oct H H H H IA-52 O L22 Oct H Me H H IA-53 O L22 GL1 Me Me H H IA-54 O L22 GL1 Me H H H IA-55 O L22 GL1 H H H H IA-56 O L22 GL1 H Me H H IA-57 O L22 GL3 Me Me H H IA-58 O L22 GL3 Me H H H IA-59 O L22 GL3 H H H H IA-60 O L22 GL3 H Me H H IA-61 O L22 GL5 Me Me H H IA-62 O L22 GL5 Me H H H IA-63 O L22 GL5 H H H H IA-64 O L22 GL5 H Me H H IA-65 O L23 Meat Me Me H H IA-66 O L23 Meat Me H H H IA-67 O L23 Meat H H H H IA-68 O L23 Meat H Me H H IA-69 O L23 This Me Me H H IA-70 O L23 This Me H H H IA-71 O L23 This H H H H IA-72 O L23 This H Me H H IA-73 O L23 Hex Me Me H H IA-74 O L23 Hex Me H H H IA-75 O L23 Hex H H H H IA-76 O L23 Hex H Me H H IA-77 O L23 EHx Me Me H H IA-78 O L23 EHx Me H H H IA-79 O L23 EHx H H H H IA-80 O L23 EHx H Me H H IA-81 O L23 Oct Me Me H H IA-82 O L23 Oct Me H H H IA-83 O L23 Oct H H H H IA-84 O L23 Oct H Me H H IA-85 O L23 GL1 Me Me H H

X ^A L ^A R ^1A R ^2A R ^4A R ^6A R ^12A IA-86 O L23 GL1 Me H H H IA-87 O L23 GL1 H H H H IA-88 O L23 GL1 H Me H H IA-89 O L23 GL3 Me Me H H IA-90 O L23 GL3 Me H H H IA-91 O L23 GL3 H H H H IA-92 O L23 GL3 H Me H H IA-93 O L23 GL5 Me Me H H IA-94 O L23 GL5 Me H H H IA-95 O L23 GL5 H H H H IA-96 O L23 GL5 H Me H H IA-97 O L24 Meat Me Me H H IA-98 O L24 Meat Me H H H IA-99 O L24 Meat H H H H IA-100 O L24 Meat H Me H H IA-101 O L24 This Me Me H H IA-102 O L24 This Me H H H IA-103 O L24 This H H H H IA-104 O L24 This H Me H H IA-105 O L24 Hex Me Me H H IA-106 O L24 Hex Me H H H IA-107 O L24 Hex H H H H IA-108 O L24 Hex H Me H H IA-109 O L24 EHx Me Me H H IA-110 O L24 EHx Me H H H IA-111 O L24 EHx H H H H IA-112 O L24 EHx H Me H H IA-113 O L24 Oct Me Me H H IA-114 O L24 Oct Me H H H IA-115 O L24 Oct H H H H IA-116 O L24 Oct H Me H H IA-117 O L24 GL1 Me Me H H IA-118 O L24 GL1 Me H H H IA-119 O L24 GL1 H H H H IA-120 O L24 GL1 H Me H H

X ^A L ^A R ^1A R ^2A R ^4A R ^6A R ^12A IA-121 O L24 GL3 Me Me H H IA-122 O L24 GL3 Me H H H IA-123 O L24 GL3 H H H H IA-124 O L24 GL3 H Me H H IA-125 O L24 GL5 Me Me H H IA-126 O L24 GL5 Me H H H IA-127 O L24 GL5 H H H H IA-128 O L24 GL5 H Me H H IA-129 S L21 Meat Me Me H H IA-130 S L21 Meat Me H H H IA-131 S L21 Meat H H H H IA-132 S L21 Meat H Me H H IA-133 S L21 This Me Me H H IA-134 S L21 This Me H H H IA-135 S L21 This H H H H IA-136 S L21 This H Me H H IA-137 S L21 Hex Me Me H H IA-138 S L21 Hex Me H H H IA-139 S L21 Hex H H H H IA-140 S L21 Hex H Me H H IA-141 S L21 EHx Me Me H H IA-142 S L21 EHx Me H H H IA-143 S L21 EHx H H H H IA-144 S L21 EHx H Me H H IA-145 S L21 Oct Me Me H H IA-146 S L21 Oct Me H H H IA-147 S L21 Oct H H H H IA-148 S L21 Oct H Me H H IA-149 S L21 GL1 Me Me H H IA-150 S L21 GL1 Me H H H IA-151 S L21 GL1 H H H H IA-152 S L21 GL1 H Me H H IA-153 S L21 GL3 Me Me H H IA-154 S L21 GL3 Me H H H IA-155 S L21 GL3 H H H H

X ^A L ^A R ^1A R ^2A R ^4A R ^6A R ^12A IA-156 S L21 GL3 H Me H H IA-157 S L21 GL5 Me Me H H IA-158 S L21 GL5 Me H H H IA-159 S L21 GL5 H H H H IA-160 S L21 GL5 H Me H H IA-161 S L22 Meat Me Me H H IA-162 S L22 Meat Me H H H IA-163 S L22 Meat H H H H IA-164 S L22 Meat H Me H H IA-165 S L22 This Me Me H H IA-166 S L22 This Me H H H IA-167 S L22 This H H H H IA-168 S L22 This H Me H H IA-169 S L22 Hex Me Me H H IA-170 S L22 Hex Me H H H IA-171 S L22 Hex H H H H IA-172 S L22 Hex H Me H H IA-173 S L22 EHx Me Me H H IA-174 S L22 EHx Me H H H IA-175 S L22 EHx H H H H IA-176 S L22 EHx H Me H H IA-177 S L22 Oct Me Me H H IA-178 S L22 Oct Me H H H IA-179 S L22 Oct H H H H IA-180 S L22 Oct H Me H H IA-181 S L22 GL1 Me Me H H IA-182 S L22 GL1 Me H H H IA-183 S L22 GL1 H H H H IA-184 S L22 GL1 H Me H H IA-185 S L22 GL3 Me Me H H IA-186 S L22 GL3 Me H H H IA-187 S L22 GL3 H H H H IA-188 S L22 GL3 H Me H H IA-189 S L22 GL5 Me Me H H IA-190 S L22 GL5 Me H H H

X ^A L ^A R ^1A R ^2A R ^4A R ^6A R ^12A IA-191 S L22 GL5 H H H H IA-192 S L22 GL5 H Me H H IA-193 S L23 Meat Me Me H H IA-194 S L23 Meat Me H H H IA-195 S L23 Meat H H H H IA-196 S L23 Meat H Me H H IA-197 S L23 This Me Me H H IA-198 S L23 This Me H H H IA-199 S L23 This H H H H IA-200 S L23 This H Me H H IA-201 S L23 Hex Me Me H H IA-202 S L23 Hex Me H H H IA-203 S L23 Hex H H H H IA-204 S L23 Hex H Me H H IA-205 S L23 EHx Me Me H H IA-206 S L23 EHx Me H H H IA-207 S L23 EHx H H H H IA-208 S L23 EHx H Me H H IA-209 S L23 Oct Me Me H H IA-210 S L23 Oct Me H H H IA-211 S L23 Oct H H H H IA-212 S L23 Oct H Me H H IA-213 S L23 GL1 Me Me H H IA-214 S L23 GL1 Me H H H IA-215 S L23 GL1 H H H H IA-216 S L23 GL1 H Me H H IA-217 S L23 GL3 Me Me H H IA-218 S L23 GL3 Me H H H IA-219 S L23 GL3 H H H H IA-220 S L23 GL3 H Me H H IA-221 S L23 GL5 Me Me H H IA-222 S L23 GL5 Me H H H IA-223 S L23 GL5 H H H H IA-224 S L23 GL5 H Me H H IA-225 S L24 Meat Me Me H H

X ^A L ^A R ^1A R ^2A R ^4A R ^6A R ^12A IA-226 S L24 Meat Me H H H IA-227 S L24 Meat H H H H IA-228 S L24 Meat H Me H H IA-229 S L24 This Me Me H H IA-230 S L24 This Me H H H IA-231 S L24 This H H H H IA-232 S L24 This H Me H H IA-233 S L24 Hex Me Me H H IA-234 S L24 Hex Me H H H IA-235 S L24 Hex H H H H IA-236 S L24 Hex H Me H H IA-237 S L24 EHx Me Me H H IA-238 S L24 EHx Me H H H IA-239 S L24 EHx H H H H IA-240 S L24 EHx H Me H H IA-241 S L24 Oct Me Me H H IA-242 S L24 Oct Me H H H IA-243 S L24 Oct H H H H IA-244 S L24 Oct H Me H H IA-245 S L24 GL1 Me Me H H IA-246 S L24 GL1 Me H H H IA-247 S L24 GL1 H H H H IA-248 S L24 GL1 H Me H H IA-249 S L24 GL3 Me Me H H IA-250 S L24 GL3 Me H H H IA-251 S L24 GL3 H H H H IA-252 S L24 GL3 H Me H H IA-253 S L24 GL5 Me Me H H IA-254 S L24 GL5 Me H H H IA-255 S L24 GL5 H H H H IA-256 S L24 GL5 H Me H H IA-257 O L21 EHx Me SA H H IA-258 O L21 EHx Me Me SA H IA-259 O L21 EHx Me Me H SA IA-260 O L21 EHx Me H SA H

X ^A L ^A R ^1A R ^2A R ^4A R ^6A R ^12A IA-261 O L21 EHx Me H H SA IA-262 O L21 Oct Me SA H H IA-263 O L21 Oct Me Me SA H IA-264 O L21 Oct Me Me H SA IA-265 O L21 Oct Me H SA H IA-266 O L21 Oct Me H H SA IA-267 O L21 EHx Me CA H H IA-268 O L21 EHx Me Me CA H IA-269 O L21 EHx Me Me H CA IA-270 O L21 EHx Me H CA H IA-271 O L21 EHx Me H H CA IA-272 O L21 Oct Me CA H H IA-273 O L21 Oct Me Me CA H IA-274 O L21 Oct Me Me H CA IA-275 O L21 Oct Me H CA H IA-276 O L21 Oct Me H H CA IA-277 O L22 EHx Me SA H H IA-278 O L22 EHx Me Me SA H IA-279 O L22 EHx Me Me H SA IA-280 O L22 EHx Me H SA H IA-281 O L22 EHx Me H H SA IA-282 O L22 Oct Me SA H H IA-283 O L22 Oct Me Me SA H IA-284 O L22 Oct Me Me H SA IA-285 O L22 Oct Me H SA H IA-286 O L22 Oct Me H H SA IA-287 O L22 EHx Me CA H H IA-288 O L22 EHx Me Me CA H IA-289 O L22 EHx Me Me H CA IA-290 O L22 EHx Me H CA H IA-291 O L22 EHx Me H H CA IA-292 O L22 Oct Me CA H H IA-293 O L22 Oct Me Me CA H IA-294 O L22 Oct Me Me H CA IA-295 O L22 Oct Me H CA H IA-296 O L22 Oct Me H H CA

In the following Tables 20 to 28, "L21" represents a group represented by the formula (L21), "L22" represents a group represented by the formula (L22), "L23" refers to a group represented by the formula indicates, "L24" indicates a group represented by the formula (L24), "O" represents an oxygen atom, "S" denotes a sulfur atom, "H" represents a hydrogen atom, "SA" is -SO ₃ H "," CA "represents -CO ₂ H, and" PHK-1 "to" PHK-16 "represent groups represented by the formulas (PHK-1) to (PHK-16), respectively.

X ^A L ^A Ar ^1A R ^12A IB-1 O L21 PHK1 H IB-2 O L21 PHK2 H IB-3 O L21 PHK3 H IB-4 O L21 PHK4 H IB-5 O L21 PHK5 H IB-6 O L21 PHK6 H IB-7 O L21 PHK7 H IB-8 O L21 PHK8 H IB-9 O L21 PHK9 H IB-10 O L21 PHK10 H IB-11 O L21 PHK1 SA IB-12 O L21 PHK2 SA IB-13 O L21 PHK3 SA IB-14 O L21 PHK4 SA IB-15 O L21 PHK5 SA IB-16 O L21 PHK6 SA IB-17 O L21 PHK7 SA IB-18 O L21 PHK8 SA IB-19 O L21 PHK9 SA IB-20 O L21 PHK10 SA

X ^A L ^A Ar ^1A R ^12A IB-21 O L21 PHK1 CA IB-22 O L21 PHK2 CA IB-23 O L21 PHK3 CA IB-24 O L21 PHK4 CA IB-25 O L21 PHK5 CA IB-26 O L21 PHK6 CA IB-27 O L21 PHK7 CA IB-28 O L21 PHK8 CA IB-29 O L21 PHK9 CA IB-30 O L21 PHK10 CA IB-31 O L22 PHK1 H IB-32 O L22 PHK2 H IB-33 O L22 PHK3 H IB-34 O L22 PHK4 H IB-35 O L22 PHK5 H IB-36 O L22 PHK6 H IB-37 O L22 PHK7 H IB-38 O L22 PHK8 H IB-39 O L22 PHK9 H IB-40 O L22 PHK10 H IB-41 O L22 PHK1 SA IB-42 O L22 PHK2 SA IB-43 O L22 PHK3 SA IB-44 O L22 PHK4 SA IB-45 O L22 PHK5 SA IB-46 O L22 PHK6 SA IB-47 O L22 PHK7 SA IB-48 O L22 PHK8 SA IB-49 O L22 PHK9 SA IB-50 O L22 PHK10 SA IB-51 O L22 PHK1 CA IB-52 O L22 PHK2 CA IB-53 O L22 PHK3 CA IB-54 O L22 PHK4 CA IB-55 O L22 PHK5 CA

X ^A L ^A Ar ^1A R ^12A IB-56 O L22 PHK6 CA IB-57 O L22 PHK7 CA IB-58 O L22 PHK8 CA IB-59 O L22 PHK9 CA IB-60 O L22 PHK10 CA IB-61 O L23 PHK1 H IB-62 O L23 PHK2 H IB-63 O L23 PHK3 H IB-64 O L23 PHK4 H IB-65 O L23 PHK5 H IB-66 O L23 PHK6 H IB-67 O L23 PHK7 H IB-68 O L23 PHK8 H IB-69 O L23 PHK9 H IB-70 O L23 PHK10 H IB-71 O L23 PHK1 SA IB-72 O L23 PHK2 SA IB-73 O L23 PHK3 SA IB-74 O L23 PHK4 SA IB-75 O L23 PHK5 SA IB-76 O L23 PHK6 SA IB-77 O L23 PHK7 SA IB-78 O L23 PHK8 SA IB-79 O L23 PHK9 SA IB-80 O L23 PHK10 SA IB-81 O L23 PHK1 CA IB-82 O L23 PHK2 CA IB-83 O L23 PHK3 CA IB-84 O L23 PHK4 CA IB-85 O L23 PHK5 CA IB-86 O L23 PHK6 CA IB-87 O L23 PHK7 CA IB-88 O L23 PHK8 CA IB-89 O L23 PHK9 CA IB-90 O L23 PHK10 CA

X ^A L ^A Ar ^1A R ^12A IB-91 O L24 PHK1 H IB-92 O L24 PHK2 H IB-93 O L24 PHK3 H IB-94 O L24 PHK4 H IB-95 O L24 PHK5 H IB-96 O L24 PHK6 H IB-97 O L24 PHK7 H IB-98 O L24 PHK8 H IB-99 O L24 PHK9 H IB-100 O L24 PHK10 H IB-101 O L24 PHK1 SA IB-102 O L24 PHK2 SA IB-103 O L24 PHK3 SA IB-104 O L24 PHK4 SA IB-105 O L24 PHK5 SA IB-106 O L24 PHK6 SA IB-107 O L24 PHK7 SA IB-108 O L24 PHK8 SA IB-109 O L24 PHK9 SA IB-110 O L24 PHK10 SA IB-111 O L24 PHK1 CA IB-112 O L24 PHK2 CA IB-113 O L24 PHK3 CA IB-114 O L24 PHK4 CA IB-115 O L24 PHK5 CA IB-116 O L24 PHK6 CA IB-117 O L24 PHK7 CA IB-118 O L24 PHK8 CA IB-119 O L24 PHK9 CA IB-120 O L24 PHK10 CA IB-121 S L21 PHK1 H IB-122 S L21 PHK2 H IB-123 S L21 PHK3 H IB-124 S L21 PHK4 H IB-125 S L21 PHK5 H

X ^A L ^A Ar ^1A R ^12A IB-126 S L21 PHK6 H IB-127 S L21 PHK7 H IB-128 S L21 PHK8 H IB-129 S L21 PHK9 H IB-130 S L21 PHK10 H IB-131 S L21 PHK1 SA IB-132 S L21 PHK2 SA IB-133 S L21 PHK3 SA IB-134 S L21 PHK4 SA IB-135 S L21 PHK5 SA IB-136 S L21 PHK6 SA IB-137 S L21 PHK7 SA IB-138 S L21 PHK8 SA IB-139 S L21 PHK9 SA IB-140 S L21 PHK10 SA IB-141 S L21 PHK1 CA IB-142 S L21 PHK2 CA IB-143 S L21 PHK3 CA IB-144 S L21 PHK4 CA IB-145 S L21 PHK5 CA IB-146 S L21 PHK6 CA IB-147 S L21 PHK7 CA IB-148 S L21 PHK8 CA IB-149 S L21 PHK9 CA IB-150 S L21 PHK10 CA IB-151 S L22 PHK1 H IB-152 S L22 PHK2 H IB-153 S L22 PHK3 H IB-154 S L22 PHK4 H IB-155 S L22 PHK5 H IB-156 S L22 PHK6 H IB-157 S L22 PHK7 H IB-158 S L22 PHK8 H IB-159 S L22 PHK9 H IB-160 S L22 PHK10 H

X ^A L ^A Ar ^1A R ^12A IB-161 S L22 PHK1 SA IB-162 S L22 PHK2 SA IB-163 S L22 PHK3 SA IB-164 S L22 PHK4 SA IB-165 S L22 PHK5 SA IB-166 S L22 PHK6 SA IB-167 S L22 PHK7 SA IB-168 S L22 PHK8 SA IB-169 S L22 PHK9 SA IB-170 S L22 PHK10 SA IB-171 S L22 PHK1 CA IB-172 S L22 PHK2 CA IB-173 S L22 PHK3 CA IB-174 S L22 PHK4 CA IB-175 S L22 PHK5 CA IB-176 S L22 PHK6 CA IB-177 S L22 PHK7 CA IB-178 S L22 PHK8 CA IB-179 S L22 PHK9 CA IB-180 S L22 PHK10 CA IB-181 S L23 PHK1 H IB-182 S L23 PHK2 H IB-183 S L23 PHK3 H IB-184 S L23 PHK4 H IB-185 S L23 PHK5 H IB-186 S L23 PHK6 H IB-187 S L23 PHK7 H IB-188 S L23 PHK8 H IB-189 S L23 PHK9 H IB-190 S L23 PHK10 H IB-191 S L23 PHK1 SA IB-192 S L23 PHK2 SA IB-193 S L23 PHK3 SA IB-194 S L23 PHK4 SA IB-195 S L23 PHK5 SA

X ^A L ^A Ar ^1A R ^12A IB-196 S L23 PHK6 SA IB-197 S L23 PHK7 SA IB-198 S L23 PHK8 SA IB-199 S L23 PHK9 SA IB-200 S L23 PHK10 SA IB-201 S L23 PHK1 CA IB-202 S L23 PHK2 CA IB-203 S L23 PHK3 CA IB-204 S L23 PHK4 CA IB-205 S L23 PHK5 CA IB-206 S L23 PHK6 CA IB-207 S L23 PHK7 CA IB-208 S L23 PHK8 CA IB-209 S L23 PHK9 CA IB-210 S L23 PHK10 CA IB-211 S L24 PHK1 H IB-212 S L24 PHK2 H IB-213 S L24 PHK3 H IB-214 S L24 PHK4 H IB-215 S L24 PHK5 H IB-216 S L24 PHK6 H IB-217 S L24 PHK7 H IB-218 S L24 PHK8 H IB-219 S L24 PHK9 H IB-220 S L24 PHK10 H IB-221 S L24 PHK1 SA IB-222 S L24 PHK2 SA IB-223 S L24 PHK3 SA IB-224 S L24 PHK4 SA IB-225 S L24 PHK5 SA IB-226 S L24 PHK6 SA IB-227 S L24 PHK7 SA IB-228 S L24 PHK8 SA IB-229 S L24 PHK9 SA IB-230 S L24 PHK10 SA

X ^A L ^A Ar ^1A R ^12A IB-231 S L24 PHK1 CA IB-232 S L24 PHK2 CA IB-233 S L24 PHK3 CA IB-234 S L24 PHK4 CA IB-235 S L24 PHK5 CA IB-236 S L24 PHK6 CA IB-237 S L24 PHK7 CA IB-238 S L24 PHK8 CA IB-239 S L24 PHK9 CA IB-240 S L24 PHK10 CA IB-241 O L21 PHK13 H IB-242 O L21 PHK14 H IB-243 O L21 PHK15 H IB-244 O L21 PHK16 H IB-245 O L22 PHK13 H IB-246 O L22 PHK14 H IB-247 O L22 PHK15 H IB-248 O L22 PHK16 H IB-249 O L23 PHK13 H IB-250 O L23 PHK14 H IB-251 O L23 PHK15 H IB-252 O L23 PHK16 H IB-253 O L24 PHK13 H IB-254 O L24 PHK14 H IB-255 O L24 PHK15 H IB-256 O L24 PHK16 H

X ^A L ^A Ar ^1A R ^12A IB-257 S L21 PHK13 H IB-258 S L21 PHK14 H IB-259 S L21 PHK15 H IB-260 S L21 PHK16 H IB-261 S L22 PHK13 H IB-262 S L22 PHK14 H IB-263 S L22 PHK15 H IB-264 S L22 PHK16 H IB-265 S L23 PHK13 H IB-266 S L23 PHK14 H IB-267 S L23 PHK15 H IB-268 S L23 PHK16 H IB-269 S L24 PHK13 H IB-270 S L24 PHK14 H IB-271 S L24 PHK15 H IB-272 S L24 PHK16 H

As the compound (I), a compound represented by the formula (IA ') shown in the following Table 29 or an alkali metal salt thereof can be mentioned.

In the following Table 29, "L1" represents a group represented by the formula (L1), "O" represents an oxygen atom, "Me" represents a methyl group, "Et" Ethyl-1-hexyl group, "Oct" represents an octyl group, and "GL1" represents a group represented by the formula (GL-1) , GL2 represents a group represented by the formula (GL-2), GL3 represents a group represented by the formula (GL-3), GL5 represents a group represented by the formula (GL- &Quot; H &quot; represents a hydrogen atom.

X ^A L ^A R ^1A R ^2A R ^4A R ^6A R ^12A I-145 O L1 Meat Me H Me H I-146 O L1 Meat Me Me Me H I-147 O L1 This Me H Me H I-148 O L1 This Me Me Me H I-149 O L1 Hex Me H Me H I-150 O L1 Hex Me Me Me H I-151 O L1 Oct Me H Me H I-152 O L1 Oct Me Me Me H I-153 O L1 GL1 H H H H I-154 O L1 GL1 Me Me Me H I-155 O L1 GL2 Me H What H I-156 O L1 GL2 Me Me Me H I-157 O L1 GL3 Me H Me H I-158 O L1 GL3 Me Me Me H I-159 O L1 GL5 Me H Me H I-160 O L1 GL5 Me Me Me H I-161 O L1 EHx Me H Me H I-162 O L1 EHx Me Me Me H I-175 S L1 Meat Me H Me H I-176 S L1 Meat Me Me Me H I-177 S L1 This Me H Me H I-178 S L1 This Me Me Me H I-179 S L1 Hex Me H Me H I-180 S L1 Hex Me Me Me H I-181 S L1 Oct Me H Me H I-182 S L1 Oct Me Me Me H I-183 S L1 GL1 H H H H I-184 S L1 GL1 Me Me Me H I-185 S L1 GL2 Me H What H I-186 S L1 GL2 Me Me Me H I-187 S L1 GL3 Me H Me H I-188 S L1 GL3 Me Me Me H I-189 S L1 GL5 Me H Me H I-190 S L1 GL5 Me Me Me H I-191 S L1 EHx Me H Me H I-192 S L1 EHx Me Me Me H

For example, the compound (I-2) is a compound represented by the following formula (I-2).

For example, the compound (IA-1) is a compound represented by the following formula (IA-1).

For example, the compound (IB-1) is a compound represented by the following formula (IB-1).

Among the compounds (I) in which L is a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, from the viewpoints of the solubility of the compound (I) in the solvent and the lightness of the color filter formed from the colored curable resin composition, (I-2), the compound (I-5), the compound (I-6), the compound (I-9) (1-12), compound (I-25), compound (1-26), compound (I-29), compound (I-18) The compound (I-65), the compound (I-66), the compound (I-67), the compound (I- 71), Compound (I-72), Compound (I-73), Compound (I-74) The compound (I-75), the compound (I-77), the compound (I-78), the compound (I-79) (1-14), compound (I-144), compound (I-145) to compound (I-166), compound (I-4) (1-12), compound (I-16), compound (I-20), compound (I-24), compound (I- The compound (I-1), the compound (I-2), the compound (I-5), the compound (I-6), the compound (I- (I-18), compound (I-21), compound (I-22), compound (I- The compound (I-45), the compound (I-46), the compound (I-49), the compound (I-50) (I-70), the compound (I-74), the compound (I-77), the compound (I-78) (1-141), compounds (I-144), compounds (I-145) to compounds (I-148) (1-16), compound (I-4), compound (I-8), compound (I-16) 142) is more preferable,

The compound (I-1), the compound (I-2), the compound (I-5), the compound (I-6), the compound (I- (I-26), compound (I-65), compound (I-66), compound (I-73), compound (I- (1-14), compound (I-144), compound (I-145) to compound (I-148) More preferably a compound (I-24), a compound (I-28) and a compound (I-142)

Particularly preferred are the compounds (I-1) and (I-2).

Among the compounds (I) wherein L is a divalent hydrocarbon group or sulfonyl group having 1 to 20 carbon atoms and Z is a group represented by the formula (Z1), the solubility of the compound (I) in a solvent and the color From the viewpoint of the brightness of the filter, the compound (IA-1), the compound (IA-2), the compound (IA-5), the compound (IA- (IA-13), compounds (IA-14), compounds (IA-17), compounds (IA-18), compounds (IA-21), compounds (IA-22) (IA-34), the compound (IA-37), the compound (IA-38), the compound (IA-33) -41), compound (IA-4 (IA-5), Compound (IA-45), Compound (IA-46), Compound ), The compound (IA-58), the compound (IA-61), the compound (IA-62), the compound (IA-65) , The compound (IA-73), the compound (IA-74), the compound (IA-77), the compound (IA-78) The compounds (IA-86), the compounds (IA-89), the compounds (IA-90), the compounds (IA-93), the compounds (IA-94) (IA-101), compound (IA-102 , The compound (IA-105), the compound (IA-109), the compound (IA-110) The compound (IA-118), the compound (IA-121), the compound (IA-125), the compound The compound (IA-261), the compound (IA-262), the compound (IA-264) IA-272), compound (IA-274), compound (IA-276), compound (IA- (IA-292), compound (IA-284), compound (IA-284) ), Compound (IA-296), Compound (IA-301), Compound (IA-302), Compound (IA-305), Compound (IA- , Compounds (IA-313), compounds (IA-314) and compounds (IA-333) to compounds (IA-404)

The compound (IA-9), the compound (IA-10), the compound (IA-13), the compound (IA-14), the compound (IA-26), compounds (IA-29), compounds (IA-30), compounds (IA-41), compounds (IA-42), compounds (IA-45) IA-49, IA-50, IA-57, IA-58, IA-61, IA-62, IA- (IA-7), Compound (IA-77), Compound (IA-78), Compound (IA- 93), Compound (IA-94), Compound (IA-114), Compound (IA-121), Compound (IA-110), Compound Compound (IA-252), Compound (IA-252), Compound (IA-262) 264), compound (IA-266), compound (IA-267), compound (IA-269), compound (IA-271) ), Compound (IA-277), Compound (IA-279), Compound (IA-281), Compound (IA-282) The compounds (IA-297), the compounds (IA-291), the compounds (IA-292) (IA-302), compounds (IA-305), compounds (IA-306), compounds (IA-309), compounds (IA-310), compounds (IA-313) IA-333) to (IA-404) are more preferable,

The compound (IA-13), the compound (IA-14), the compound (IA-17), the compound (IA-18), the compound (IA-45) The compound (IA-50), the compound (IA-77), the compound (IA-78), the compound (IA-81) IA-263), the compound (IA-264), the compound (IA-264) The compound (IA-286), the compound (IA-286), the compound (IA-286) 301 - compound (IA-330) and the compound (IA-333) ~ the compound (IA-404) is more preferred,

The compound (IA-13), the compound (IA-14), the compound (IA-17), the compound (IA-18), the compound (IA-45) (IA-50) is particularly preferable.

Among the compounds (I) in which L is a divalent hydrocarbon group or sulfonyl group having 1 to 20 carbon atoms and Z is a group represented by the formula (Z2), the solubility of the compound (I) in a solvent and the color The compound (IB-1), the compound (IB-2), the compound (IB-3), the compound (IB- (IB-7), the compound (IB-8), the compound (IB-10), the compound (IB- (IB-14), compound (IB-15), compound (IB-16), compound (IB-17), compound -31), Compound (IB-32), Compound The compound (IB-33), the compound (IB-34), the compound (IB-36) (IB-40), compound (IB-41), compound (IB-42), compound (IB-43), compound (IB- IB-47), compound (IB-48), compound (IB-49) and compound (IB-50)

The compound (IB-1), the compound (IB-2), the compound (IB-3), the compound (IB-4), the compound (IB- (IB-8), compound (IB-9), compound (IB-10), compound (IB-11), compound (IB- (IB-33), the compound (IB-34), the compound (IB-35), the compound (IB-36) -40), the compound (IB-41) and the compound (IB-42)

The compound (IB-1), the compound (IB-2), the compound (IB-31) and the compound (IB-32) are more preferred.

In the compound (I), L is a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group, and Z is a group represented by the formula (Z1) or a group represented by the formula (Z2) 1) (hereinafter referred to as compound (Ia-1)) and a compound represented by formula (Ia-2) (hereinafter referred to as compound (Ia-2)) are novel compounds, And is suitable as a colorant component of the colored curable resin composition.

(In the formula (Ia-1), L ^a represents ^a divalent hydrocarbon group or a sulfonyl group (-SO ₂ -) having 1 to 20 carbon atoms, X, R ⁷ to R ¹³ have the same meanings as defined above, Z ^a Represents a group represented by the formula (Z1).)

(In formula (Ia-2), L ^a , X and R ⁷ to R ¹³ have the same meanings as defined above, and Z ^b represents a group represented by formula (Z2).)

Compound (Ia-1) Among these, ^{R 1} is -CH ₂ constituting the alkyl group, the alkyl group having a carbon number of 1 to 16 - is preferably a compound (Ia-1) which may be substituted with oxygen atoms, and the ^{R 1} having 6 to (Ia-1) which is an alkyl group having 1 to 10 carbon atoms.

Among the compounds (Ia-2), preferred is a compound (Ia-2) wherein Ar ¹ is a phenyl group having an alkyl group having 1 to 8 carbon atoms at the ortho position or a phenyl group having an alkyl group having 1 to 8 carbon atoms at the ortho position and meta position (Ia-2) wherein Ar ¹ is a phenyl group having a methyl group, an ethyl group or an isopropyl group at the ortho position, or a phenyl group having a methyl group, an ethyl group or an isopropyl group at the ortho position and meta position.

Compound (I) can be prepared by reacting a compound represented by formula (II) (hereinafter referred to as compound (II)) with a compound represented by formula (III) (hereinafter referred to as compound (III) . Compound (II) wherein L is a divalent hydrocarbon group or sulfonyl group having 1 to 20 carbon atoms, that is, the compound represented by the following formula (IIa) and the compound (III) are all novel compounds.

(Wherein L, L ^a , X, Z, R ⁷ to R ⁹ and R ¹¹ to R ¹³ have the same meanings as defined above, and R ¹⁵ and R ¹⁶ each independently represent an alkyl group having 1 to 20 carbon atoms .)

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹⁵ and R ¹⁶ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert- An alkyl group of 1 to 6 is preferred. R ¹⁵ and R ¹⁶ are preferably the same group.

Examples of the base include organic bases such as triethylamine and piperidine, and the amount of the base to be used is usually 0.1 mol to 20 mol based on 1 mol of the compound (II).

The amount of the compound (III) to be used is usually 2 to 10 moles, preferably 2 to 4 moles, per 1 mole of the compound (II).

The reaction between the compound (II) and the compound (III) is carried out usually in the presence of a solvent, and examples of the solvent include nitrile solvents such as acetonitrile, methanol, ethanol, 2-propanol, Alcohols such as tetrahydrofuran, ketone solvents such as acetone, ester solvents such as ethyl acetate, aliphatic hydrocarbon solvents such as hexane and the like, aromatic hydrocarbon solvents such as toluene, halogenated alcohols such as methylene chloride and chloroform, And amide solvents such as N, N-dimethylformaldehyde and N-methylpyrrolidone. Nitrile solvents, alcohol solvents and aromatic hydrocarbon solvents are preferable, and acetonitrile, methanol and toluene are more preferable Do. The amount to be used is usually 1 part by mass to 50 parts by mass with respect to 1 part by mass of the compound (II).

The reaction temperature is usually 0 ° C to 200 ° C, preferably 0 ° C to 150 ° C. The reaction time is usually from 0.5 hour to 36 hours.

After completion of the reaction, the compound (I) can be taken out by, for example, mixing a solvent in which the compound (I) is difficult to dissolve and the obtained reaction mixture and filtering the mixture.

Compound (III) can be produced by reacting a compound represented by formula (IV) (hereinafter referred to as compound (IV)) with a formylating agent.

(Wherein Z and R ⁷ to R ⁹ have the same meanings as defined above.)

The formylating agent includes phosphoryl chloride, and the amount thereof is usually 1 to 5 mol per 1 mol of the compound (IV).

The reaction of the compound (IV) with the formylating agent is usually carried out in the presence of a solvent, and examples of the solvent include N, N-dimethylformamide. The amount to be used is usually 1 part by mass to 10 parts by mass with respect to 1 part by mass of compound (IV).

The reaction temperature is usually 0 ° C to 100 ° C, and the reaction time is usually 0.5 hours to 24 hours.

After completion of the reaction, the compound (III) can be taken out, for example, by neutralizing the reaction mixture, extracting it with an insoluble organic solvent such as ethyl acetate, and concentrating the obtained organic layer.

Compound (IV) can be produced by reacting a compound represented by formula (V) (hereinafter referred to as compound (V)) with boron tribromide and then hydrolyzing.

(Wherein Z and R ⁷ to R ⁹ have the same meanings as defined above, and R ¹⁷ represents an alkyl group having 1 to 4 carbon atoms.)

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

The amount of boron 3-bromide to be used is usually 1 to 5 mol based on 1 mol of the compound (V).

The reaction between the compound (V) and boron tribromide is usually carried out in a solvent, and as the solvent, a halogenated hydrocarbon solvent such as dichloromethane can be used. The amount of the solvent to be used is usually 1 to 50 parts by mass based on 1 part by mass of the compound (V).

The reaction temperature is usually -78 ° C to 50 ° C, and the reaction time is usually 1 to 24 hours.

After completion of the reaction, the compound (IV) can be taken out, for example, by mixing the reaction mixture and water, separating and concentrating the obtained organic layer.

The compound (V) wherein Z is the formula (Z1) can be obtained by, for example, reacting a compound represented by the formula (VI) (hereinafter referred to as the compound (VI)) with a compound represented by the formula (VII) )) In the presence of a palladium catalyst and a base.

The compound (V) wherein Z is the formula (Z1) can be obtained by, for example, reacting a compound represented by the formula (VIII) (hereinafter referred to as a compound (VIII) )) In the presence of a base.

(Wherein R ¹ to R ⁹ and R ¹⁷ have the same meanings as defined above, and X ² and X ³ each independently represent a halogen atom, a methanesulfonyloxy group, a toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group .

Examples of the halogen atom represented by X ² and X ³ include a chlorine atom, a bromine atom and an iodine atom.

The reaction of the compound (VI) with the compound (VII) can be carried out according to a method of amination of a known aromatic halide (for example, J. Org. Chem. 2003, 68, 1163-1164, etc.). Specifically, a palladium catalyst such as palladium (II) acetate and a phosphorus ligand (for example, 2,8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo [ .3.3] undecane, etc., a base such as potassium tert-butoxide, a compound (VI), a compound (VII) and a solvent such as toluene. The reaction temperature is usually 50 ° C to 150 ° C, and the reaction time is usually 0.5 to 24 hours. After completion of the reaction, the compound (V) can be taken out, for example, by mixing the reaction mixture and water, separating the organic layer, and concentrating the obtained organic layer.

The reaction of the compound (VIII) with the compound (IX) can be carried out in accordance with a method of alkylation of a known amine compound (for example, J. Org. Chem.2011, 76, 8015-8021, etc.). Specifically, a base such as triethylamine, sodium hydride, sodium methoxide, potassium tert-butoxide, sodium hydroxide or potassium hydroxide, a compound (VIII), a compound (IX) and a solvent such as dimethylsulfoxide The reaction can be carried out. The reaction temperature is usually 0 ° C to 100 ° C, and the reaction time is usually 0.5 to 72 hours. After completion of the reaction, the compound (V) can be taken out, for example, by mixing the reaction mixture with water and, if necessary, an organic solvent insoluble in water, separating the organic layer and concentrating the obtained organic layer.

The compound (V) wherein Z is a formula (Z2) can be obtained by, for example, reacting a compound represented by the formula (XV) (hereinafter referred to as a compound (XV) )) In the presence of a base.

（식 중, Ａｒ^１, Ｒ^７~Ｒ^９ 및 Ｒ^１７은 상기와 동일한 의미를 나타내고, Ｘ^３는 할로겐원자, 메탄술포닐옥시기, 톨루엔술포닐옥시기 또는 트리플루오르메탄술포닐옥시기를 나타낸다.）

(Wherein Ar ¹ , R ⁷ to R ⁹ and R ¹⁷ have the same meanings as defined above, and X ³ represents a halogen atom, a methanesulfonyloxy group, a toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group.)

Examples of the halogen atom represented by X &lt; ³ &gt; include a chlorine atom, a bromine atom and an iodine atom.

The reaction of the compound (XV) with the compound (XVI) can be carried out according to a coupling reaction between a known aromatic amine and an aromatic halide (for example, J.Mater. Chem. 1997, 7, 2343-2354, etc.) . Concretely, the reaction can be carried out by mixing copper, a base such as potassium carbonate, a compound (XV), a compound (XVI) and a solvent such as dichlorobenzene. The reaction may be carried out in the presence of a phase transfer catalyst such as 18-crown-6. The amount of the compound (XVI) to be used is usually 2 to 5 moles per 1 mole of the compound (XV). The reaction temperature is usually 50 ° C to 200 ° C, and the reaction time is usually 0.5 to 96 hours. After completion of the reaction, the compound (V) can be taken out, for example, by filtering the reaction mixture and washing with an acid to obtain an organic layer and concentrating the obtained organic layer.

The compound (II) can be produced by reacting a compound represented by the formula (X) (hereinafter sometimes referred to as a compound (X)) with a compound represented by the formula (XI) ) (Hereinafter sometimes referred to as compound (XII)) in a solvent.

(Wherein R ¹¹ to R ¹³ , R ¹⁵ , R ¹⁶ , L and X have the same meanings as defined above, and R ²⁰ represents an alkyl group having 1 to 4 carbon atoms.)

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ²⁰ include a methyl group, an ethyl group, a propyl group and a butyl group.

The amount of the compound (XI) to be used is usually 1 to 2.5 mol, preferably 1 to 1.5 mol, per 1 mol of the compound (X). The amount of the compound (XII) to be used is usually 1 to 2.5 mol, preferably 1 to 1.5 mol, per 1 mol of the compound (X). The compound (XI) and the compound (XII) are preferably the same compound, and the amount thereof is usually 2 to 5 mol, preferably 2 to 3 mol, per 1 mol of the compound (X).

As the solvent, an alcohol solvent such as methanol can be used. The amount of the solvent to be used is usually 1 to 100 parts by mass based on 1 part by mass of the compound (X).

The reaction temperature is usually -20 ° C to 100 ° C, and the reaction time is usually 1 to 72 hours.

After completion of the reaction, the compound (II) can be taken out, for example, by mixing the reaction mixture and water as required and then extracting the mixture from water-insoluble organic solvent such as ethyl acetate and concentrating the obtained organic layer . After completion of the reaction, the compound (II) may be taken out, for example, by mixing the reaction mixture with water or methanol, followed by filtration.

The compound (XI) and the compound (XII) can be produced according to a known method such as the method described in J. Med. Chem. 2012, 55, 3398-3413.

<Colorant>

The colored curable resin composition of the present invention comprises a colorant, and the colorant includes the compound (I). The colorant (hereinafter also referred to as &quot; colorant (A) &quot;) includes the compound (I) as an active ingredient. The colorant (A) may be composed of only the compound (I), or may contain a dye or pigment other than the compound (I). The colorant (A) preferably contains a pigment in addition to the compound (I). The content of the compound (I) in the colorant (A) is usually 1 to 100 mass%, preferably 3 to 100 mass%, more preferably 3 to 70 mass%, and more preferably 3 to 60 mass% desirable.

The dyes other than the compound (I) may be selected from the group consisting of Solvent, Acid, Basic, Reactive, Direct (in the Color Index) (published by The Society of Dyers and Colourists) Direct, Disperse, or Vat. Specifically, dyes of the following color index (CI) numbers are listed below.

C. I. Solvent Yellow 25, 79, 81, 82, 83, 89;

C.I. Acid Yellow 7, 23, 25, 42, 65, 76;

C. I. Reactive Yellow 2, 76, 116;

C. I. Direct Yellow 4, 28, 44, 86, 132;

C.I. Disperse Yellow 54, 76;

C. I. Solvent Orange 41, 54, 56, 99;

C.I. Acid Orange 56, 74, 95, 108, 149, 162;

C.I. Reactive Orange 16;

C.I. Direct Orange 26;

C. I. Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;

C. I. Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289;

C.I. Acid Violet 102;

C.I. Solvent Green 1, 5;

C.I. Acid Green 3, 5, 9, 25, 28;

C. I. Basic Green 1;

C.I. Bat Green 1st.

Pigments include known pigments, for example those pigments classified as pigments in the color index (The Society of Dyers and Colourists).

Specific examples of the CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;

Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 Red pigments;

Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60;

Violet pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38;

Green pigments such as CI Pigment Green 7, 36, 58;

Brown pigments such as CI Pigment Brown 23, 25, and the like;

And C.I. Pigment Black 1, 7 black pigment.

Among them, phthalocyanine pigments are preferable, and at least one kind selected from the group consisting of halogenated copper phthalocyanine pigments and halogenated zinc phthalocyanine pigments is more preferable, and CI Pigment Green 7, CI Pigment Green 36 and C And P. I. Pigment Green 58. [0060] These pigments are suitable as a green coloring agent. By using a coloring agent containing these pigments, the transmission spectrum can be optimized easily, and a color filter having excellent light resistance and chemical resistance can be formed.

If necessary, the pigment may be subjected to a surface treatment using a rosin treatment, a pigment derivative in which an acidic group or a basic group is introduced, a graft treatment on a pigment surface with a polymer compound or the like, an atomization treatment using a sulfuric acid atomization method or the like, A cleaning treatment with water or the like, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed. The particle size of the pigment is preferably substantially uniform. The pigment may be a pigment dispersion in a state in which it is uniformly dispersed in a pigment dispersant solvent by containing a pigment dispersant and performing a dispersion treatment. Each of the pigments may be dispersed singly or plural kinds of dispersions may be mixed and dispersed.

Examples of the pigment dispersant include cation dispersing agents such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigments. These pigment dispersants may be used in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shinko Chemical Industry Co., Ltd.), propylene (manufactured by Kyoei Iseki Chemical Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA (manufactured by CIBA) Adisuper (manufactured by Ajinomoto Fine Techno Co., Ltd.) and Disperbyk (manufactured by Big Chem Co., Ltd.). When a pigment dispersant is used, its amount to be used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the pigment. When the amount of the pigment dispersant is within the above range, a more uniformly dispersed pigment dispersion tends to be obtained.

&Lt; Coloring curable resin composition &

The colored curable resin composition of the present invention may contain, in addition to the above colorant (A), a resin (hereinafter also referred to as "resin (B)") and a polymerizable compound (hereinafter also referred to as "polymerizable compound (C) ), A polymerization initiator (hereinafter also referred to as "polymerization initiator (D)"), and a solvent (hereinafter also referred to as "solvent (E)"). The colored curable resin composition of the present invention may contain a leveling agent in addition to these components. The colored curable resin composition of the present invention may contain a polymerization initiator in addition to these components.

The content of the colorant (A) in the colored curable resin composition is usually 1% by mass or more and 70% by mass or less, preferably 1% by mass or more and 60% by mass or less, more preferably 5% 60 mass% or less, particularly preferably 5 mass% or more and 50 mass% or less. When the content of the colorant (A) is within the above range, desired spectral or color density can be more easily obtained. In the present specification, the "total amount of solid content" refers to the total amount of the components from which the solvent has been removed from the colored curable resin composition of the present invention. The total amount of the solid components and the combined flow rate of the components can be measured by known analytical means such as liquid chromatography, gas chromatography, and the like.

&Lt; Resin (B) &gt;

The resin (B) contained in the colored curable resin composition of the present invention is preferably an alkali-soluble resin, more preferably an addition polymer having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride Do. Examples of such resins include the following resins [K1] to [K6].

Resin [K1]: at least one kind (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter also referred to as "(a)"), a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond A copolymer of the monomer (b) (hereinafter also referred to as &quot; (b) &quot;)

The resin (K2): (a), (b) and the monomer (c) copolymerizable with the monomer (a) Copolymer

Resin [K3]: The copolymer of (a) and (c)

Resin [K4]: Resin (b) is obtained by reacting the copolymer of (a) and (c)

Resin [K5]: A resin obtained by reacting (a) the copolymer of (b) and (c)

Resin [K6]: a resin obtained by reacting (a) a copolymer of (b) and (c) with a carboxylic acid anhydride.

(A) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid;

But are not limited to, 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, Unsaturated dicarboxylic acids such as dimethyl tetrahydrophthalic acid and 1,4-cyclohexenedicarboxylic acid;

2,6-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept- Cyclic unsaturated compounds containing a carboxyl group such as 6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept- ;

Examples of the anhydride 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, and 5, 6-dicarboxybicyclo [2.2.1] hepto-2-anhydride, and other unsaturated dicarboxylic acid anhydrides;

Unsaturated mono [(meth) acryloyloxyalkyl] ester of a divalent or higher polyvalent carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] ;

and unsaturated acrylates containing a hydroxy group and a carboxyl group in the same molecule such as? - (hydroxymethyl) acrylic acid.

Among them, acrylic acid, methacrylic acid and maleic anhydride are preferable from the viewpoints of copolymerization reactivity and solubility of the obtained resin in an aqueous alkali solution.

(B) refers to a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (e.g., oxirane ring, oxetane ring, tetrahydrofuran ring, etc.) and an ethylenic unsaturated bond. (B) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group. In the present specification, the term "(meth) acrylic acid" means at least one kind selected from the group consisting of acrylic acid and methacrylic acid, and the term "(meth) acryloyl" Also have the same meaning.

(B2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter referred to as &quot; (b2) &quot;), ), And a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter also referred to as "(b3)").

(B1-1) (hereinafter also referred to as "(b1-1)") having a structure in which a straight chain or branched aliphatic unsaturated hydrocarbon is epoxidized, and a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (Hereinafter also referred to as &quot; (b1-2) &quot;).

(Meth) acrylate,? -Methyl glycidyl (meth) acrylate,? -Ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl Vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- Styrenes such as 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 and 2,4,6- There deulsu the lease (glycidyl oxy methyl) styrene.

(Meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and the like can be given as examples of (b1-2) vinyl cyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane, Acrylate, a compound represented by the formula (1) and a compound represented by the formula (2).

(Wherein R ^a and R ^b each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group. X ^a and X ^b each independently represent a single bond, -R ^c -, -R ^c -O-, -R ^c -S- or * -R ^c -NH-. R ^c represents an alkanediyl group having 1 to 6 carbon atoms. * Denotes the binding hand with O.)

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl and tert-butyl. Examples of the alkyl group in which the hydrogen atom is substituted with a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, 1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group.

R ^a and R ^b are each independently a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, Di-yl group, and hexane-1, 6-diyl group.

X ^a and X ^b each independently represent a single bond, a methylene group, an ethylene group, * -CH ₂ -O- or * -CH ₂ CH ₂ -O-, and a single bond or * -CH ₂ CH ₂ - O-. In the above formula, * represents a bonding bond with O.

Examples of the compound represented by the formula (1) include compounds represented by the formulas (1-1) to (1-15) The compounds represented by formulas (1-5), (1-7), (1-9) and (1-11) to (1-15) (1-7), (1-9) and (1-15) are more preferable.

Examples of the compound represented by formula (2) include compounds represented by formulas (2-1) to (2-15), and among them, compounds represented by formulas (2-1), (2-3) The compounds represented by formulas (2-5), (2-7), (2-9) and (2-11) to (2-15) (2-7), (2-9) and (2-15) are more preferable.

The compound represented by the formula (1) and the compound represented by the formula (2) may be used alone or in combination of the compound represented by the formula (1) and the compound represented by the formula (2). When these are used in combination, the ratio of the compound represented by the formula (1) and the compound represented by the formula (2) (the compound represented by the formula (1): the compound represented by the formula (2) Is from 5:95 to 95: 5, more preferably from 10:90 to 90:10, and even more preferably from 20:80 to 80:20.

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

(B3) is preferably a monomer having a tetrahydropyryl group and a (meth) acryloyloxy group. Examples of the monomer (b3) include tetrahydrofurfuryl acrylate (for example, Viscot V # 150, Ltd.) and tetrahydrofurfuryl methacrylate.

(B1) is preferably (b1) and (b1) is preferably (b1) because it is preferable that (b1) is the storage stability of the colored curable resin composition from the viewpoint that the reliability of heat resistance, chemical resistance, -2).

(Meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (Meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl hexyl (meth) acrylate, referred to as tricyclo [5.2.1.0 ^{2, 6]} decane-8-yl (meth) acrylate (trivial name in the art as "dicyclopentanyl (meth) acrylate" . Further, "tricyclo decyl (meth) acrylate" is sometimes referred to), tricyclo [5.2.1.0 ^{2, 6]} decene-8-yl (meth) acrylate in (the art, as the trivial name " (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobonyl (meth) acrylate, adamantyl (meth) acrylate, allyl (Meth) acrylic acid esters such as pargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate;

(Meth) acrylic acid esters having a hydroxy group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] 2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept- , 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] 2,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-di -Diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5 -Methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept- Cyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2 2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1 ] Hept-2-ene, and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide compounds such as 6-maleimidocaproic acid, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1, 3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.

Among these, from the viewpoint of the copolymerization reactivity and heat resistance, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6]} decane-8-yl (meth) acrylate, N- Phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferred.

In the resin [K1], the proportion of the structural unit derived from each of the resin [K1]

(A): 2 to 60 mol%

And 40 to 98 mol% of the structural unit derived from the structural unit (b)

(A): 10 to 50 mol%

More preferably 50 to 90 mol% of a structural unit derived from the structural unit (b).

When the ratio of the structural unit of the resin [K1] is within the above range, the storage stability of the colored curable resin composition, developability in forming a colored pattern, and solvent resistance of the obtained color filter tend to be more excellent.

The resin [K1] can be synthesized by, for example, a method described in "Experimental Method of Polymer Synthesis" (published by Otsu Kogyo Co., Ltd., 1st Edition, 1st Edition, March 1, 1972) . &Lt; / RTI &gt;

Specifically, a predetermined amount of (a) and (b), a polymerization initiator and a solvent are put into a reaction vessel and oxygen is replaced by, for example, nitrogen, thereby forming a deoxidized atmosphere. While stirring, I can do it. The polymerization initiator, solvent and the like to be used herein are not particularly limited and those generally used in the field can be used. Examples of the polymerization initiator include azo compounds (such as 2, 2'-azobisisobutylonitrile, 2, 2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides The solvent may be any one which dissolves the respective monomers, and examples of the solvent to be described later include a solvent for the colored curable resin composition of the present invention.

The resulting copolymer may be a solution after the reaction as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by re-precipitation or the like. Particularly, by using the solvent contained in the colored curable resin composition of the present invention as a solvent at the time of the polymerization, the solution after the reaction can be directly used for preparing the colored curable resin composition of the present invention, Can be simplified.

In the resin [K2], the proportion of the structural unit derived from each of the resins [K2]

2 to 45 mol% of a structural unit derived from the structural unit (a)

(B): 2 to 95 mol%

Is preferably 1 to 65 mol% of a structural unit derived from the structural unit (c)

(A): 5 to 40 mol%

(B): 5 to 80 mol%

More preferably from 5 to 60 mol% of a structural unit derived from the structural unit (c).

When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the colored curable resin composition, developability in forming the colored pattern, and solvent resistance, heat resistance and mechanical strength of the resulting color filter There is an excellent tendency.

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

In the resin [K3], the ratio of the respective structural units derived from the resin [K3]

(A): 2 to 60 mol%

And 40 to 98 mol% of the structural unit derived from the structural unit (c)

(A): 10 to 50 mol%

More preferably 50 to 90 mol% of a structural unit derived from the structural unit (c).

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

The resin [K4] can be produced by obtaining a copolymer of (a) and (c) and adding a cyclic ether moiety having 2 to 4 carbon atoms in (b) to a carboxylic acid and / or carboxylic acid anhydride having (a) . Specifically, it can be produced as follows. First, the copolymer of (a) and (c) is prepared in the same manner as the method described as the method for producing the resin [K1]. In this case, it is preferable that the proportion of the structural unit derived from each of them is the same as that of the resin [K3]. Next, a cyclic ether compound having 2 to 4 carbon atoms in (b) is allowed to react with a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer. (B), a catalyst for the reaction of a carboxylic acid or a carboxylic anhydride with a cyclic ether compound (for example, tris (dimethyl) Resin [K4] can be prepared by placing a polymerization inhibitor (for example, hydroquinone or the like) or the like in a flask, for example, at 60 to 130 ° C for 1 to 10 hours .

(B) is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). (B) in this range, the balance of the storage stability, developability in forming a pattern, solvent resistance of obtained patterns, heat resistance, mechanical strength and sensitivity is better There is a tendency to disappear. (B) used in the resin (K4) is preferably (b1) and (b1-1) is more preferable since the reactivity of the cyclic ether moiety is high and the unreacted (b)

The amount of the catalyst to be used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c).

The reaction conditions such as the method of introduction of the respective reagents, the reaction temperature, and the reaction time can be appropriately adjusted in consideration of the production facility or the amount of heat generated by polymerization. In addition, in the same manner as in the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production facility or the amount of heat generated by polymerization.

Resin [K5] is a first step, and a copolymer of (b) and (c) is obtained in the same manner as in the above-mentioned production method of Resin [K1]. In the same way as the above, the solution obtained after the reaction may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) obtained by re-precipitation or the like may be used. The proportion of the structural units derived from the structural units (b) and (c)

(B): 5 to 95 mol%

, And a structural unit derived from the structural unit (c): 5 to 95 mol%

(B): 10 to 90 mol%

And a structural unit derived from the structural unit (c): 10 to 90 mol%.

Further, by reacting the carboxylic acid or carboxylic acid anhydride (a) of (a) with the cyclic ether moiety derived from (b) of the copolymer (b) and (c) under the same conditions as in the production of the resin [K4] Resin [K5] can be obtained.

The amount of (a) to be reacted with the copolymer is preferably 5 to 80 moles per 100 moles of (b). (B) used in the resin (K5) is preferably (b1), and (b1-1) is more preferable because the reactivity of the cyclic ether moiety is high and unreacted (b)

Resin [K6] is a resin obtained by reacting a resin [K5] with a carboxylic acid anhydride. A carboxylic acid anhydride is reacted with a hydroxy group generated by reaction of a cyclic ether moiety and a carboxylic acid or a carboxylic anhydride.

Examples of the carboxylic anhydride 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 and 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride. The amount of the carboxylic acid anhydride to be used is preferably 0.5 to 1 mole based on 1 mole of the amount of (a).

Examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth) (Meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / benzyl (meth) acrylate / Acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl -Epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid / vinyltoluene copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / (Meth) acrylic acid / styrene copolymer (Meth) acrylate / (meth) acrylate copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (K3); resins obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer and tricyclodecyl (meth) acrylate / styrene / (Meth) acrylate, glycidyl (meth) acrylate is added to a tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (Meth) acrylate / glycidyl (meth) acrylate and a resin (K4) such as a resin to which a (meth) acrylate / glycidyl A resin obtained by reacting (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate; a resin [K5] such as tricyclodecyl (K6) such as a resin obtained by reacting a resin obtained by reacting (meth) acrylic acid with a copolymer of acrylate / glycidyl (meth) acrylate and tetrahydrophthalic anhydride.

The resin (B) is preferably selected from the group consisting of a resin [K1], a resin [K2] and a resin [K3] . When these resins are used, the colored curable resin composition is excellent in developability. From the viewpoint of the adhesion between the coloring pattern and the substrate, the resin [K2] is more preferable.

The weight average molecular weight of the resin (B) in terms of polystyrene is usually from 3,000 to 100,000, preferably from 5,000 to 50,000, more preferably from 5,000 to 35,000, Is from 5,000 to 30,000, particularly preferably from 6,000 to 30,000. When the molecular weight is in the above range, the hardness of the coating film is improved, the residual film ratio is high, the solubility to the developing solution of the unexposed portion is good, and the resolution of the coloring pattern 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 from 20 to 170 mg-KOH / g, more preferably from 30 to 170 mg-KOH / g, and particularly preferably from 40 to 170 mg-KOH / g, KOH / g is preferable, and it is preferably 50 to 150 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, still more preferably 60 to 135 mg-KOH / g, 70 to 135 mg-KOH / g is preferable. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 10 to 60% by mass, and particularly preferably 13 to 60% by mass, based on the total amount of the solid components, Is from 17 to 55 mass%. When the content of the resin (B) is in the above range, the coloring pattern is easily formed, and the resolution and residual film ratio of the coloring pattern tends to be improved.

&Lt; Polymerizable compound (C) &gt;

The polymerizable compound (C) is a compound which can be polymerized by an active radical and / or an acid generated in the polymerization initiator, and examples thereof include a polymerizable compound having an ethylenic unsaturated bond, and a (meth) acrylic ester structure Are preferred. The polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate , N-vinylpyrrolidone, and (a), (a) and (c) described above. Examples of the polymerizable compound having two ethylenic unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A and 3-methylpentanediol di (meth) acrylate. Examples of the polymerizable compound having three or more ethylenic unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (metha) acrylate, tripentaerythritol octa (metha) acrylate, tripentaerythritol hepta (metha) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritolone Acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (metha) acrylate, propylene glycol- Erythritol tetra (meth) acrylate Agent, a deulsu a propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.

The content of the polymerizable compound (C) in the colored curable resin composition of the present invention is usually 5 to 65 mass%, preferably 7 to 65 mass%, more preferably 10 to 60 mass%, based on the total solid content, By mass, more preferably from 13 to 60% by mass, and particularly preferably from 17 to 55% by mass. The mass ratio of the resin (B) to the polymerizable compound (C) (resin (B): polymerizable compound (C)) is usually 20:80 to 80:20, 80:20. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a color pattern and the chemical resistance of the color filter tend to be improved.

&Lt; Polymerization initiator (D) &gt;

The polymerization initiator (D) is not particularly limited as far as it is a compound capable of generating active radicals, acids and the like by the action of light or heat and capable of initiating polymerization, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and nonimidazole compounds.

The O-acyloxime compound is a compound having a structure represented by formula (d1). Herein, * denotes a combined hand.

As the O-acyloxime compound,

 N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine, N-benzoyloxy- N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1- -9H-carbazol-3-yl] ethan-1-imine, N-acetoxy- 1- [ Benzoyl) -9H-carbazole-3-yl] ethane-1-imine, N- acetoxy-1- [ Yl] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H- Pentylpropan-1-one-2-imine. Commercially available products such as Sigma Cure OXE01, OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy- -Imine and at least one member selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2- - (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferable.

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

Examples of the compound having a structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- 2-benzylbutan-1-one and 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan- . (Commercially available from BASF Co., Ltd.) may be used.

Examples of the compound having a structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- (4-isopropenylphenyl) propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl- ,?,? -diethoxyacetophenone and benzyldimethylketal.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (d2).

As the imidazole compound, a compound represented by formula (d5) may be mentioned.

(In the formula, R ⁵¹ to R ⁵⁶ represent an aryl group having 6 to 10 carbon atoms which may have a substituent.)

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a trityl group, a xylyl group, an ethylphenyl group and a naphthyl group, preferably a phenyl group. Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. The halogen atom includes, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and is preferably a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group and a butoxy group, and preferably a methoxy group.

Examples of the imidazole compound include 2, 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, (2-chlorophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole (see JPH06-75372-A and JPH06-75373- , 4 ', 5', 5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4'5,5'-tetra (alkoxyphenyl) Bis (2-chlorophenyl) -4,4 ', 5,5-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis 5'-tetra (trialkoxyphenyl) biimidazole (for example, see JPS48-38403-B, JPS62-174204-A and the like) and the 4,4'5,5'-up phenyl group are bonded to the carboalkoxy group An imidazole compound (e.g., Cotton, deulsu the references, JPH07-10913-A). Among them, a compound represented by the following formula and a mixture thereof are preferable.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- Bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) - &lt; / RTI &gt; 2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2, (Trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4- - [2- (3, 4-dimethoxyphenyl) Ethenyl] -1, there may be mentioned 3, 5-triazine.

As the acylphosphine oxide compound, 2,4,6-trimethylbenzoyldiphenylphosphine oxide can be mentioned.

Examples of other polymerization initiators include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone , 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, Compounds such as quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone and camphorquinone, 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate and titanocene compounds. These are preferably used in combination with a polymerization initiator (particularly an amine-based polymerization initiator) to be described later.

The polymerization initiator (D) preferably includes at least one member selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and nonimidazole compounds, O-acyloxime compounds.

The content of the polymerization initiator (D) is usually 0.1 to 40 parts by mass, preferably 0.1 to 30 parts by mass, per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) Preferably 1 to 30 parts by mass, particularly preferably 1 to 20 parts by mass.

<Polymerization Initiation Assay>

The polymerization initiator is a compound or sensitizer used for promoting polymerization of the polymerizable compound (C) initiated by the polymerization initiator (D). When the colored curable resin composition of the present invention contains a polymerization initiator, it is generally used in combination with the polymerization initiator (D).

Examples of the polymerization initiator include an amine-based polymerization initiator, an alkoxyanthracene-based polymerization initiator, a thioxanthone-based initiator, and a carboxylic acid-based polymerization initiator.

Examples of the amine-based polymerization initiator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethylbenzoate, (Dimethylamino) benzophenone (commonly referred to as Mihirazuketone), 4,4'-bis (diethylamino) benzoate, 4,4'- Phenanone, and 4,4'-bis (ethylmethylamino) benzophenone. Of these, 4,4'-bis (diethylamino) benzophenone is preferable. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may be used.

Examples of the alkoxyanthracene-based polymerization initiator include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9 , 10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

Examples of the thioxanthone polymerization initiator include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone and 1- Propoxyloxanthone.

As the carboxylic acid-based polymerization initiator, there can be used at least one compound selected from the group consisting of phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid , Chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

When the polymerization initiator is used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) . When the content of the polymerization initiator is within this range, a colored pattern can be formed with a higher sensitivity, and the productivity of the color filter tends to be improved.

&Lt; Solvent (E) &gt;

The solvent (E) is not limited, and a solvent commonly used in the field can be used. Specifically, an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- and -COO- in the molecule), an ether ester (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not including -COO-), alcohol solvent (containing OH in the molecule, O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, and dimethylsulfoxide.

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

Examples of the ether solvent 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 monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydrofuran , 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, You can have a brush.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, Methyl propionate, methyl propionate, methyl 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-petanone, acetone, 2- Cyclopentanone, cyclohexanone, and isophorone.

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

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

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

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

Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-phenanone, N, N- dimethylformamide and N- Propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 3-ethoxypropionic acid Ethyl and N-methylpyrrolidone are more preferable.

The content of the solvent (E) is usually 70 to 95 mass%, preferably 75 to 92 mass%, and more preferably 75 to 90 mass%, based on the total amount of the colored curable resin composition. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color characteristic is not insufficient when the color filter is formed, and the display characteristics tend to be good.

<Leveling agent>

Examples of the leveling agent include a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

As the silicone surfactant, a surfactant having a siloxane bond in the molecule can be exemplified. Concretely, TORAYI Silicon DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (trade name: manufactured by Torei Dow Corning), KP321, KP322, KP323, KP324, KP340, KP341 (manufactured by Shinko Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (made by Momentive E Performance Materials Japan Joint- .

As the fluorochemical surfactant, a surfactant having a fluorocarbon chain in the molecule may be mentioned. Concretely, the following materials are used: ProRad (registered trademark) FC430, FC431 (made by Sumitomo 3M Corporation), Megafox (registered trademark) F142D, Copper F171, Copper F172, Copper F173, Copper F177, Copper F183, Copper (Registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Material Electronics Co., Ltd.), SAFLON (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute).

Examples of the silicone surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafox (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC) can be used.

The content of the leveling agent is usually 0.0005 mass% or more and 0.6 mass% or less, preferably 0.001 mass% or more and 0.5 mass% or less, and more preferably 0 mass% or more, relative to the total amount of the colored curable resin composition. Is not less than 0.001 mass% and not more than 0.2 mass%, more preferably not less than 0.002 mass% nor more than 0.1 mass%, and particularly preferably not less than 0.005 mass% nor more than 0.07 mass%. When the content of the leveling agent is within the above range, the flatness of the color filter can be improved.

<Other components>

The colored curable resin composition of the present invention may contain additives known in the art such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, if necessary.

&Lt; Process for producing colored curable resin composition &gt;

The colored curable resin composition of the present invention can be obtained, for example, by mixing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E) A polymerization initiator, and other components. In addition to the colorant (A), pigments and dyes may also be mixed. The pigment is preferably used in the form of a pigment dispersion in which a part or all of the solvent (E) is mixed in advance and dispersed with a bead mill or the like until the average particle diameter of the pigment becomes about 0.2 탆 or less. At this time, if necessary, a part or all of the pigment dispersant and the resin (B) may be blended.

The compound (I) is preferably dissolved in a part or all of the solvent (E) to prepare a solution. It is preferable to filter the solution with a filter having a pore diameter of about 0.01 to 1 mu m.

The colored curable resin composition after mixing is preferably filtered with a filter having a pore diameter of about 0.01 to 10 mu m.

<Manufacturing Method of Color Filter>

Examples of a method for producing a colored pattern using the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, a printing method, and the like. Among them, a photolithographic method is preferable. The photolithography method is a method in which a colored curable resin composition is coated on a substrate, and then dried to form a colored composition layer, and the colored composition layer is exposed through a photomask to perform development. In the photolithographic method, a colored coating film which is a cured product of the colored composition layer can be formed by not using a photomask at the time of exposure and / or by not developing it. The coloring pattern or colored coating film thus formed is the color filter of the present invention.

The film thickness of the color filter to be produced can be appropriately adjusted depending on the purpose or use, and is usually 0.1 to 30 탆, preferably 0.1 to 20 탆, more preferably 0.5 to 6 탆.

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass and soda lime glass whose surface is coated with silica, resin plates such as polycarbonate, polymethylmethacrylate and polyethylene terephthalate, silicon, Aluminum, silver, silver / copper / palladium alloy thin film, or the like is formed. A separate color filter layer, a resin layer, a transistor, a circuit, and the like may be formed on these substrates.

The formation of each color pixel by the photolithographic method can be carried out by a known or common apparatus or condition. For example, it can be manufactured as follows.

First, a colored curable resin composition is coated on a substrate, and heated and dried (pre-baked) and / or reduced-pressure drying to remove volatile components such as a solvent and dried to obtain a smooth colored composition layer. Examples of the application method include a spin coating method, a slit coating method, and a slit and spin coating method. The temperature in the case of heating and drying is preferably 30 to 120 占 폚, more preferably 50 to 110 占 폚. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. In the case of carrying out the reduced-pressure drying, it is preferably carried out at a temperature of 20 to 25 캜 under a pressure of 50 to 150 Pa. The film thickness of the coloring composition layer is not particularly limited and may be appropriately selected depending on the intended thickness of the color filter.

Next, the coloring composition layer is exposed through a photomask for forming a desired coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used. As a light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light having a wavelength of less than 350 nm may be cut using a filter that cuts the wavelength region, or light having a wavelength of about 436 nm, a wavelength around 408 nm, and a wavelength around 365 nm may be band-pass filtered ). Specific examples of the light source include mercury lamps, light emitting diodes, metal halide lamps, and halogen lamps. It is preferable to use an exposure apparatus such as a mask aligner or a stepper because uniform light rays can be uniformly irradiated to the entire exposure surface or the photomask can be precisely aligned with the substrate on which the coloring composition layer is formed. The colored composition layer after exposure is brought into contact with a developing solution to develop a colored pattern on the substrate. By the development, the unexposed portion of the colored composition layer is dissolved and removed in the developer. As the developing solution, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide or the like is preferable. The concentration of the alkaline compound is preferably 0.01 to 10% by mass, and more preferably 0.02 to 5% by mass. The developer may contain a surfactant. The developing method may be any of a paddle method, a dipping method and a spray method. Further, the substrate may be inclined at an arbitrary angle during development. It is preferable to rinse after development.

It is preferable to perform post-baking on the obtained coloring pattern. The post bake temperature is preferably 150 to 250 DEG C, more preferably 160 to 235 DEG C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

The color filter formed from the colored curable resin composition of the present invention is useful as a color filter used in a display device (e.g., a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image pickup device.

[Example]

Hereinafter, the present invention will be described more specifically by way of examples. In the examples, &quot;% &quot; and &quot; part &quot; are by mass% and mass part, respectively, unless otherwise specified.

In the following synthesis examples, the structure of the compound was confirmed by NMR (JMM-ECA-500; manufactured by Japan Electronics Co., Ltd.) or mass spectrometry (LC; Agilent 1200 type, MASS; LC / MSD6130 type manufactured by Agilent).

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin in terms of polystyrene were measured by the GPC method under the following conditions.

Apparatus: HLC-8120GPC (manufactured by TOSOH CORPORATION)

Column: TSK-GELG2000HXL

Column temperature: 40 DEG C

Solvent: tetrahydrofuran

Flow rate: 1.0 mL / min

Solid content concentration of analytical sample: 0.001 to 0.01 mass%

Injection volume: 50 μL

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by TOSOH CORPORATION)

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

Synthesis Example 1

10.1 parts of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 51.0 parts of methanol were mixed, and 12.6 parts of 3-ethoxy-3-iminopropionic acid ethyl hydrochloride Was added. Thereafter, the reaction mixture was stirred for 5 hours at 10 DEG C or lower, 24 hours at room temperature, and 24 hours at 60 DEG C. [ After cooling the reaction mixture to room temperature, 300 parts of water and 270 parts of ethyl acetate were added, and an ethyl acetate layer was collected. To the aqueous layer was added 135 parts of ethyl acetate, and an ethyl acetate layer was collected. To the aqueous layer (water layer), 135 parts of ethyl acetate was added, and an ethyl acetate layer was collected. The ethyl acetate layers were combined, washed with 300 parts of water three times, dried over magnesium sulfate and filtered. The solvent of the filtrate was distilled to obtain a residue. The residue was purified by column chromatography to obtain 14.5 parts of a compound represented by the formula (pt1).

&Lt; Identification of compound represented by formula (pt1) &gt;

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 559.1

Exact Mass: 558.1

75.0 parts of dimethylsulfoxide and 8.45 parts of potassium hydroxide were mixed in a nitrogen atmosphere, and the mixture was stirred at room temperature for 0.5 hours. To this mixture, 25.0 parts of 3-methoxydiphenylamine was added, and the mixture was stirred at room temperature for 0.5 hours. To this mixture, 21.5 parts of iodine ethane was added, and the mixture was stirred at room temperature for 2 hours. To the resultant mixture was added 4.23 parts of potassium hydroxide, and the mixture was stirred at room temperature for 1 hour, then 10.8 parts of iodine ethane was added, and the mixture was stirred at room temperature for 12 hours. To the obtained mixture, 4.23 parts of potassium hydroxide was added, and the mixture was stirred at room temperature for 1 hour, then 10.8 parts of iodine ethane was added, and the mixture was stirred at room temperature for 2 hours. To the obtained mixture, 4.23 parts of potassium hydroxide was added, and the mixture was stirred at room temperature for 1 hour. Then, 10.8 parts of iodine ethane was added, and the mixture was stirred at room temperature for 13 hours. To the resulting mixture, 158 parts of water and 135 parts of ethyl acetate were added, and an ethyl acetate layer was collected. To the aqueous layer was added 90 parts of ethyl acetate, and an ethyl acetate layer was collected. The ethyl acetate layers were combined and washed three times with 100 parts of water. This ethyl acetate solution was dried with magnesium sulfate and filtered. The solvent of the filtrate was distilled to obtain 28.4 parts of a compound represented by the formula (pt3-1).

&Lt; Identification of compound represented by formula (pt3-1) &gt;

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 228.1

Exact Mass: 227.1

28.4 parts of the compound represented by the formula (pt3-1) and 302 parts of methylene chloride were mixed in a nitrogen atmosphere. While maintaining the mixture at 4 to 10 占 폚, 44.8 parts of boron tribromide was added, followed by stirring at room temperature for 12 hours. The resulting mixture was added to a mixture of 341 parts of water and 302 parts of methylene chloride while maintaining the temperature of the mixture of 341 parts of water and 302 parts of methylene chloride at 4 to 19 占 폚. This mixture was stirred at room temperature for 2 hours to collect a methylene chloride layer. The methylene chloride solution was washed four times with 227 parts of 10 wt% saline, dried with magnesium sulfate, and filtered. The solvent of the filtrate was distilled to obtain 23.3 parts of a compound represented by the formula (pt4-1).

<Identification of Compound Represented by Formula (pt4-1)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 214.1

Exact Mass: 213.1

Under nitrogen atmosphere, 25.1 parts of phosphorus chloride was added to 47.7 parts of N, N-dimethylformamide while maintaining the temperature at 6 to 15 占 폚. To this mixture, a mixture of 23.3 parts of the compound represented by the formula (pt4-1) and 31.4 parts of N, N-dimethylformamide was added while maintaining the temperature of the mixture at 6 to 25 占 폚. The mixture was stirred at 40 캜 for 2 hours and then cooled to room temperature. The resulting mixture was added to a mixture of 109 parts of a 48 wt% aqueous solution of sodium hydroxide and 410 parts of water while maintaining the temperature at 14 to 19 占 폚 and stirred for 1 hour. To the resultant mixture was added 67.2 parts of 35 wt% hydrochloric acid while maintaining the temperature at 12 to 17 캜. To the resulting mixture, 210 parts of ethyl acetate and celite were added and the mixture was filtered. The obtained filtrate was washed twice with 233 parts of 10 wt% saline, dried over magnesium sulfate, and filtered. The solvent of the obtained filtrate was distilled to obtain a residue. The residue was purified by column chromatography to obtain 23.9 parts of a compound represented by the formula (pt5-1).

<Identification of compound represented by formula (pt5-1)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 242.1

Exact Mass: 241.1

10.9 parts of the compound represented by the formula (pt5-1), 12.0 parts of the compound represented by the formula (pt1), 0.915 part of piperidine and 83.8 parts of toluene were mixed in a nitrogen atmosphere. This mixture was stirred at 100 ° C for 19 hours. The solvent of the mixed solution was distilled to obtain a residue. The residue was purified by column chromatography to obtain 10.6 parts of a compound represented by the formula (I-1).

&Lt; Identification of the compound represented by formula (I-1) &gt;

¹ H-NMR (CDCl ₃ , 270 MHz)? 1.31 (6H), 3.84 (4H), 6.58-6.61 (4H), 7.16-7.24 (4H), 7.31-7.39 (6H), 7.46-7.52 7.55 (2H), 7.99 (2H), 8.63 (2H)

Synthesis Example 2

42.4 parts of 2,4-dimethylaniline, 35.4 parts of triethylamine and 132 parts of N, N-dimethylformamide were mixed and stirred at 50 ° C. 56.8 parts of iodine ethane was added while maintaining the temperature of the mixture at 50 to 60 DEG C, and then the mixture was stirred at 60 DEG C for 65 hours. After the mixture was cooled to room temperature, 1000 parts of water and 433 parts of toluene were added, and the toluene layer was collected. The toluene layer was washed three times with 1000 parts of an aqueous saturated sodium chloride solution, and then the solvent was distilled off using a rotary vacuum concentrator. The obtained residue was purified by column chromatography to obtain 18.8 parts of a compound represented by the formula (pt2-2).

<Identification of Compound Represented by Formula (pt2-2)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 150.1

Exact Mass: 149.1

In a nitrogen atmosphere, 29.8 parts of the compound represented by the formula (pt2-2), 37.4 parts of 3-bromoanisole, 1.35 parts of palladium (II) acetate, 33.7 parts of potassium tert- 3.42 parts of 2,8,8,9-triisopropyl-2,5, 8,9-tetraaza-1-phosphabicyclo [3.3.3] undecane (1.0M toluene solution) and 520 parts of toluene The mixture was stirred at 100 캜 for 6 hours. This mixed solution was cooled to room temperature and then added to 1000 parts of water. After filtering the mixed solution, the toluene layer was collected. The toluene solution was washed with a saturated aqueous solution of sodium hydrogencarbonate, dried with magnesium sulfate, and filtered. The filtrate was distilled using a rotary vacuum concentrator, and the obtained residue was purified by column chromatography to obtain 41.9 parts of a compound represented by the formula (pt3-2).

<Identification of Compound Represented by Formula (pt3-2)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 256.2

Exact Mass: 255.2

(Pt4-2) and (pt3-2) were carried out in the same manner as in Synthesis Example 1, except that the compound represented by the formula (pt3-1) was replaced with the compound represented by the formula (pt3-2) (Pt5-2) and a compound represented by the formula (I-2).

&Lt; Identification of each compound &gt;

The compound represented by the formula (pt4-2)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 242.2

Exact Mass: 241.2

The compound represented by the formula (pt5-2)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 270.2

Exact Mass: 269.1

The compound represented by the formula (I-2)

_{^{1 H-NMR (CDCl 3,}} 270 MHz) δ 1.30 (6H), 2.09 (6H), 2.39 (6H), 3.59 (2H), 3.86 (2H), 6.42 (4H), 7.00 (2H), 7.12 (2H ), 7.18 (2H), 7.30-7.37 (4H), 7.54 (2H), 7.98

Synthesis Example 3

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, a nitrogen gas was flowed in an appropriate amount to make a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added and heated to 85 캜 with stirring. Then, in the flask, 19 parts of methacrylic acid, the resin composition comprising 3,4-tricyclo [5.2.1.0 ^{2, 6]} decane-8-yl acrylate and 3,4-epoxy-tricyclo [5.2 ^{1, 2, 6} ] decan-9-yl acrylate (content ratio: 50:50 in molar ratio) in 40 parts of propylene glycol monomethyl ether acetate was added dropwise at about 5 hours . On the other hand, a solution prepared by dissolving 26 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was dropped into a flask using a dropping pump for about 5 hours did. After the dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin B1) having a solid content of 43.5%. The resin B1 thus obtained had a weight average molecular weight of 8000, a molecular weight distribution of 1.98, and an acid value in terms of solid content of 53 mgKOH / g.

Synthesis Example 4

In an atmosphere of nitrogen, 24.0 parts of m-anisidine, 99.7 parts of 4-iodo-m-xylene, 117 parts of potassium carbonate, 27.3 parts of copper powder, 4.64 parts of 18- And 511 parts of benzene were mixed and stirred at 175 占 폚 for 19 hours. Thereafter, 35.1 parts of potassium carbonate, 8.19 parts of copper powder, 1.39 parts of 18-crown-6, and 22.0 parts of o-dichlorobenzene were added, and the mixture was stirred at 175 캜 for 17 hours. The mixture was cooled to room temperature and filtered. 450 parts of ethyl acetate was added to the filtrate, and the mixture was washed three times with 450 parts of 2N hydrochloric acid and three times with 470 parts of 18 wt% sodium chloride aqueous solution. The obtained ethyl acetate solution was dried over magnesium sulfate and filtered. The solvent was distilled off from the filtrate using a rotary vacuum concentrator, and the obtained residue was purified by column chromatography to obtain 64.1 parts of a compound represented by the formula (pt3-3).

<Identification of compound represented by formula (pt3-3)

(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 332.2

Exact Mass: 331.2

(Pt4-3) and (pt3-3) were carried out in the same manner as in Synthesis Example 1, except that the compound represented by the formula (pt3-1) was replaced with the compound represented by the formula (pt3-3) (Pt5-3) and a compound represented by the formula (I-82).

&Lt; Identification of each compound &gt;

The compound represented by the formula (pt4-3)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 318.2

Exact Mass: 317.2

The compound represented by the formula (pt5-3)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 346.2

Exact Mass: 345.2

The compound represented by the formula (I-82)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 1121.4

Exact Mass: 1120.4

Synthesis Example 5

(Pt4-4), (pt4-4), (pt5-4) and (pt5-4) were carried out in the same manner as in Synthesis Example 1 except that iodoethane was replaced with 2-ethoxyethyl bromide in Synthesis Example 1, ) And a compound represented by the formula (I-141).

&Lt; Identification of each compound &gt;

The compound represented by the formula (pt3-4)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 272.2

Exact Mass: 271.2

The compound represented by the formula (pt4-4)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 258.1

Exact Mass: 257.1

The compound represented by the formula (pt5-4)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 286.1

Exact Mass: 285.1

The compound represented by the formula (I-141)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 1001.3

Exact Mass: 1000.3

Synthesis Example 6

(Pt2-5), (pt3-5), and (pt3-5) were carried out in the same manner as in Synthesis Example 2 except that 2,4,6-trimethylaniline was used instead of 2,4- (Pt4-5), a compound represented by the formula (pt5-5) and a compound represented by the formula (I-146).

&Lt; Identification of each compound &gt;

The compound represented by the formula (pt2-5)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 164.1

Exact Mass: 163.1

The compound represented by the formula (pt3-5)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 270.2

Exact Mass: 269.2

The compound represented by the formula (pt4-5)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 256.2

Exact Mass: 255.2

The compound represented by the formula (pt5-5)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 284.2

Exact Mass: 283.2

The compound represented by the formula (I-146)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 997.3

Exact Mass: 996.3

Synthesis Example 7

Synthesis was carried out in the same manner as in Synthesis Example 4 except that 4-iodo-m-xylene was replaced with 2-iodo-1,3,5-trimethylbenzene in Synthesis Example 4 to obtain a compound represented by Formula (pt3-6), Formula pt4-6), a compound represented by the formula (pt5-6) and a compound represented by the formula (I-86).

&Lt; Identification of each compound &gt;

The compound represented by the formula (pt3-6)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 360.2

Exact Mass: 359.2

The compound represented by the formula (pt4-6)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 346.2

Exact Mass: 345.2

The compound represented by the formula (pt5-6)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 374.2

Exact Mass: 373.2

The compound represented by the formula (I-86)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 1177.4

Exact Mass: 1176.4

Example 1

4.98 parts of bis (3-amino-4-hydroxyphenyl) sulfone and 28.1 parts of methanol were mixed. To the resulting mixture was gradually added 8.18 parts of 3-ethoxy-3-iminopropionic acid ethyl hydrochloride at 10 占 폚 or lower with stirring. The resulting mixture was stirred at 10 占 폚 or lower for 7 hours, at room temperature for 24 hours, and at 60 占 폚 for 24 hours. After the obtained reaction mixture was cooled to room temperature, the precipitated crystals were taken out by filtration. The crystals taken out were washed with methanol and dried under reduced pressure at 60 ° C to obtain 6.77 parts of a compound represented by the formula (pt1-1a).

<Identification of Compound Represented by Formula (pt1-1a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 473.1

Exact Mass: 472.1

42.4 parts of 2,4-dimethylaniline, 35.4 parts of triethylamine and 132 parts of N, N-dimethylformamide were mixed and stirred at 50 占 폚. 70.2 parts of 1-bromo-2-ethylhexane was added while maintaining the temperature of the mixture at 50 to 60 DEG C, and then the mixture was stirred at 60 DEG C for 65 hours. After the mixture was cooled to room temperature, 1000 parts of water and 433 parts of toluene were added to separate the toluene layer. The toluene layer was washed three times with 1000 parts of a saturated aqueous sodium chloride solution, and then the solvent was distilled off with a rotary vacuum concentrator. The obtained residue was purified by column chromatography to obtain 50.6 parts of a compound represented by the formula (pt2-1a).

(pt2-1a)

(pt2-1a)

<Identification of compound represented by formula (pt2-1a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 234.2

Exact Mass: 233.2

46.7 parts of a compound represented by the formula (pt2-1a), 37.4 parts of 3-bromoanisole, 1.35 parts of palladium (II) acetate, 33.7 parts of potassium tert-butoxide, 3.42 parts of 2,8,8,9-triisopropyl-2,5, 8,9-tetraaza-1-phosphabicyclo [3.3.3] undecane (1.0M toluene solution) and 520 parts of toluene The mixture was stirred at 100 캜 for 6 hours. The resulting mixture was cooled to room temperature and then added to 1000 parts of water. The resulting mixture was filtered, and then the toluene layer was separated. The toluene layer was washed with saturated aqueous sodium hydrogencarbonate solution, dried over magnesium sulfate and filtered. The solvent was distilled off from the filtrate using a rotary vacuum concentrator, and the obtained residue was purified by column chromatography to obtain 30.9 parts of a compound represented by the formula (pt3-1a).

<Identification of compound represented by formula (pt3-1a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 340.3

Exact Mass: 339.3

17.0 parts of the compound represented by the formula (pt3-1a) and 199 parts of dichloromethane were mixed in a nitrogen atmosphere. Boron tribromide (1.0 M dichloromethane solution) was added in an amount equivalent to the molar amount of the compound represented by formula (pt3-1a) while maintaining the mixture at 15 to 23 占 폚. Thereafter, this mixed solution was stirred at room temperature for 8 hours. The obtained mixture was added to 250 parts of ice water (ice water), and the dichloromethane layer was separated. The dichloromethane layer was washed with 250 parts of water, dried over magnesium sulfate and filtered. The solvent was distilled off using a rotary vacuum concentrator. The obtained residue was purified by column chromatography to obtain 13.9 parts of a compound represented by the formula (pt4-1a).

<Identification of compound represented by formula (pt4-1a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 326.3

Exact Mass: 325.2

13.9 parts of the compound represented by the formula (pt4-1a) and 26.4 parts of N, N-dimethylformamide were mixed. While maintaining the mixture at 23 to 55 캜, 13.1 parts of phosphorus chloride was added. Thereafter, this mixture was stirred at 60 占 폚 for 6 hours. The mixture was cooled to room temperature, added to 150 parts of ice water, and neutralized with a 48% aqueous solution of sodium hydroxide. To this mixture was added 300 parts of ethyl acetate, and the mixture was filtered, and the ethyl acetate layer was separated from the obtained filtrate. This ethyl acetate solution was washed with 300 parts of water, dried over magnesium sulfate and filtered. The solvent was distilled off using a rotary vacuum concentrator. The resulting residue was purified by column chromatography to obtain 11.6 parts of a compound represented by the formula (pt5-1a).

<Identification of Compound Represented by Formula (pt5-1a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 354.2

Exact Mass: 353.2

9.65 parts of a compound represented by the formula (pt5-1a), 6.14 parts of a compound represented by the formula (pt1-1a), 0.553 parts of piperidine and 51.1 parts of toluene were mixed in a nitrogen atmosphere. This mixture was stirred at 100 ° C for 19 hours. This mixed solution was added to 231 parts of methanol. By removing the supernatant, the resulting precipitate was taken out. To the precipitate, 231 parts of methanol was added and stirred, and the mixture was subjected to suction filtration. The obtained residue was washed with 20 parts of methanol and obtained as a residue of suction filtration. The residue was purified by column chromatography to obtain 9.10 parts of a compound represented by the formula (IA-13).

<Identification of Compound Represented by Formula (IA-13)

¹ H-NMR (CDCl ₃ , 270 MHz)? 0.82-0.92 (12H), 1.26-1.52 (16H), 1.77 (2H), 2.05 (6H), 2.38 (2H), 7.62 (2H), 7.62 (2H), 6.42 (2H), 6.42-6.45 (2H), 7.02 )

Example 2

(Pt2-2a), (pt3-2a), and (pt3-2a) were carried out in the same manner as in Example 1 except that 1-bromo-2-ethylhexane was used instead of 1- (Pt4-2a), (pt5-2a) and (IA-17).

&Lt; Identification of each compound &gt;

The compound represented by the formula (pt2-2a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 234.2

Exact Mass: 233.2

The compound represented by the formula (pt3-2a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 340.3

Exact Mass: 339.3

The compound represented by the formula (pt4-2a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 326.3

Exact Mass: 325.2

The compound represented by the formula (pt5-2a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 354.2

Exact Mass: 353.2

The compound represented by the formula (IA-17)

_{^{1 H-NMR (CDCl 3,}} 270 MHz) δ 0.88 (6H), 1.28-1.32 (20H), 1.72 (4H), 2.07 (6H), 2.38 (6H), 3.44 (2H), 3.77 (2H), 6.39 (2H), 7.96 (2H), 8.39 (2H), 8.62 (2H)

Example 3

(Pt2-3a) and (pt3-3a) were obtained in the same manner as in Example 1, except that 1-bromo-2-ethylhexane was used instead of 1- 3a), a compound represented by the formula (pt4-3a), a compound represented by the formula (pt5-3a) and a compound represented by the formula (IA-297).

&Lt; Identification of each compound &gt;

The compound represented by the formula (pt2-3a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 192.2

Exact Mass: 191.2

The compound represented by the formula (pt3-3a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 298.2

Exact Mass: 297.2

The compound represented by the formula (pt4-3a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 284.2

Exact Mass: 283.2

The compound represented by the formula (pt5-3a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 312.2

Exact Mass: 311.2

The compound represented by the formula (IA-297)

_{^{1 H-NMR (CDCl 3,}} 270 MHz) δ 0.96 (12H), 1.57-1.69 (6H), 2.08 (6H), 2.39 (6H), 3.47 (2H), 3.80 (2H), 6.39 (4H), 6.99 (2H), 7.12 (2H), 7.17 (2H), 7.34 (2H), 7.66

Example 4

39.9 parts (0.200 mole) of 3-methoxydiphenylamine, 13.5 parts (0.240 mole) of potassium hydroxide and 550 parts of dimethylsulfoxide were mixed in a nitrogen atmosphere, and the mixture was stirred at room temperature for 2 hours. 42.5 parts (0.220 mol) of 1-bromo-2-ethylhexane was added to the mixture, and the mixture was stirred at room temperature for 6 hours. 42.5 parts (0.220 mol) of 1-bromo-2-ethylhexane and 20.2 parts (0.360 mol) of potassium hydroxide were added to the mixture, and the mixture was stirred at room temperature for 14 hours. 63.7 parts (0.330 mol) of 1-bromo-2-ethylhexane and 20.2 parts (0.360 mol) of potassium hydroxide were added to the mixture, and the mixture was stirred at room temperature for 24 hours. To this mixture, 1000 parts of water and 450 parts of toluene were added, and the toluene layer was collected. This toluene solution was washed twice with a saturated aqueous solution of sodium hydrogencarbonate (1500 parts), dried over magnesium sulfate, and filtered. The solvent of the obtained filtrate was distilled to obtain a residue. The residue was purified by column chromatography to obtain 59.8 parts of a compound represented by the formula (pt3-4a).

<Identification of Compound Represented by Formula (pt3-4a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 312.2

Exact Mass: 311.2

(Pt4-4a), (pt5-4a), and (pt5-4a) were obtained in the same manner as in Example 1 except that the compound represented by the formula (pt3-1a) ) And a compound represented by the formula (IA-15).

&Lt; Identification of each compound &gt;

The compound represented by the formula (pt4-4a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 298.2

Exact Mass: 297.2

The compound represented by the formula (pt5-4a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 326.2

Exact Mass: 325.2

The compound represented by the formula (IA-15)

_{^{1 H-NMR (CDCl 3,}} 270 MHz) δ 0.82-0.88 (12H), 1.22-1.52 (16H), 1.80 (2H), 3.69 (4H), 6.58-6.63 (4H), 7.21-7.24 (4H), 7.31-7.37 (4H), 7.45-7.50 (4H), 7.67 (2H), 7.97 (2H), 8.40

Example 5

(Pt3-5a), (pt4-5a), and (pt4-5a) were carried out in the same manner as in Example 4 except that 1-bromo-2-ethylhexane was replaced with 1-bromododecane, (Pt5-5a) and a compound represented by the formula (IA-299).

&Lt; Identification of each compound &gt;

The compound represented by the formula (pt3-5a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 368.3

Exact Mass: 367.3

The compound represented by the formula (pt4-5a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 354.3

Exact Mass: 353.3

The compound represented by the formula (pt5-5a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 382.3

Exact Mass: 381.3

The compound represented by the formula (IA-299)

¹ H-NMR (CDCl ₃ , 270 MHz)? 0.87 (6H), 1.25-1.30 (36H), 1.72 (4H), 3.72 (4H), 6.54-6.58 (4H), 7.20-7.23 7.39 (4H), 7.46-7.51 (4H), 7.67 (2H), 7.97 (2H), 8.40

Example 6

(Pt2-6a) and (pt3-6a) were obtained in the same manner as in Example 1 except that 1-bromo-2-ethylhexane was replaced with 2-ethoxyethyl bromide in Example 1, ), The formula (pt4-6a), the formula (pt5-6a) and the formula (IA-306).

&Lt; Identification of each compound &gt;

The compound represented by the formula (pt2-6a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 194.2

Exact Mass: 193.1

The compound represented by the formula (pt3-6a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 300.2

Exact Mass: 299.2

The compound represented by the formula (pt4-6a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 286.2

Exact Mass: 285.2

The compound represented by the formula (pt5-6a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 314.2

Exact Mass: 313.2

The compound represented by the formula (IA-306)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 971.3

Exact Mass: 970.3

Example 7

10.0 parts of 2,2-bis (3-amino-4-hydroxyphenyl) propane and 51.0 parts of methanol were mixed and stirred at a temperature of 5 ° C or lower, to obtain ethyl 3-ethoxy-3-iminopropionate hydrochloride 2 parts were added. Thereafter, the reaction mixture was stirred for 13 hours at 10 占 폚 or lower, 24 hours at room temperature, and 24 hours at 60 占 폚. The reaction mixture was cooled to room temperature. The reaction mixture was distilled using a rotary vacuum concentrator. The obtained residue was purified by column chromatography to obtain 6.46 parts of a compound represented by the formula (pt 1-7a).

&Lt; Identification of compound represented by formula (pt1-7a) &gt;

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 451.2

Exact Mass: 450.2

In the same manner as in Example 1 except that the compound represented by the formula (pt1-1a) was replaced with the compound represented by the formula (pt1-7a) and 1-bromo-2-ethylhexane was replaced with 1-bromooctane Was carried out in the same manner as in Example 1 to obtain a compound represented by the formula (IA-49).

<Identification of Compound Represented by Formula (IA-49)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 1029.6

Exact Mass: 1028.5

Example 8

5.02 parts of 9,9-bis (3-amino-4-hydroxyphenyl) fluorene and 30.0 parts of methanol were mixed and stirred at 5 占 폚 or lower with 3-ethoxy-3-iminopropionic acid ethyl hydrochloride 6 . The reaction mixture was then stirred for 14 hours at 10 占 폚 or lower, 24 hours at room temperature, and 24 hours at 60 占 폚. The reaction mixture was cooled to room temperature. The reaction mixture was distilled using a rotary vacuum concentrator. The obtained residue was purified by column chromatography to obtain 2.33 parts of a compound represented by the formula (pt1-8a).

<Identification of compound represented by formula (pt1-8a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 573.2

Exact Mass: 572.2

In the same manner as in Example 1 except that the compound represented by the formula (pt1-1a) was replaced with the compound represented by the formula (pt1-8a), 1-bromo-2-ethylhexane was replaced with 1-bromooctane Was carried out in the same manner as in Example 1 to obtain a compound represented by the formula (IA-81).

Identification of the compound represented by the formula (IA-81)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 1151.6

Exact Mass: 1150.6

Example 9

Example 1 was repeated except that 2,4-dimethylaniline was replaced by 2,4,6-trimethylaniline and 1-bromo-2-ethylhexane was replaced by 1-bromooctane in Example 1 The compound represented by the formula (pt2-9a), the formula (pt3-9a), the formula (pt4-9a), the formula (pt5-9a) and the formula (I-308) was obtained in the same manner.

&Lt; Identification of each compound &gt;

The compound represented by the formula (pt2-9a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 248.2

Exact Mass: 247.2

The compound represented by the formula (pt3-9a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 354.3

Exact Mass: 353.3

The compound represented by the formula (pt4-9a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 340.3

Exact Mass: 339.3

The compound represented by the formula (pt5-9a)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 368.3

Exact Mass: 367.3

The compound represented by the formula (IA-308)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 1079.5

Exact Mass: 1078.5

Example 10

The compound represented by formula (pt1-1a) was obtained in the same manner as in Example 1, except that the compound represented by formula (pt1-7a) was replaced by 2,4,6-trimethylaniline, A compound represented by the formula (IA-311) was obtained in the same manner as in Example 1 except that 1-bromo-2-ethylhexane was replaced with 1-bromooctane.

<Identification of Compound Represented by Formula (IA-311)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 1057.6

Exact Mass: 1056.6

&Lt; Evaluation of heat resistance &

(IA-13), (IA-17) and (IA-297) obtained in Examples 1 to 10 were measured using a differential thermal thermogravimetry (TG / DTA6200R, , IA-15, IA-299, IA-306, IA-49, IA-81, IA-308 and IA-311 The compound to be displayed and differential scanning calorimetry of coumarin 6 (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were measured. The amount of sample used for one measurement was 5 mg. The measurement temperature was first started at 25 占 폚, the temperature was raised at a rate of 10 占 폚 per minute, and the measurement was performed up to 600 占 폚. Temperature in weight loss under in weight reduction of 5%, the temperature _{T 5} (air-to), according to the air temperature _{T 10} which is 10% weight reduction (air down), the nitrogen atmosphere is in the air, this is a 5% _{T 5} (Under nitrogen), and a temperature T ₁₀ (under nitrogen) at which the weight loss rate was 10% in a nitrogen atmosphere. The results are shown in Table 30.

compound T ₅ (under air)
(° C) T ₁₀ (under air)
(° C) T ₅ (under nitrogen)
(° C) T ₁₀ (under nitrogen)
(° C) IA-13 393 406 420 426 IA-17 390 404 412 420 IA-297 391 405 405 413 IA-15 389 404 408 415 IA-299 381 397 409 418 IA-306 380 397 402 411 IA-49 388 401 404 412 IA-81 373 388 399 405 IA-308 383 400 401 410 IA-311 381 395 402 410 Coumarin 6 327 344 331 348

From the results shown in Table 30, it can be seen that the compound (Ia-1) of the present invention has a high thermal stability.

Example 11

4.98 parts of bis (3-amino-4-hydroxyphenyl) sulfone and 28.1 parts of methanol were mixed, and 8.18 parts of 3-ethoxy-3-iminopropionic acid hydrochloride was slowly added did. Thereafter, the reaction mixture was stirred for 7 hours at 10 占 폚 or lower, 24 hours at room temperature, and 24 hours at 60 占 폚. The reaction mixture was cooled to room temperature, and the precipitated crystals were obtained as a residue of suction filtration. The residue was washed with methanol and dried under reduced pressure at 60 ° C to obtain 6.77 parts of a compound represented by the formula (pt1-1b).

&Lt; Identification of compound represented by formula (pt1-1b) &gt;

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 473.1

Exact Mass: 472.1

In an atmosphere of nitrogen, 24.0 parts of m-anisidine, 99.7 parts of 4-iodo-m-xylene, 117 parts of potassium carbonate, 27.3 parts of copper powder, 4.64 parts of 18- And 511 parts of benzene were mixed and stirred at 175 占 폚 for 19 hours. Thereafter, 35.1 parts of potassium carbonate, 8.19 parts of copper powder, 1.39 parts of 18-crown-6, and 22.0 parts of o-dichlorobenzene were added, and the mixture was stirred at 175 캜 for 17 hours. The mixture was cooled to room temperature and filtered. 450 parts of ethyl acetate was added to the filtrate, and the mixture was washed three times with 450 parts of 2N hydrochloric acid and three times with 470 parts of 18 wt% sodium chloride aqueous solution. The obtained ethyl acetate solution was dried with magnesium sulfate and filtered. The solvent was distilled off using a rotary vacuum concentrator and the resulting residue was purified by column chromatography to obtain 64.1 parts of a compound represented by the formula (pt2-1b).

<Identification of compound represented by formula (pt2-1b)

(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 332.2

Exact Mass: 331.2

31.7 parts of the compound represented by the formula (pt2-1b) and 190 parts of dehydrated dichloromethane were mixed under a nitrogen atmosphere at 0 占 폚. Subsequently, 199 parts of a 17 wt% boron dichloride dichloromethane solution was added, and the mixture was stirred for 1 hour. Thereafter, the mixture was stirred at room temperature for 12 hours. This mixture was added to 1100 parts of ice water, and then 740 parts of chloroform was added to extract the chloroform layer. The resulting chloroform solution was washed twice with 470 parts of an aqueous 18 wt% sodium chloride solution, dried with magnesium sulfate, and filtered. The solvent was distilled off using a rotary vacuum concentrator and the resulting residue was purified by column chromatography to obtain 30.0 parts of a compound represented by the formula (pt3-1b).

<Identification of compound represented by formula (pt3-1b)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 318.2

Exact Mass: 317.2

7.46 parts of the compound represented by the formula (pt3-1b) and 14.4 parts of N, N-dimethylformamide were mixed at 5 to 10 캜 under a nitrogen atmosphere. While maintaining the temperature of the mixture at 5 to 10 占 폚, 7.21 parts of phosphorus chloride was added. Thereafter, the mixture was stirred at 10 ° C or lower for 1 hour, at room temperature for 1 hour, and at 80 ° C for 1 hour. After cooling the reaction mixture to room temperature, 100 parts of ice water was added, and the mixture was neutralized with a 48% aqueous solution of sodium hydroxide. To this mixture, 180 parts of ethyl acetate was added, and then celite was added, followed by stirring. The mixture was filtered to extract an ethyl acetate layer. The ethyl acetate layer was dried with magnesium sulfate and filtered. The filtrate was subjected to solvent distillation using a rotary vacuum concentrator, and the obtained residue was purified by column chromatography to obtain 6.26 parts of a compound represented by the formula (pt4-1b).

<Identification of Compound Represented by Formula (pt4-1b)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 346.2

Exact Mass: 345.2

6.01 parts of the compound represented by the formula (pt4-1b), 4.04 parts of the compound represented by the formula (pt1-1b), 0.357 part of piperidine and 33.4 parts of toluene were mixed, Stirring time. The mixture was cooled to room temperature and then added to 153 parts of methanol. The precipitate was obtained as a residue of suction filtration. The obtained residue was purified by column chromatography to obtain 7.76 parts of a compound represented by the formula (IB-2).

<Identification of Compound Represented by Formula (IB-2)

_{^{1 H-NMR (CDCl 3,}} 270 MHz) δ 2.13 (12H), 2.34 (12H), 6.38 (2H), 6.52 (2H), 6.92-7.02 (8H), 7.10 (4H), 7.37 (2H), 7.67 (2H), 7.98 (2H), 8.40 (2H), 8.64 (2H)

Example 12

10.0 parts of 2,2-bis (3-amino-4-hydroxyphenyl) propane and 51.0 parts of methanol were mixed and stirred at 5 占 폚 or lower under heating to give ethyl 3-ethoxy-3-iminopyropionic acid hydrochloride 18.2 parts were added. Thereafter, the reaction mixture was stirred for 13 hours at 10 占 폚 or lower, 24 hours at room temperature, and 24 hours at 60 占 폚. The reaction mixture was cooled to room temperature. The reaction mixture was distilled using a rotary vacuum concentrator. The obtained residue was purified by column chromatography to obtain 6.46 parts of a compound represented by the formula (pt1-2b).

Identification of compound represented by formula (pt1-2b)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 451.2

Exact Mass: 450.2

(IB-32) was performed in the same manner as in Example 11 except that the compound represented by the formula (pt1-1b) was replaced with the compound represented by the formula (pt1-2b) &Lt; / RTI &gt;

<Identification of Compound Represented by Formula (IB-32)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 1013.4

Exact Mass: 1012.4

Example 13

5.02 parts of 9,9-bis (3-amino-4-hydroxyphenyl) fluorene and 30.0 parts of methanol were mixed and stirred at 5 占 폚 or lower with 3-ethoxy-3-iminopropionic acid ethyl hydrochloride 6 . The reaction mixture was then stirred for 14 hours at 10 占 폚 or lower, 24 hours at room temperature, and 24 hours at 60 占 폚. The reaction mixture was cooled to room temperature. The reaction mixture was distilled using a rotary vacuum concentrator. The resulting residue was purified by column chromatography to obtain 2.33 parts of a compound represented by the formula (pt1-3b).

<Identification of compound represented by formula (pt1-3b)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 573.2

Exact Mass: 572.2

The procedure of Example 11 was repeated except that the compound represented by the formula (pt1-1b) was replaced with the compound represented by the formula (pt1-3b) to obtain the compound represented by the formula (IB-62) &Lt; / RTI &gt;

<Identification of Compound Represented by Formula (IB-62)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 1135.4

Exact Mass: 1134.4

Example 14

(Pt2-4b) and the formula (pt3-4b) were obtained in the same manner as in Example 11 except that 4-iodo-m-xylene was replaced with 2-iodo-1,3,5- -4b), the formula (pt4-4b) and the compound represented by the formula (IB-6).

&Lt; Identification of each compound &gt;

The compound represented by the formula (pt2-4b)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 360.2

Exact Mass: 359.2

The compound represented by the formula (pt3-4b)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 346.2

Exact Mass: 345.2

The compound represented by the formula (pt4-4b)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 374.2

Exact Mass: 373.2

The compound represented by the formula (IB-6)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 1091.4

Exact Mass: 1090.4

Example 15

In Example 11, the compound represented by the formula (pt1-1b) was replaced with the compound represented by the formula (pt1-2b), and 4-iodine-m-xylene was replaced with 2-iodo-1,3,5-trimethyl Benzene in place of the compound represented by the formula (IB-36), a compound represented by the formula (IB-36) was obtained.

<Identification of Compound Represented by Formula (IB-36)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 1069.5

Exact Mass: 1068.5

&Lt; Evaluation of heat resistance &

(IB-2), (IB-32) and (IB-62) obtained in Examples 11 to 15 were measured using a differential thermal thermogravimetry (TG / DTA6200R, , The compound represented by the formula (IB-6) and the compound represented by the formula (IB-36) and coumarin 6 (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.). The amount of sample used for one measurement was 5 mg. The measurement temperature was first started at 25 占 폚, the temperature was raised at a rate of 10 占 폚 per minute, and the temperature was measured up to 600 占 폚. A temperature T ₅ (in air) at which the weight reduction rate is 5% in air, a temperature T ₁₀ (in air) at which the weight reduction rate is 10% in air, a temperature T ₅ at which the weight reduction rate is 5% ) And a temperature T ₁₀ (under nitrogen) at which the weight loss rate is 10% in a nitrogen atmosphere. The results are shown in Table 31.

compound T ₅ (under air)
(° C) T ₁₀ (under air)
(° C) T ₅ (under nitrogen)
(° C) T ₁₀ (under nitrogen)
(° C) IB-2 408 418 416 424 IB-32 405 412 412 420 IB-62 395 405 404 411 IB-6 401 412 409 415 IB-36 400 409 407 416 Coumarin 6 327 344 331 348

From the results shown in Table 31, it can be seen that the compound (Ia-2) of the present invention has a high thermal stability.

&Lt; Preparation of colored curable resin composition &gt;

Example 16

Pigment: 27 parts of C. I. Pigment Green 7 (pigment)

12 parts of an acrylic pigment dispersant,

Resin (B): 9.5 parts of resin B1 (in terms of solid content), and

Solvent (E): Propylene glycol monomethyl ether acetate 180 parts

A pigment dispersion in which the pigment is sufficiently dispersed by using a bead mill;

Colorant (A): 3.0 parts of a compound represented by the formula (I-1);

Resin (B): Resin B1 (40 parts in solid content);

Polymerizable compound (C): 49 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Yakuza);

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Ilgacure (registered trademark) OXE-01; BASF; O- ) 9.8 parts;

Solvent (E): 670 parts of propylene glycol monomethyl ether acetate and

Leveling agent): 0.15 part of a polyether-modified silicone oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.)

Were mixed to obtain a colored curable resin composition.

Examples 17 to 33

Except that C.I. Pigment Green 7 (pigment) in Example 16 was replaced with the pigment shown in Table 32, and the compound represented by the formula (I-1) was replaced with the compound shown in Table 32 16, a colored curable resin composition was obtained.

Pigment The compound (I) Example 16 C. I. Pigment Green 7 The compound represented by the formula (I-1) Example 17 C. I. Pigment Green 36 The compound represented by the formula (I-1) Example 18 C. I. Pigment Green 58 The compound represented by the formula (I-1) Example 19 C. I. Pigment Green 7 The compound represented by the formula (I-2) Example 20 C. I. Pigment Green 36 The compound represented by the formula (I-2) Example 21 C. I. Pigment Green 58 The compound represented by the formula (I-2) Example 22 C. I. Pigment Green 7 The compound represented by the formula (I-82) Example 23 C. I. Pigment Green 36 The compound represented by the formula (I-82) Example 24 C. I. Pigment Green 58 The compound represented by the formula (I-82) Example 25 C. I. Pigment Green 7 The compound represented by the formula (I-141) Example 26 C. I. Pigment Green 36 The compound represented by the formula (I-141) Example 27 C. I. Pigment Green 58 The compound represented by the formula (I-141) Example 28 C. I. Pigment Green 7 The compound represented by the formula (I-146) Example 29 C. I. Pigment Green 36 The compound represented by the formula (I-146) Example 30 C. I. Pigment Green 58 The compound represented by the formula (I-146) Example 31 C. I. Pigment Green 7 The compound represented by the formula (I-86) Example 32 C. I. Pigment Green 36 The compound represented by the formula (I-86) Example 33 C. I. Pigment Green 58 The compound represented by the formula (I-86)

Examples 34 to 63

The procedure of Example 16 was repeated except that C.I. Pigment Green 7 (pigment) was replaced with the pigment shown in Table 33 and the compound represented by formula (I-1) To obtain a colored curable resin composition.

Pigment The compound (I) Example 34 C. I. Pigment Green 7 The compound represented by the formula (IA-13) Example 35 C. I. Pigment Green 36 The compound represented by the formula (IA-13) Example 36 C. I. Pigment Green 58 The compound represented by the formula (IA-13) Example 37 C. I. Pigment Green 7 The compound represented by the formula (IA-17) Example 38 C. I. Pigment Green 36 The compound represented by the formula (IA-17) Example 39 C. I. Pigment Green 58 The compound represented by the formula (IA-17) Example 40 C. I. Pigment Green 7 The compound represented by the formula (IA-15) Example 41 C. I. Pigment Green 36 The compound represented by the formula (IA-15) Example 42 C. I. Pigment Green 58 The compound represented by the formula (IA-15) Example 43 C. I. Pigment Green 7 The compound represented by the formula (IA-297) Example 44 C. I. Pigment Green 36 The compound represented by the formula (IA-297) Example 45 C. I. Pigment Green 58 The compound represented by the formula (IA-297) Example 46 C. I. Pigment Green 7 The compound represented by the formula (IA-299) Example 47 C. I. Pigment Green 36 The compound represented by the formula (IA-299) Example 48 C. I. Pigment Green 58 The compound represented by the formula (IA-299) Example 49 C. I. Pigment Green 7 The compound represented by the formula (IA-306) Example 50 C. I. Pigment Green 36 The compound represented by the formula (IA-306) Example 51 C. I. Pigment Green 58 The compound represented by the formula (IA-306) Example 52 C. I. Pigment Green 7 The compound represented by the formula (IA-49) Example 53 C. I. Pigment Green 36 The compound represented by the formula (IA-49) Example 54 C. I. Pigment Green 58 The compound represented by the formula (IA-49) Example 55 C. I. Pigment Green 7 The compound represented by the formula (IA-81) Example 56 C. I. Pigment Green 36 The compound represented by the formula (IA-81) Example 57 C. I. Pigment Green 58 The compound represented by the formula (IA-81) Example 58 C. I. Pigment Green 7 The compound represented by the formula (IA-308) Example 59 C. I. Pigment Green 36 The compound represented by the formula (IA-308) Example 60 C. I. Pigment Green 58 The compound represented by the formula (IA-308) Example 61 C. I. Pigment Green 7 The compound represented by the formula (IA-311) Example 62 C. I. Pigment Green 36 The compound represented by the formula (IA-311) Example 63 C. I. Pigment Green 58 The compound represented by the formula (IA-311)

Examples 64 to 78

In the same manner as in Example 16 except that the C.I. Pigment Green 7 (pigment) was replaced with the pigment shown in Table 34, and the compound represented by the formula (I-1) To obtain a colored curable resin composition.

Pigment The compound (I) Example 64 C. I. Pigment Green 7 The compound represented by the formula (IB-2) Example 65 C. I. Pigment Green 36 The compound represented by the formula (IB-2) Example 66 C. I. Pigment Green 58 The compound represented by the formula (IB-2) Example 67 C. I. Pigment Green 7 The compound represented by the formula (IB-32) Example 68 C. I. Pigment Green 36 The compound represented by the formula (IB-32) Example 69 C. I. Pigment Green 58 The compound represented by the formula (IB-32) Example 70 C. I. Pigment Green 7 The compound represented by the formula (IB-62) Example 71 C. I. Pigment Green 36 The compound represented by the formula (IB-62) Example 72 C. I. Pigment Green 58 The compound represented by the formula (IB-62) Example 73 C. I. Pigment Green 7 The compound represented by the formula (IB-6) Example 74 C. I. Pigment Green 36 The compound represented by the formula (IB-6) Example 75 C. I. Pigment Green 58 The compound represented by the formula (IB-6) Example 76 C. I. Pigment Green 7 The compound represented by the formula (IB-36) Example 77 C. I. Pigment Green 36 The compound represented by the formula (IB-36) Example 78 C. I. Pigment Green 58 The compound represented by the formula (IB-36)

&Lt; Measurement of film thickness &

The film thickness was measured using a DEKTAK 3 (manufactured by Japan Vacuum Technology Co., Ltd.).

&Lt; Preparation of resin composition for sublimation test (SJS) &gt;

Resin: methacrylic acid / benzyl methacrylate (molar ratio: 30/70) copolymer (manufactured by DAOKA CHEMICAL INDUSTRIES CO., Average molecular weight: 10700, acid value: 70 mgKOH / g) 33.8% propylene glycol monomethyl ether acetate solution 40 .2 parts;

Polymerizable compound: 5.8 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Gosei Chemical Industry Co., Ltd.);

Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE01;

Leveling agent: 0.01 part of polyether-modified silicone (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.);

Solvent: 46.6 parts of propylene glycol monomethyl ether;

Solvent: Propylene glycol monomethyl ether acetate 6.8 parts

To obtain a resin composition for sublimation test (SJS).

<Formation of Resin Coating Film (SJSM) for Sublimation Test>

The above-obtained resin composition for sublimation test (SJS) was coated on a glass substrate (Eagle XG; Corning) of 2 inch square by spin coating, and the volatile components were volatilized at 100 ° C for 3 minutes. After cooling, the substrate was irradiated with light at an exposure dose of 150 mJ / cm ² (365 nm standard) using an exposure machine (TME-150RSK; And heated in an oven at 220 DEG C for 2 hours to form a sublimation test resin coating film (SJSM) (film thickness 2.2 mu m).

Example 79 <Preparation of coloring pattern and evaluation of sublimation property>

The colored curable resin composition obtained in Example 16 was coated on a glass substrate (Eagle XG; Corning) of 2 inch square by spin coating, and then pre-baked at 100 ° C for 3 minutes to form a colored composition layer. After cooling, the distance between the substrate on which the colored composition layer was formed and the quartz glass photomask was set to 200 mu m and an exposure amount (365 nm) of 80 mJ / cm &lt; ² &gt; was measured under an atmospheric environment using an exposure machine (TME- Basis). A photomask having a line and space pattern of 100 mu m was used. The colored composition layer after exposure was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 캜 for 70 seconds to develop and wash. And the film thickness was measured. Table 35 shows the results.

This coloring covert film and the sublimation test water mapping film (SJSM) obtained above were opposed to each other with an interval of 70 mu m therebetween, and post-baking was performed at 220 DEG C for 40 minutes to obtain a coloring pattern. (SJSM) before and after heating was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). When the color difference (DELTA Eab *) is 5.0 or more, it indicates that the colorant has sublimation properties. Table 35 shows the results. In Table 35, in each example,? Means that the coloring agent has no sublimation property, and X means that the coloring agent has sublimation property.

Examples 80 to 142

A colored pattern was obtained in the same manner as in Example 79 except that the colored curable resin composition obtained in Example 16 was replaced with the colored curable resin compositions shown in Tables 35 to 37, Sublimability evaluation was performed. The results are shown in Tables 35 to 37.

Colored curable resin composition Film thickness
(Μm) Sublimation Example 79 The coloring curable resin composition obtained in Example 16 1.9 ○ Example 80 The coloring curable resin composition obtained in Example 17 1.9 ○ Example 81 The coloring curable resin composition obtained in Example 18 1.9 ○ Example 82 The coloring curable resin composition obtained in Example 19 1.9 ○ Example 84 The coloring curable resin composition obtained in Example 20 1.9 ○ Example 85 The coloring curable resin composition obtained in Example 21 1.9 ○ Example 86 The coloring curable resin composition obtained in Example 22 1.9 ○ Example 87 The coloring curable resin composition obtained in Example 23 1.9 ○ Example 88 The coloring curable resin composition obtained in Example 24 1.9 ○ Example 89 The coloring curable resin composition obtained in Example 25 1.9 ○ Example 90 The coloring curable resin composition obtained in Example 26 1.9 ○

Colored curable resin composition Film thickness
(Μm) Sublimation Example 91 The coloring curable resin composition obtained in Example 27 1.9 ○ Example 92 The coloring curable resin composition obtained in Example 28 1.9 ○ Example 93 The colored curable resin composition obtained in Example 29 1.9 ○ Example 94 The colored curable resin composition obtained in Example 30 1.9 ○ Example 95 The coloring curable resin composition obtained in Example 31 1.9 ○ Example 96 The coloring curable resin composition obtained in Example 32 1.9 ○ Example 97 The coloring curable resin composition obtained in Example 33 1.9 ○ Example 98 The coloring curable resin composition obtained in Example 34 1.9 ○ Example 99 The coloring curable resin composition obtained in Example 35 1.9 ○ Example 100 The coloring curable resin composition obtained in Example 36 1.9 ○ Example 101 The coloring curable resin composition obtained in Example 37 1.9 ○ Example 102 The coloring curable resin composition obtained in Example 38 1.9 ○ Example 103 The coloring curable resin composition obtained in Example 39 1.9 ○ Example 104 The colored curable resin composition obtained in Example 40 1.9 ○ Example 105 The coloring curable resin composition obtained in Example 41 1.9 ○ Example 106 The coloring curable resin composition obtained in Example 42 1.9 ○ Example 107 The coloring curable resin composition obtained in Example 43 1.9 ○ Example 108 The coloring curable resin composition obtained in Example 44 1.9 ○ Example 109 The colored curable resin composition obtained in Example 45 1.9 ○ Example 110 The coloring curable resin composition obtained in Example 46 1.9 ○ Example 111 The colored curable resin composition obtained in Example 47 1.9 ○ Example 112 The coloring curable resin composition obtained in Example 48 1.9 ○ Example 113 Synthesis of The colored curable resin composition obtained in Example 49 1.9 ○ Example 114 The coloring curable resin composition obtained in Example 50 1.9 ○ Example 115 The colored curable resin composition obtained in Example 51 1.9 ○ Example 116 The coloring curable resin composition obtained in Example 52 1.9 ○ Example 117 The coloring curable resin composition obtained in Example 53 1.9 ○ Example 118 The coloring curable resin composition obtained in Example 54 1.9 ○ Example 119 The colored curable resin composition obtained in Example 55 1.9 ○ Example 120 The coloring curable resin composition obtained in Example 56 1.9 ○ Example 121 The coloring curable resin composition obtained in Example 57 1.9 ○ Example 122 The coloring curable resin composition obtained in Example 58 1.9 ○ Example 123 The colored curable resin composition obtained in Example 59 1.9 ○ Example 124 The colored curable resin composition obtained in Example 60 1.9 ○ Example 125 The coloring curable resin composition obtained in Example 61 1.9 ○

Colored curable resin composition Film thickness
(Μm) Sublimation Example 126 The coloring curable resin composition obtained in Example 62 1.9 ○ Example 127 The colored curable resin composition obtained in Example 63 1.9 ○ Example 128 The coloring curable resin composition obtained in Example 64 1.9 ○ Example 129 The colored curable resin composition obtained in Example 65 1.9 ○ Example 130 The coloring curable resin composition obtained in Example 66 1.9 ○ Example 131 The coloring curable resin composition obtained in Example 67 1.9 ○ Example 132 The coloring curable resin composition obtained in Example 68 1.9 ○ Example 133 The coloring curable resin composition obtained in Example 69 1.9 ○ Example 134 The colored curable resin composition obtained in Example 70 1.9 ○ Example 135 The coloring curable resin composition obtained in Example 71 1.9 ○ Example 136 The coloring curable resin composition obtained in Example 72 1.9 ○ Example 137 The coloring curable resin composition obtained in Example 73 1.9 ○ Example 138 The coloring curable resin composition obtained in Example 74 1.9 ○ Example 139 The coloring curable resin composition obtained in Example 75 1.9 ○ Example 140 The coloring curable resin composition obtained in Example 76 1.9 ○ Example 141 The coloring curable resin composition obtained in Example 77 1.9 ○ Example 142 [ The coloring curable resin composition obtained in Example 78 1.9 ○

Comparative Example 1

Colorant: 3.6 parts of coumarin 6;

Resin (B): Resin (B1) (in terms of solid content) 180 parts;

Solvent (E): 230 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 590 parts of N, N-dimethylformamide;

And

Leveling agent: polyether-modified silicone oil 0.063 part (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

Were mixed to obtain a colored resin composition.

The colored resin composition obtained above was coated on a glass substrate (Eagle XG; Corning) of 2 inch square by spin coating, and then pre-baked at 100 ° C for 3 minutes to form a colored composition layer. The film thickness was measured using DEKTAK 3 (manufactured by Nippon Vacuum Technology Co., Ltd.) and found to be 1.9 탆.

The coloring degree of the coating film and the sublimation test water mapping film (SJSM) obtained as described above were opposed to each other with an interval of 70 mu m, and post-baking was performed at 220 DEG C for 40 minutes. (SJSM) before and after heating was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). As a result, it was confirmed that the color difference [Delta] Eab * was 5.0 or more, and coumarin 6 as a coloring agent had sublimation properties.

From the above results, it was found that the color-curable resin composition of the present invention can form a color filter without sublimation of the coloring agent.

[Industrial Availability]

According to the present invention, the color filter can be formed without sublimation of the coloring agent. Therefore, the color filter is suitably used for a display device such as a liquid crystal display device.

Claims (27)

A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator and a solvent comprising a compound represented by formula (I).
.

(Wherein L represents a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms, a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group (-SO ₂ -),
X represents an oxygen atom or a sulfur atom,
R ⁷ to R ¹³ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group (-CONH ₂ ), a sulfamoyl group (-SO ₂ NH ₂ ), -SO ₃ M, -CO ₂ M , A hydroxyl group, a formyl group, an amino group or a monovalent hydrocarbon group having 1 to 20 carbon atoms,
-CH ₂ - constituting the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ¹⁴ ) -, a sulfonyl group or a carbonyl group,
The hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group,
R ¹⁴ represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms, and when a plurality of R ^{14 s} exist, they may be the same or different,
M represents a hydrogen atom or an alkali metal atom, and when a plurality of M exist, they may be the same or different,
Z is represented by the formula (Z1):

(Wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms, -CH ₂ - constituting the alkyl group may be substituted with an oxygen atom,
R ² to R ⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group, A monovalent hydrocarbon group,
The -CH ₂ - constituting the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ³⁰ ) -, a sulfonyl group or a carbonyl group,
The hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group,
R ³⁰ represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms, and when a plurality of R ^{30 s} exist, they may be the same or different,
M represents a hydrogen atom or an alkali metal atom, and when a plurality of M exist, they may be the same or different, and * represents a bonding hand.)
Or a group represented by the formula (Z2):

(Wherein Ar ¹ represents a phenyl group having an alkyl group having 1 to 8 carbon atoms at an ortho position, a meta position or both of them, and * represents a binding site).
Represents a group represented by the formula: The method according to claim 1,
L is a divalent fluorinated hydrocarbon group having 1 to 20 carbon atoms. The method according to claim 1,
L is a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group. 4. The method according to any one of claims 1 to 3,
And Z is a group represented by the formula (Z1). 5. The method according to any one of claims 1 to 4,
R ¹ is an alkyl group having 1 to 16 carbon atoms, and -CH ₂ - constituting the alkyl group may be substituted with an oxygen atom. 3. The method of claim 2,
Z is a group represented by the formula (Z1), and R &lt; ^{1 &gt;} is an alkyl group having 1 to 8 carbon atoms. The method of claim 3,
Z is a group represented by the formula (Z1), and R &lt; ^{1 &gt;} is an alkyl group having 6 to 10 carbon atoms. 4. The method according to any one of claims 1 to 3,
And Z is a group represented by the formula (Z2). The method according to any one of claims 1, 2, 3, and 8,
Ar ¹ is a phenyl group having an alkyl group having 1 to 8 carbon atoms at the ortho position or a phenyl group having an alkyl group having 1 to 8 carbon atoms at an ortho position and a meta position. 10. The method of claim 9,
Wherein the alkyl group having 1 to 8 carbon atoms is a methyl group, an ethyl group or an isopropyl group. 11. The method according to any one of claims 1 to 10,
A coloring curable resin composition comprising a colorant and a pigment. 12. The method of claim 11,
Wherein the pigment is at least one selected from the group consisting of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment. 12. The method of claim 11,
Wherein the pigment is at least one selected from the group consisting of a chlorinated copper phthalocyanine pigment, a copper phthalocyanine pigment, and a zinc bromide phthalocyanine pigment. 14. The method according to any one of claims 11 to 13,
Wherein the pigment is a green pigment. 15. The method according to any one of claims 11 to 14,
Wherein the pigment is at least one selected from the group consisting of C. I. Pigment Green 7, C. I. Pigment Green 36 and C.I. Pigment Green 58. A color filter formed from the colored curable resin composition according to any one of claims 1 to 15. A liquid crystal display device comprising the color filter according to claim 16. A compound represented by the formula (Ia-1).

(Wherein L ^a represents ^a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group (-SO ₂ -),
X represents an oxygen atom or a sulfur atom,
R ⁷ to R ¹³ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group (-CONH ₂ ), a sulfamoyl group (-SO ₂ NH ₂ ), -SO ₃ M, -CO ₂ M , A hydroxyl group, a formyl group, an amino group or a monovalent hydrocarbon group having 1 to 20 carbon atoms,
-CH ₂ - constituting the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ¹⁴ ) -, a sulfonyl group or a carbonyl group,
The hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group,
R ¹⁴ represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms, and when a plurality of R ^{14 s} exist, they may be the same or different,
M represents a hydrogen atom or an alkali metal atom, and when a plurality of M exist, they may be the same or different,
Z ^a represents a group represented by the formula (Z1).

(Wherein R &lt; ¹ &gt; represents an alkyl group having 1 to 20 carbon atoms,
-CH ₂ - constituting the alkyl group may be substituted with an oxygen atom,
R ² to R ⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group, A monovalent hydrocarbon group,
The -CH ₂ - constituting the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ³⁰ ) -, a sulfonyl group or a carbonyl group,
The hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group,
R ³⁰ represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms, and when a plurality of R ^{30 s} exist, they may be the same or different,
M represents a hydrogen atom or an alkali metal atom, and when a plurality of M exist, they may be the same or different, and * indicates a bonding hand)) 19. The method of claim 18,
R ¹ is an alkyl group having 1 to 16 carbon atoms, and -CH ₂ - constituting the alkyl group may be substituted with an oxygen atom. 19. The method of claim 18,
And R &lt; ^{1 &gt;} is an alkyl group having 6 to 10 carbon atoms. A compound represented by the formula (Ia-2).

(Wherein L ^a represents ^a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group (-SO ₂ -),
X represents an oxygen atom or a sulfur atom,
R ⁷ to R ¹³ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group (-CONH ₂ ), a sulfamoyl group (-SO ₂ NH ₂ ), -SO ₃ M, -CO ₂ M , A hydroxyl group, a formyl group, an amino group or a monovalent hydrocarbon group having 1 to 20 carbon atoms,
-CH ₂ - constituting the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ¹⁴ ) -, a sulfonyl group or a carbonyl group,
The hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group,
R ¹⁴ represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms, and when a plurality of R ^{14 s} exist, they may be the same or different,
M represents a hydrogen atom or an alkali metal atom, and when a plurality of M exist, they may be the same or different,
Z ^b represents a group represented by the formula (Z2).

(Wherein Ar ¹ represents a phenyl group having an alkyl group having 1 to 8 carbon atoms at an ortho position, a meta position, or both of them, and * indicates a bond)) 22. The method of claim 21,
Wherein Ar ¹ is a phenyl group having an alkyl group having 1 to 8 carbon atoms at the ortho position or a phenyl group having an alkyl group having 1 to 8 carbon atoms at an ortho position and a meta position. 23. The method of claim 22,
Wherein the alkyl group having 1 to 8 carbon atoms is a methyl group, an ethyl group or an isopropyl group. A colorant comprising a compound according to any one of claims 18 to 23. 25. The method of claim 24,
Also provided is a colorant comprising a pigment. A compound represented by the formula (IIa).

(Wherein L ^a represents ^a divalent hydrocarbon group or a sulfonyl group having 1 to 20 carbon atoms,
X represents an oxygen atom or a sulfur atom; R ¹¹ to R ¹³ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, , A formyl group, an amino group or a monovalent hydrocarbon group of 1 to 20 carbon atoms,
-CH ₂ - constituting the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ¹⁴ ) -, a sulfonyl group or a carbonyl group,
The hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group,
R ¹⁴ represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms,
When a plurality of R &lt; ¹⁴ &gt; exist, they may be the same or different,
M represents a hydrogen atom or an alkali metal atom, and when a plurality of M exist, they may be the same or different,
R ¹⁵ and R ¹⁶ each independently represent an alkyl group having 1 to 20 carbon atoms. A compound represented by the formula (III).

(Wherein R ⁷ to R ⁹ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group, A monovalent hydrocarbon group of 1 to 20 carbon atoms,
-CH ₂ - constituting the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ¹⁴ ) -, a sulfonyl group or a carbonyl group,
The hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group or an amino group.
R ¹⁴ represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms, and when a plurality of R ¹⁴ exist, they may be the same or different.
M represents a hydrogen atom or an alkali metal atom, and when a plurality of M exist, they may be the same or different,
Z is represented by the formula (Z1):

(Wherein R &lt; ¹ &gt; represents an alkyl group having 1 to 20 carbon atoms,
-CH ₂ - constituting the alkyl group may be substituted with an oxygen atom,
R ² to R ⁶ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group, A monovalent hydrocarbon group,
The -CH ₂ - constituting the hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ³⁰ ) -, a sulfonyl group or a carbonyl group,
The hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, a formyl group,
R ³⁰ represents a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms, and when a plurality of R ^{30 s} exist, they may be the same or different,
M represents a hydrogen atom or an alkali metal atom, and when a plurality of M exist, they may be the same or different, and * represents a bonding hand.)
Or a group represented by the formula (Z2):

(Wherein Ar ¹ represents a phenyl group having an alkyl group having 1 to 8 carbon atoms at an ortho-position, a meta-position, or both, and * represents a bond).
Represents a group represented by the formula: