CN103576454B

CN103576454B - Colored curable resin composition

Info

Publication number: CN103576454B
Application number: CN201310325247.6A
Authority: CN
Inventors: 织田胜成; 藤田拓麻; 秋山裕次
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2012-07-31
Filing date: 2013-07-30
Publication date: 2019-01-04
Anticipated expiration: 2033-07-30
Also published as: KR20140016833A; TW201410673A; JP2014044419A; KR102041384B1; CN103576454A; JP6221470B2; TWI588142B

Abstract

A kind of colored curable resin composition, it contains colorant, resin, polymerizable compound and polymerization initiator, and the colorant contains the compound and C.I. pigment Yellow 12 9 with cumarin skeleton such as compound that formula (1), formula (1 '), formula (2), formula (3), formula (4) or formula (5) indicate.(in formula, L indicates divalent alkyl etc., and AA indicates that aryl etc., X indicate oxygen atom, sulphur atom etc., R¹~R⁴Separately indicate hydrogen atom, 1 valency alkyl etc., R⁵~R⁹Separately indicate hydrogen atom, halogen atom, 1 valency alkyl etc..〕.

Description

Colored curable resin composition

Technical field

The present invention relates to colored curable resin compositions.

Background technique

Colored curable resin composition is used for the colour filter such as manufacturing liquid crystal display device.Such staining and curing Property resin combination it has been known that there is containing as the halogenated ZnPc pigment of colorant and the colored curable tree of Yellow azo dye Oil/fat composition (JP2010-168531-A).

About previously known above-mentioned colored curable resin composition, obtained by the colored curable resin composition The brightness of colour filter may not being capable of fully meet demand.

Summary of the invention

The present invention provides following (1)~(29).

(1) a kind of colored curable resin composition draws containing colorant, resin, polymerizable compound and polymerization Agent is sent out, the colorant contains compound and C.I. pigment Yellow 12 9 with cumarin skeleton.

(2) colored curable resin composition described in (1), wherein colorant also contains pigment.

(3) colored curable resin composition described in (2), wherein pigment be selected from by halogenated copper phthalocyanine pigment and At least one of the group of halogenated ZnPc pigment composition.

(4) colored curable resin composition described in (2) or (3), wherein pigment is selected from by chloro copper phthalocyanine face At least one of material, bromo copper phthalocyanine and group of bromo ZnPc pigment composition.

(5) colored curable resin composition described in any one of (2)~(4), wherein pigment is viridine green.

(6) colored curable resin composition described in any one of (2)~(5), wherein pigment is selected from by C.I. At least one of the group that pigment Green 7, C.I. pigment green 36 and C.I. naphthol green 58 form.

(7) colored curable resin composition described in any one of (2)~(6), wherein pigment is C.I. naphthol green 7。

(8) colored curable resin composition described in any one of (1)~(7), wherein there is cumarin bone The compound of frame is the compound that formula (1) indicates.

The compound that following formula (1) indicates:

[in formula (1),

The divalent alkyl of L expression carbon atom number 1~20.The methylene of the divalent alkyl is constituted by oxygen atom, sulphur atom ,-N (R¹⁰)-, sulfonyl or carbonyl it is substituted or unsubstituted, hydrogen atom contained by the divalent alkyl is by cyano, nitro, carbamoyl, ammonia Sulfonyl, sulfo group, carboxyl, hydroxyl, chlorine atom, bromine atom, imidazoles -1- base or amino are substituted or unsubstituted.

X indicates oxygen atom, sulphur atom or-N (R¹⁰)-。

The aryl of AA expression carbon atom number 6~20.Hydrogen atom contained by the aryl is by halogen atom, cyano, nitro, amino first Acyl group, sulfamoyl, sulfo group, carboxyl, hydroxyl, imidazoles -1- base, amino or carbon atom number 1~20 1 valency alkyl replace or without taking Generation.The methylene of 1 valency alkyl is constituted by oxygen atom, sulphur atom ,-N (R¹⁰)-, sulfonyl or carbonyl it is substituted or unsubstituted, this 1 Hydrogen atom contained by valency alkyl can by halogen atom, cyano, nitro, carbamoyl, sulfamoyl, sulfo group, carboxyl, hydroxyl, Imidazoles -1- base or amino are substituted or unsubstituted.

R¹~R⁴Separately indicate 1 valency alkyl or R of hydrogen atom or carbon atom number 1~20¹With R³Bonding and with Ring or R is collectively formed in the nitrogen-atoms of carbon atom and adjoining on adjacent phenyl ring²With R⁴Bonding and on adjacent phenyl ring Carbon atom and the nitrogen-atoms of adjoining ring is collectively formed.The methylene of 1 valency alkyl is constituted by oxygen atom, sulphur atom ,-N (R¹⁰)-, sulfonyl or carbonyl it is substituted or unsubstituted, hydrogen atom contained by 1 valency alkyl is by halogen atom, cyano, nitro, amino first Acyl group, sulfamoyl, sulfo group, carboxyl, hydroxyl, imidazoles -1- base or amino are substituted or unsubstituted.

R⁵~R⁹Separately indicate hydrogen atom, halogen atom, cyano, nitro, carbamoyl, sulfamoyl, sulfo group, Carboxyl, hydroxyl, amino or carbon atom number 1~20 1 valency alkyl or R⁵With R⁶It is bonded and is collectively formed with adjacent carbon atom Ring or R⁷With R⁸It is bonded and ring is collectively formed with adjacent carbon atom.The methylene for constituting 1 valency alkyl is former by oxygen atom, sulphur Son ,-N (R¹⁰)-, sulfonyl or carbonyl it is substituted or unsubstituted, hydrogen atom contained by 1 valency alkyl by halogen atom, cyano, nitro, Carbamoyl, sulfamoyl, sulfo group, carboxyl, hydroxyl, imidazoles -1- base or amino are substituted or unsubstituted.

R¹⁰Indicate 1 valency alkyl of hydrogen atom or carbon atom number 1~20.There are multiple R¹⁰When, they are mutually identical or not Together.]

(9) colored curable resin composition described in any one of (1)~(7), wherein there is cumarin bone The compound of frame is the compound that formula (1 ') indicates.

The compound that following formula (1 ') indicates:

[in formula (1 '), R¹~R⁹, X and L respectively indicate meaning same as described above.]

(10) colored curable resin composition described in (8) or (9), wherein X is oxygen atom or sulphur atom.

(11) colored curable resin composition described in any one of (8)~(10), wherein X is oxygen atom.

(12) colored curable resin composition described in any one of (8)~(11), wherein L be with or without The methylene or sulfonyl of substituent group.

(13) colored curable resin composition described in any one of (8)~(12), wherein L is dimethylmethylene Or sulfonyl.

(14) colored curable resin composition described in any one of (8)~(13), wherein R⁵~R⁹It is hydrogen atom.

(15) colored curable resin composition described in any one of (1)~(7), wherein there is cumarin bone The compound of frame is the compound that formula (2) indicate.

The compound that following formula (2) indicates:

[in formula (2), Q¹And Q²Separately indicate hydrogen atom or-CO₂M, Q¹And Q²Any of indicate- CO₂M。

R¹¹~R¹⁴Separately indicate 1 valency alkyl or R of hydrogen atom or carbon atom number 1~20¹¹And R¹³Bonding And ring or R is collectively formed with the nitrogen-atoms of carbon atom and adjoining on adjacent phenyl ring¹²And R¹⁴Bonding and with adjoining Phenyl ring on carbon atom and the nitrogen-atoms of adjoining ring is collectively formed.The methylene for constituting 1 valency alkyl is former by oxygen atom, sulphur Son ,-N (R¹⁵)-, sulfonyl or carbonyl it is substituted or unsubstituted, hydrogen atom contained by 1 valency alkyl by halogen atom, cyano, nitro, Carbamoyl, sulfamoyl ,-SO₃M、-CO₂M, hydroxyl or amino are substituted or unsubstituted.

R¹⁵Indicate 1 valency alkyl of hydrogen atom or carbon atom number 1~20.There are multiple R¹⁵When, they are same to each other or not Together.

M indicates hydrogen atom or alkali metal atom.]

(16) colored curable resin composition described in any one of (1)~(7), wherein there is cumarin bone The compound of frame is the compound that formula (3) indicate.

The compound that following formula (3) indicates:

[in formula (3),

The divalent alkyl of L ' expression carbon atom number 1~20.The methylene of the divalent alkyl is constituted by oxygen atom, sulphur atom ,-N (R²⁵)-, sulfonyl or carbonyl it is substituted or unsubstituted, hydrogen atom contained by the divalent alkyl is by halogen atom, cyano, nitro, amino first Acyl group, sulfamoyl ,-SO₃M’、-CO₂M ', hydroxyl or amino are substituted or unsubstituted.Wherein, hydrogen atom contained by the divalent alkyl At least one of be replaced by fluorine atoms.

X ' indicates the 16th race's atom ,-N (R in the periodic table of elements²⁵)-or-C (R²⁵)(R²⁶)-。

R¹⁶~R²⁴Separately indicate hydrogen atom, halogen atom, cyano, nitro, carbamoyl, sulfamoyl ,- SO₃M’、-CO₂M ', hydroxyl, amino or carbon atom number 1~20 1 valency alkyl or R¹⁶And R¹⁸Bonding and with adjacent phenyl ring On carbon atom and the nitrogen-atoms of adjoining ring or R is collectively formed¹⁷And R¹⁹Bonding and it is former with the carbon on adjacent phenyl ring Ring is collectively formed in son and adjacent nitrogen-atoms.The methylene of 1 valency alkyl is constituted by oxygen atom, sulphur atom ,-N (R²⁷)-, sulphur Acyl group or carbonyl are substituted or unsubstituted, and hydrogen atom contained by 1 valency alkyl is by halogen atom, cyano, nitro, carbamoyl, ammonia Sulfonyl ,-SO₃M’、-CO₂M ', hydroxyl or amino are substituted or unsubstituted.

R²⁵And R²⁶Separately indicate 1 valency alkyl of hydrogen atom or carbon atom number 1~20.Constitute 1 valency alkyl Methylene by oxygen atom, sulphur atom ,-N (R²⁷)-, sulfonyl or carbonyl it is substituted or unsubstituted, hydrogen contained by 1 valency alkyl is former Son is by halogen atom, cyano, nitro, carbamoyl, sulfamoyl ,-SO₃M’、-CO₂M ', hydroxyl or amino are substituted or unsubstituted.

R²⁷Indicate 1 valency alkyl of hydrogen atom or carbon atom number 1~20.There are multiple R²⁷When, they are same to each other or not Together.

M ' indicates hydrogen atom or alkali metal atom.]

(17) colored curable resin composition described in (16), wherein X ' is oxygen atom, sulphur atom ,-N (R²⁵)-or-C (R²⁵)(R²⁶)-。

(18) colored curable resin composition described in (16) or (17), wherein X ' is oxygen atom, sulphur atom or-N (R²⁵)-。

(19) colored curable resin composition described in any one of (16)~(18), wherein X ' be oxygen atom or Sulphur atom.

(20) colored curable resin composition described in any one of (16)~(19), wherein X ' is oxygen atom.

(21) colored curable resin composition described in any one of (16)~(20), wherein L ' is bis- (fluoroforms Base) methylene.

(22) colored curable resin composition described in any one of (16)~(21), wherein R¹⁸~R²⁴It is hydrogen Atom.

(23) colored curable resin composition described in any one of (1)~(7), wherein there is cumarin The compound that the compound of skeleton is formula (4) or formula (5) indicates.

The compound that following formula (4) indicates:

The compound that following formula (5) indicates:

[in formula (4) and formula (5),

X " indicates the 16th race's atom ,-N (R in the periodic table of elements³⁴)-or-C (R³⁴)(R³⁵)-。

R²⁸~R⁴¹Separately indicate hydrogen atom, halogen atom, cyano, nitro, carbamoyl, sulfamoyl ,- SO₃M”、-CO₂M ", hydroxyl, amino or carbon atom number 1~20 1 valency alkyl or R²⁸And R³⁰Bonding and with adjacent phenyl ring On carbon atom and the nitrogen-atoms of adjoining ring or R is collectively formed²⁹And R³¹It is bonded and is formed comprising adjacent carbon atom With the ring of adjacent nitrogen-atoms and carbon atom.The methylene of 1 valency alkyl is constituted by oxygen atom, sulphur atom ,-N (R⁴²)-, sulphur Acyl group or carbonyl are substituted or unsubstituted, and hydrogen atom contained by 1 valency alkyl is by halogen atom, cyano, nitro, carbamoyl, ammonia Sulfonyl ,-SO₃M”、-CO₂M ", hydroxyl, imidazoles -1- base or amino are substituted or unsubstituted.Wherein, R³⁶~R⁴¹At least one of It is-SO₃M”。

R⁴²Indicate 1 valency alkyl of hydrogen atom or carbon atom number 1~20.There are multiple R⁴²When, they are same to each other or not Together.

M " indicates hydrogen atom or alkali metal atom.]

(24) colored curable resin composition described in (23), wherein X " is oxygen atom, sulphur atom ,-N (R³⁴)-or-C (R³⁴)(R³⁵)-。

(25) colored curable resin composition described in (23) or (24), wherein X " is oxygen atom.

(26) colored curable resin composition described in any one of (23)~(25), wherein R⁴⁰For-SO₃M”。

(27) colored curable resin composition described in any one of (1)~(26), wherein relative to dyestuff and face The total amount of material, the content for the compound that any of formula (1)~(5) indicate are 1 mass % or more, 65 mass % or less.

(28) a kind of colour filter, use colored curable resin composition described in any one of (1)~(27) and It is formed.

(29) a kind of liquid crystal display device, it includes the colour filters described in (28).

According to the present invention it is possible to provide the colored curable resin composition that can manufacture the colour filter of high brightness.

Specific embodiment

Colored curable resin composition of the invention contain colorant (A), resin (B) and polymerizable compound (C), Polymerization initiator (D).

Colorant (A) includes compound and C.I. pigment Yellow 12 9 with cumarin skeleton.

Colored curable resin composition of the invention preferably further contains selected from by solvent (E) and levelling agent (F) At least one of group of composition.

Colored curable resin composition of the invention can further contain polymerization trigger auxiliary agent (D1).

In this specification, for the compound illustrated as each ingredient, as long as no special explanation in advance, being all can be with What independent or multiple combinations used.

Colorant (A) includes that the compound of formula (1), formula (1 '), formula (2), formula (3), formula (4) or formula (5) expression (has below When be referred to as " compound (1) ", " compound (1 ') ", " compound (2) ", " compound (3) ", " compound (4) " or " compound ) etc. (5) " with the compound and C.I. pigment Yellow 12 9 of cumarin skeleton, preferably further include pigment (P).

Compound (1) is indicated by formula (1), further includes its tautomer or their salt.

Compound (1 ') is indicated by formula (1 '), further includes its tautomer or their salt.

Sulfo group is indicated by-SO₃The group that M " ' is indicated.

Carboxyl is indicated by-CO₂The group that M " ' is indicated.

M " ' indicates hydrogen atom or alkali metal atom, preferably hydrogen atom, sodium atom or potassium atom, more preferable hydrogen atom.

As the group that L is indicated, for example there are the groups and these groups that are for example indicated respectively by formula (L1)~formula (L29) Contained hydrogen atom is by cyano, nitro, carbamoyl, sulfamoyl, sulfo group, carboxyl, hydroxyl, chlorine atom, bromine atom, miaow Azoles -1- base or amino replace obtained group.In formula (L1)~formula (L29), ● indicate bonding position.

It is preferred that L is the methylene or sulfonyl that can have substituent group.

As it is described preferably, concrete example has the group indicated respectively by formula (L1) and formula (L3)~formula (L14).Its In, the group that preferred formula (L1) and formula (L3)~formula (L14) indicate, more preferable formula (L1), formula (L3), formula (L10), formula (L13) and the group of formula (L14) expression, even more preferably formula (L1), formula (L3), formula (L13) and formula (L14) indicate Group.When L is these groups, raw material is easy to get.

X indicates oxygen atom, sulphur atom or-N (R¹⁰)-, preferably oxygen atom and sulphur atom.Wherein, more preferable oxygen atom.X When for oxygen atom, there is the tendency of high brightness of green color filter.

As the aryl of the AA carbon atom number 6~20 indicated, for example there are what is for example indicated respectively by formula (A1)~formula (A12) Hydrogen atom contained by group and these groups by halogen atom, cyano, nitro, carbamoyl, sulfamoyl, sulfo group, carboxyl, Hydroxyl, imidazoles -1- base, amino or carbon atom number 1~20 the group that replaces of 1 valency alkyl.Constitute the methylene of 1 valency alkyl Base can be by oxygen atom, sulphur atom ,-N (R¹⁰)-, sulfonyl or carbonyl replace, hydrogen atom contained by 1 valency alkyl can be by halogen Atom, cyano, nitro, carbamoyl, sulfamoyl, sulfo group, carboxyl, hydroxyl, imidazoles -1- base or amino replace.Wherein, excellent The group for selecting formula (A12) to indicate.When AA is the group that formula (A12) is indicated, there is the higher tendency of thermal decomposition temperature.There are also sublimabilities Low tendency.

[in formula (A1)~formula (A12), R¹~R⁹And X is same as above respectively, ● indicate the bonding position with L.]

As R¹~R⁹In halogen atom, for example there are fluorine atom, chlorine atom, bromine atom, iodine atoms.

As R¹~R⁹In carbon atom number 1~20 1 valency alkyl, for example there are such as methyl, ethyl, propyl, isopropyl, Isopropenyl, 1- acrylic, 2- acrylic, butyl, isobutyl group, sec-butyl, tert-butyl, (2- ethyl) butyl, 2- cyclobutenyl, 1, 3- butadienyl, amyl, isopentyl, 3- amyl, neopentyl, tertiary pentyl, 1- methyl amyl, 2- methyl amyl, 2- pentenyl, (3- ethyl) amyl, hexyl, isohesyl, 5- methylhexyl, (2- ethyl) hexyl, heptyl, (3- ethyl) heptyl, octyl, nonyl, The aliphatic alkyls such as decyl, undecyl, dodecyl, octadecyl；

Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cyclohexenyl group, suberyl, 1- methylcyclohexyl, 2- methyl cyclohexane Base, 3- methylcyclohexyl, 4- methylcyclohexyl, 1,2- Dimethylcyclohexyl, 1,3- Dimethylcyclohexyl, Isosorbide-5-Nitrae-dimethyleyelohexane Base, 2,3- Dimethylcyclohexyl, 2,4- Dimethylcyclohexyl, 2,5- Dimethylcyclohexyl, 2,6- Dimethylcyclohexyl, 3,4- bis- Methylcyclohexyl, 3,5- Dimethylcyclohexyl, 2,2- Dimethylcyclohexyl, 3,3- Dimethylcyclohexyl, 4,4- dimethyleyelohexane Base, 2,4,6- trimethylcyclohexyls, 2, the alicyclic alkyls such as 2,6,6- tetramethyl-ring hexyls, 3,3,5,5- tetramethyl-ring hexyls；

Phenyl, o-tolyl, tolyl, p-methylphenyl, xylyl, mesitylene base, adjacent cumenyl, isopropyl Phenyl, to aromatic hydrocarbyls such as cumenyl, benzyl, phenethyl, xenyl, 1- naphthalene, 2- naphthalenes；

And the group being composed of them.

As constitute these 1 valency alkyls methylene by oxygen atom, sulphur atom ,-N (R¹⁰)-, sulfonyl or carbonyl replace after Hydrogen atom contained by obtained group, 1 valency alkyl is by halogen atom, cyano, nitro, carbamoyl, sulfamoyl, sulfo group, carboxylic Obtained group after base, hydroxyl or amino substitution, for example there are for example:

Methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, penta oxygen The alkoxies such as base, (2- ethyl) hexyloxy；

The aryloxy group such as phenoxy group；

The aralkoxies such as benzyloxy；

The alkoxy carbonyls such as methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl；

The acyloxy such as acetoxyl group, benzoyloxy；

N- methylcarbamoyl, N- ethylaminocarbonyl, N- propvlcarbamovl, N- isopropylamino formyl Base, N- Butylcarbamoyl, N- butylcarbamoyl, N- s-butylamino formoxyl, N- t-Butylcarbamoyl, N- pentylcarbamoy, N- (1- ethyl propyl) carbamoyl, N- (1,1- dimethyl propyl) carbamoyl, N- (1, 2- dimethyl propyl) carbamoyl, N- (2,2- dimethyl propyl) carbamoyl, N- (1- methyl butyl) carbamyl Base, N- (2- methyl butyl) carbamoyl, N- (3- methyl butyl) carbamoyl, N- cyclopentylcarbamoyl, N- oneself Base carbamoyl, N- (1,3- dimethylbutyl) carbamoyl, N- (3,3- dimethylbutyl) carbamoyl, N- heptyl Carbamoyl, N- (1- methylhexyl) carbamoyl, N- (Isosorbide-5-Nitrae-dimethyl amyl group) carbamoyl, N- octyl amino first Acyl group, N- (2- ethylhexyl) carbamoyl, N- (1,5- dimethyl) hexylamino formoxyl, N- (1,1,2,2- tetramethyl Butyl) the N-1 substituted-amino formoxyl such as carbamoyl；

N, N- formyl-dimethylamino, N, N- ethylmethylamino formoxyl, N, N- diethylamino formoxyl, N, N- Propyl-methylamino formoxyl, N, N- isopropylmethylamino formoxyl, N, N- tertbutyl methyl carbamoyl, N, N- butyl Ethylaminocarbonyl, N, N- bis- (1- methyl-propyl) carbamoyls, N, N- hept-ylmethyl carbamoyl, N, the bis- (2- of N- Ethylhexyl) N such as carbamoyl, N-2 substituted-amino formoxyl；

N- Methylsulfamoyl, N- ethylsulfamovl, N- propylsulfamov, N- isopropylsulfamoyl base, N- butyl Sulfamoyl, N- isobutyl group sulfamoyl, N- sec-butyl sulfamoyl, N- tert-butyl sulfamoyl, N- amyl sulfamoyl, N- (1- ethyl propyl) sulfamoyl, N- (1,1- dimethyl propyl) sulfamoyl, N- (1,2- dimethyl propyl) sulfamoyl, N- (2,2- dimethyl propyl) sulfamoyl, N- (1- methyl butyl) sulfamoyl, N- (2- methyl butyl) sulfamoyl, N- (3- Methyl butyl) sulfamoyl, N- Cyclopentylsulfamoyl base, N- hexyl sulfamoyl, N- (1,3- dimethylbutyl) sulfamoyl, N- (3,3- dimethylbutyl) sulfamoyl, N- heptyl sulfamoyl, N- (1- methylhexyl) sulfamoyl, N- (Isosorbide-5-Nitrae-diformazan Base amyl) sulfamoyl, N- octyl sulfamoyl, N- (2- ethylhexyl) sulfamoyl, N- (1,5- dimethyl) hexyl ammonia sulphur The N-1 such as acyl group, N- (1,1,2,2- tetramethyl butyl) sulfamoyl replace sulfamoyl；

N, N- DimethylsuIfamoyl, N, N- ethyl-methyl sulfamoyl, N, N- diethyl amino sulfonyl, N, N- propyl first Base sulfamoyl, N, N- isopropyl methyl sulfamoyl, N, N- tertbutyl methyl sulfamoyl, N, N- butyl ethyl sulfonamides Base, N, N- bis- (1- methyl-propyl) sulfamoyls, N, N- hept-ylmethyl sulfamoyl, N, bis- (2- ethylhexyl) sulfamoyls of N- Equal N, N-2 replace sulfamoyl；

N- methylamino, N- ethylamino, N- propylcarbamic, N- isopropylamino, N- butylamino, N- isobutyl group ammonia Base, N- s-butylamino, N- tert-butylamino, N- pentyl amino, N- (1- ethyl propyl) amino, N- (1,1- dimethyl propyl) Amino, N- (1,2- dimethyl propyl) amino, N- (2,2- dimethyl propyl) amino, N- (1- methyl butyl) amino, N- (2- first Base butyl) amino, N- (3- methyl butyl) amino, N- clopentylamino, N- hexylamino, N- (1,3- dimethylbutyl) ammonia Base, N- (3,3- dimethylbutyl) amino, N- heptyl amino, N- (1- methylhexyl) amino, N- (Isosorbide-5-Nitrae-dimethyl amyl group) ammonia Base, N- octyl amino, N- (2- ethylhexyl) amino, N- (1,5- dimethyl) hexylamino, N- (1,1,2,2- tetramethyl fourth Base) the N- alkyl amino such as amino；

N, N- dimethylamino, N, N- ethylmethylamino, N, N- diethylamino, N, N- propyl-methylamino, N, N- Isopropylmethylamino, N, N- tertbutyl methyl amino, N, N- butyl ethyl amino, N, N- bis- (1- methyl-propyl) amino, N, N- hept-ylmethyl amino, N, the N such as bis- (2- ethylhexyl) amino of N-, N- dialkyl amido；

N- Methylaminomethyl, N- ethylaminomethyl, N- propylcarbamic methyl, N- isopropylaminomethyl, N- butyl Amino methyl, N- isobutylamino methyl, N- s-butylamino methyl, N- tert-butylamino methyl, N- pentyl amino methyl, N- (1- ethyl propyl) amino methyl, N- (1,1- dimethyl propyl) amino methyl, N- (1,2- dimethyl propyl) amino methyl, N- (2,2- dimethyl propyl) amino methyl, N- (1- methyl butyl) amino methyl, N- (2- methyl butyl) amino methyl, N- (3- Methyl butyl) amino methyl, N- clopentylamino methyl, N- hexylamino methyl, N- (1,3- dimethylbutyl) amino methyl, N- (3,3- dimethylbutyl) amino methyl, N- heptyl amino methyl, N- (1- methylhexyl) amino methyl, N- (Isosorbide-5-Nitrae-diformazan Base amyl) amino methyl, N- octilaminomethyl, N- (2- ethylhexyl) amino methyl, N- (1,5- dimethyl) hexylamino The N- alkylamidomethyls such as methyl, N- (1,1,2,2- tetramethyl butyl) amino methyl；

N, N- dimethylaminomethyl, N, N- ethylmethylaminomethyl, N, N- diethylamino methyl, N, N- propyl first Base amino methyl, N, N- isopropylmethylamino methyl, N, N- tertbutyl methyl amino methyl, N, N- butyl ethyl amino first Base, N, N- bis- (1- methyl-propyl) amino methyls, N, N- hept-ylmethyl amino methyl, N, bis- (2- ethylhexyl) amino methyls of N- Equal N, N- dialkylaminomethyl group；

It is trifluoromethyl, perfluoro-ethyl, perfluoro propyl, perfluoroisopropyl, perfluor isopropenyl, perfluor (1- propylene) base, complete Fluorine (2- propylene) base, perfluoro butyl, perfluor isobutyl group, perfluor sec-butyl, perfluoro-t-butyl, perfluor (2- butylene) base, perfluor (1, 3- butadiene) base, perfluoropentyl, nonafluoro-t-butyl, perfluor 3- amyl, perfluor neopentyl, perfluor tertiary pentyl, perfluor (1- methyl Amyl) base, perfluor (2- methyl amyl) base, perfluor (2- amylene) base, perfluoro hexyl, perfluor isohesyl, perfluor (5- methyl oneself Base) it is base, perfluor (2- ethylhexyl) base, perfluor heptyl, perfluoro capryl, perfluor nonyl, perfluoro decyl, perfluor undecyl, complete Fluorine dodecyl, perfluor octadecyl etc. have the aliphatic alkyl of fluorine atom；

Perfluor cyclopropyl, perfluorocyclobutanearyl, perfluor cyclopenta, perfluorocyclohexyl, perfluor cyclohexenyl group, perfluor suberyl, Perfluor (1- methylcyclohexyl) base, perfluor (2- methylcyclohexyl) base, perfluor (3- methylcyclohexyl) base, perfluor (4- methyl ring Hexyl) base, perfluor (1,2- Dimethylcyclohexyl) base, perfluor (1,3- Dimethylcyclohexyl) base, perfluor (Isosorbide-5-Nitrae-dimethyleyelohexane Base) base, perfluor (2,3- Dimethylcyclohexyl) base, perfluor (2,4- Dimethylcyclohexyl) base, perfluor (2,5- dimethyleyelohexanes Base) base, perfluor (2,6- Dimethylcyclohexyl) base, perfluor (3,4- Dimethylcyclohexyl) base, perfluor (3,5- dimethyleyelohexanes Base) base, perfluor (2,2- Dimethylcyclohexyl) base, perfluor (3,3- Dimethylcyclohexyl) base, perfluor (4,4- dimethyleyelohexanes Base) base, perfluor (2,4,6- trimethylcyclohexyl) base, perfluor (2,2,6,6- tetramethyl-ring hexyl) base, perfluor (3,3,5,5- tetra- Methylcyclohexyl) alicyclic alkyl with fluorine atom such as base；

Perfluorophenyl, perfluor (o-tolyl) base, perfluor (tolyl) base, perfluor (p-methylphenyl) base, perfluor diformazan Phenyl, perfluor mesitylene base, perfluor (adjacent cumenyl) base, perfluor (cumenyl) base, perfluor (to cumenyl) base, Perfluor benzyl, perfluor phenethyl, perfluorinated biphenyl, perfluor 1- naphthalene, perfluor 2- naphthalene, 1- trifluoromethyl, 2- fluoroform Base phenyl, 3- trifluoromethyl, 4- trifluoromethyl etc. have the aromatic hydrocarbyl of fluorine atom；

Perfluoromethoxy, pentafluoroethoxy, perfluor propoxyl group, perfluoroisopropoxy groups, perfluor butoxy, perfluor isobutyl oxygen Base, perfluor sec-butoxy, perfluor tert .-butoxy, perfluor amoxy, perfluor phenoxy group, perfluor benzyloxy, 2,2,2- trifluoroethoxies Base, (perfluoro-ethyl) methoxyl group, (perfluoro propyl) methoxyl group, (perfluor (isopropyl)) methoxyl group, (perfluor (isopropenyl)) first Oxygroup, (perfluor (1- acrylic)) methoxyl group, (perfluor (2- acrylic)) methoxyl group, (perfluoro butyl) methoxyl group, (perfluor is (different Butyl)) methoxyl group, (perfluor (sec-butyl)) methoxyl group, (perfluor (tert-butyl)) methoxyl group, (perfluor (2- cyclobutenyl)) methoxy Base, (perfluor (1,3-butadiene base)) methoxyl group, (perfluoropentyl) methoxyl group, (perfluor (isopentyl)) methoxyl group, (perfluor (3- Amyl)) methoxyl group, (perfluor (neopentyl)) methoxyl group, (perfluor (tertiary pentyl)) methoxyl group, (perfluor (1- methyl amyl)) methoxy Base, (perfluor (2- methyl amyl)) methoxyl group, (perfluor (2- pentenyl)) methoxyl group, (perfluoro hexyl) methoxyl group, (perfluor is (different Hexyl)) methoxyl group, (perfluor (5- methylhexyl)) methoxyl group, (perfluor ((2- ethyl) hexyl)) methoxyl group, (perfluor heptyl) first Oxygroup, (perfluoro capryl) methoxyl group, (perfluor nonyl) methoxyl group, (perfluoro decyl) methoxyl group, (perfluor undecyl) methoxyl group, (perfluorododecyl) methoxyl group, (perfluor octadecyl) methoxyl group etc. have the substituted oxy of fluorine atom；

2,3- bis- (trifluoromethyl) phenyl methyls, bis- (trifluoromethyl) phenyl methyls of 2,4-, bis- (trifluoromethyl) benzene of 2,5- Bis- (trifluoromethyl) phenyl methyls of ylmethyl, 2,6-, bis- (trifluoromethyl) phenyl methyls of 3,4-, bis- (trifluoromethyl) phenyl of 3,5- Bis- (trifluoromethyl) phenyl methyls such as methyl etc..

As R¹And R², preferred aliphat alkyl, alicyclic alkyl or aromatic hydrocarbyl.

Hydrogen atom contained by the aliphatic alkyl can be replaced by alicyclic alkyl or aromatic hydrocarbyl.

Hydrogen atom contained by the alicyclic alkyl can be replaced by aliphatic alkyl, alicyclic alkyl or aromatic hydrocarbyl.

Hydrogen atom contained by the aromatic hydrocarbyl can be replaced by aliphatic alkyl, alicyclic alkyl or aromatic hydrocarbyl.

As R¹, the preferred aliphatic alkyl of carbon atom number 1~10.Wherein, preferably ethyl, butyl, hexyl, (2- ethyl) Hexyl and octyl, wherein more preferable ethyl, butyl, hexyl and (2- ethyl) hexyl, further preferred (2- ethyl) oneself Base.R¹When for these groups, dissolubility in a solvent is excellent.

As R², the preferred aliphatic alkyl of carbon atom number 1~10.Wherein, more preferable ethyl, butyl, hexyl, (2- second Base) hexyl and octyl, wherein further preferred ethyl, butyl, hexyl and (2- ethyl) hexyl, particularly preferred hexyl with And (2- ethyl) hexyl.R²When for these groups, dissolubility in a solvent is excellent.

It is preferred that R³~R⁹It is hydrogen atom.

As R¹⁰In carbon atom number 1~20 1 valency alkyl, for example there are for example, it is methyl, ethyl, propyl, isopropyl, different Acrylic, 1- acrylic, 2- acrylic, butyl, isobutyl group, sec-butyl, tert-butyl, (2- ethyl) butyl, 2- cyclobutenyl, 1,3- Butadienyl, amyl, isopentyl, 3- amyl, neopentyl, tertiary pentyl, 1- methyl amyl, 2- methyl amyl, 2- pentenyl, (3- Ethyl) amyl, hexyl, isohesyl, 5- methylhexyl, (2- ethyl) hexyl, heptyl, (3- ethyl) heptyl, octyl, nonyl, the last of the ten Heavenly stems The aliphatic alkyls such as base, undecyl, dodecyl, octadecyl；

And the group being composed of them.

It, will in compound (1)

It is set as " FF ", it will

Be set as " GG ", in the case where indicating compound (1) with FF-GG, as FF, for example there are for example respectively by formula (F1)~ The group that formula (F20) indicates.In formula, ● indicate bonding position.

As GG, for example there are the groups for example indicated respectively by formula (G1)~formula (G109).

Combination by compound (1) as above-mentioned FF and GG is illustrated in 1~table of table 5.In 1~table of table 5, the column FF and GG What is recorded in column is the formula number of the above-mentioned group illustrated respectively.

[table 1]

Compound	FF	GG
			1-1	F1	G1
1-2	F2	G1
			1-3	F3	G1
1-4	F4	G1
			1-5	F5	G1
1-6	F6	G1
			1-7	F7	G1
1-8	F8	G1
			1-9	F9	G1
1-10	F10	G1
			1-11	F11	G1
1-12	F12	G1
			1-13	F13	G1
1-14	F14	G1
			1-15	F15	G1
1-16	F16	G1
			1-17	F17	G1
1-18	F18	G1
			1-19	F19	G1
1-20	F20	G1
			1-21	F1	G2
1-22	F2	G3
			1-23	F3	G4
1-24	F4	G5
			1-25	F5	G6
1-26	F6	G7
			1-27	F7	G8
1-28	F8	G9
			1-29	F9	G10
1-30	F10	G1 1

[table 2]

[table 3]

[table 4]

[table 5]

Compound	FF	GG
			1-121	F1	G83
1-122	F2	G84
			1-123	F3	G85
1-124	F4	G86
			1-125	F5	G87
1-126	F6	G88
			1-127	F7	G89
1-128	F8	G90
			1-129	F9	G91
1-130	F10	G92
			1-131	F11	G93
1-132	F12	G94
			1-133	F13	G95
1-134	F14	G96
			1-135	F15	G97
1-136	F16	G98
			1-137	F17	G99
1-138	F18	G100
			1-139	F19	G101
1-140	F20	G102
			1-141	F1	G103
1-142	F2	G104
			1-143	F3	G105
1-144	F4	G106
			1-145	F5	G107
1-146	F6	G108
			1-147	F7	G109

It then, will in compound (1 ')

It is set as " HH ", in the case where indicating compound (1 ') with FF-HH-FF, as FF, for example there are for example respectively by above-mentioned The group that formula (F1)~formula (F20) indicates, as HH, for example there are the groups for example indicated respectively by formula (H1)~formula (H93).Formula In, ● indicate bonding position.

Compound (1 ') is illustrated in 6~table of table 22 as the combination of above-mentioned FF and HH.

In 6~table of table 22, what the column FF and the column HH were recorded is the formula number of the above-mentioned group illustrated respectively.

[table 6]

[table 7]

[table 8]

Compound	FF	HH
			1-208	F20	H4
1-209	F2	H5
			1-210	F1	H6
1-211	F2	H6
			1-212	F3	H6
1-213	F4	H6
			1-214	F5	H6
1-215	F6	H6
			1-216	F7	H6
1-217	F8	H6
			1-218	F9	H6
1-219	F10	H6
			1-220	F11	H6
1-221	F12	H6
			1-222	F13	H6
1-223	F14	H6
			1-224	F15	H6
1-225	F16	H6
			1-226	F17	H6
1-227	F18	H6
			1-228	F19	H6
1-229	F20	H6
			1-230	F3	H7
1-231	F4	H8
			1-232	F5	H9
1-233	F1	H10
			1-234	F2	H10
1-235	F3	H10
			1-236	F4	H10
1-237	F5	H10

[table 9]

[table 10]

[table 11]

[table 12]

Compound	FF	HH
			1-328	F18	H31
1-329	F19	H31
			1-330	F20	H31
1-331	F1	H32
			1-332	F1	H33
1-333	F2	H33
			1-334	F3	H33
1-335	F4	H33
			1-336	F5	H33
1-337	F6	H33
			1-338	F7	H33
1-339	F8	H33
			1-340	F9	H33
1-341	F10	H33
			1-342	F11	H33
1-343	F12	H33
			1-344	F13	H33
1-345	F14	H33
			1-346	F15	H33
1-347	F16	H33
			1-348	F17	H33
1-349	F18	H33
			1-350	F19	H33
1-351	F20	H33
			1-352	F1	H34
1-353	F2	H34
			1-354	F3	H34
1-355	F4	H34
			1-356	F5	H34
1-357	F6	H34

[table 13]

[table 14]

[table 15]

[table 16]

Compound	FF	HH
			1-448	F10	H45
1-449	F11	H45
			1-450	F12	H45
1-451	F13	H45
			1-452	F14	H45
1-453	F15	H45
			1-454	F16	H45
1-455	F17	H45
			1-456	F18	H45
1-457	F19	H45
			1-458	F20	H45
1-459	F9	H46
			1-460	F10	H47
1-461	F11	H48
			1-462	F12	H49
1-463	F13	H50
			1-464	F14	H51
1-465	F15	H52
			1-466	F16	H53
1-467	F17	H54
			1-468	F18	H55
1-469	F19	H56
			1-470	F20	H57
1-471	F1	H58
			1-472	F2	H59
1-473	F3	H60
			1-474	F1	H61
1-475	F2	H61
			1-476	F3	H61
1-477	F4	H61

[table 17]

[table 18]

[table 19]

[table 20]

Compound	FF	HH
			1-568	F10	H70
1-569	F11	H70
			1-570	F12	H70
1-571	F13	H70
			1-572	F14	H70
1-573	F15	H70
			1-574	F16	H70
1-575	F17	H70
			1-576	F18	H70
1-577	F19	H70
			1-578	F20	H70
1-579	F6	H71
			1-580	F7	H72
1-581	F1	H73
			1-582	F2	H73
1-583	F3	H73
			1-584	F4	H73
1-585	F5	H73
			1-586	F6	H73
1-587	F7	H73
			1-588	F8	H73
1-589	F9	H73
			1-590	F10	H73
1-591	F11	H73
			1-592	F12	H73
1-593	F13	H73
			1-594	F14	H73
1-595	F15	H73
			1-596	F16	H73
1-597	F17	H73

[table 21]

[table 22]

Compound	FF	HH
			1-628	F15	H82
1-629	F16	H83
			1-630	F17	H84
1-631	F18	H85
			1-632	F19	H86
1-633	F20	H87
			1-634	F1	H88
1-635	F2	H89
			1-636	F3	H90
1-637	F4	H91
			1-638	F5	H92
1-639	F6	H93

From raw material it is chiral from the viewpoint of, as compound (1) and compound (1 '), preferably shown in 23~table of table 27 Compound, more preferable 28~table of table, 29 compound represented.

[table 23]

[table 24]

Compound	FF	HH
			1-148	F1	H1
1-149	F2	H1
			1-156	F9	H1
1-157	F10	H1
			1-158	F11	H1
1-169	F1	H3
			1-170	F2	H3
1-177	F9	H3
			1-178	F10	H3
1-179	F11	H3
			1-189	F1	H4
1-190	F2	H4
			1-197	F9	H4
1-198	F10	H4
			1-199	F11	H4
1-210	F1	H6
			1-211	F2	H6
1-218	F9	H6
			1-219	F10	H6
1-220	F11	H6
			1-233	F1	H10
1-234	F2	H10
			1-241	F9	H10
1-242	F10	H10
			1-243	F11	H10
1-255	F1	H13
			1-256	F2	H13
1-263	F9	H13
			1-264	F10	H13
1-265	F11	H13

[table 25]

[table 26]

[table 27]

Compound	FF	HH
			1-559	F1	H70
1-560	F2	H70
			1-567	F9	H70
1-568	F10	H70
			1-569	F11	H70
1-581	F1	H73
			1-582	F2	H73
1-589	F9	H73
			1-590	F10	H73
1-591	F11	H73
			1-602	F1	H75
1-603	F2	H75
			1-610	F9	H75
1-611	F10	H75
			1-612	F11	H75

[table 28]

[table 29]

Compound (2) is indicated by formula (2), further includes its tautomer or their salt.

In formula (2), as R¹¹~R¹⁴In halogen atom, for example there are fluorine atom, chlorine atom, bromine atom, iodine atoms.

In formula (2), as R¹¹~R¹⁴In carbon atom number 1~20 1 valency alkyl, for example there are such as methyl, ethyl, third Base, isopropyl, isopropenyl, 1- acrylic, 2- acrylic, butyl, isobutyl group, sec-butyl, tert-butyl, 2- cyclobutenyl, 1,3- Butadienyl, amyl, isopentyl, (2- ethyl) butyl, 3- amyl, neopentyl, tertiary pentyl, 1- methyl amyl, 2- methyl amyl, 2- pentenyl, (3- ethyl) amyl, hexyl, isohesyl, 5- methylhexyl, (2- ethyl) hexyl, heptyl, (3- ethyl) heptyl, The aliphatic alkyls such as octyl, nonyl, decyl, undecyl, dodecyl, octadecyl；

And the group being composed of them.

As constitute these 1 valency alkyls methylene by oxygen atom, sulphur atom ,-N (R¹⁵)-, sulfonyl or carbonyl replace after Hydrogen atom contained by obtained group, 1 valency alkyl is by halogen atom, cyano, nitro, carbamoyl, sulfamoyl ,-SO₃M、- CO₂M, the base that hydroxyl or amino obtain after replacing, for example there are for example,

The aryloxy group such as phenoxy group；

The aralkoxies such as benzyloxy；

The acyloxy such as acetoxyl group, benzoyloxy；

It is trifluoromethyl, perfluoro-ethyl, perfluoro propyl, perfluoroisopropyl, perfluor isopropenyl, perfluor (1- propylene) base, complete Fluorine (2- propylene) base, perfluoro butyl, perfluor isobutyl group, perfluor sec-butyl, perfluoro-t-butyl, perfluor (2- butylene) base, perfluor (1, 3- butadiene) base, perfluoropentyl, nonafluoro-t-butyl, perfluor 3- amyl, perfluor neopentyl, perfluor tertiary pentyl, perfluor 1- methylpent Base, perfluor 2- methyl amyl, perfluor 2- pentenyl, perfluoro hexyl, perfluor isohesyl, perfluor 5- methylhexyl, perfluor 2- ethyl Hexyl, perfluor heptyl, perfluoro capryl, perfluor nonyl, perfluoro decyl, perfluor undecyl, perfluorododecyl, perfluor octadecane Base etc. has the aliphatic alkyl of fluorine atom；

2,3- bis- (trifluoromethyl) phenyl methyls, bis- (trifluoromethyl) phenyl methyls of 2,4-, bis- (trifluoromethyl) benzene of 2,5- Bis- (trifluoromethyl) phenyl methyls of ylmethyl, 2,6-, bis- (trifluoromethyl) phenyl methyls of 3,4-, bis- (trifluoromethyl) phenyl of 3,5- Methyl etc..

As R¹¹And R¹², preferred aliphat alkyl, alicyclic alkyl or aromatic hydrocarbyl.

As R¹¹, the preferred aliphatic alkyl of carbon atom number 1~10.Wherein, more preferable ethyl, butyl, hexyl, (2- second Base) hexyl and octyl, further preferred ethyl, butyl, hexyl and (2- ethyl) hexyl, particularly preferred (2- ethyl) oneself Base.R¹¹It is excellent for the compound of the present invention dissolubility in a solvent of these groups.

As R¹², the preferred aliphatic alkyl of carbon atom number 1~10.Wherein, more preferable ethyl, butyl, hexyl, (2- second Base) hexyl and octyl, further preferred ethyl, butyl, hexyl and (2- ethyl) hexyl, particularly preferred hexyl and (2- Ethyl) hexyl.R¹²It is excellent for the compound of the present invention dissolubility in a solvent of these groups.

Consider from easy manufacture view, preferably R¹³And R¹⁴For hydrogen atom.

R¹¹And R¹³It is bonded and ring or R is collectively formed with the nitrogen-atoms of carbon atom and adjoining on adjacent phenyl ring¹² And R¹⁴When being bonded and ring be collectively formed with the nitrogen-atoms of carbon atom and adjoining on adjacent phenyl ring,

As *-R¹¹-R¹³- * and *-R¹²-R¹⁴- *, for example there are *-CH₂-CH₂-*、*-CF₂-CF₂-*、*-CH₂-C (CH₂)₅- * or *-CH₂-C(CH₃)₂- * etc., preferably *-CH₂-CH₂- * and *-CH₂-C(CH₃)₂- *, particularly preferred *-CH₂-C (CH₃)₂-*.* bonding position is indicated.

As R¹⁵In carbon atom number 1~20 1 valency alkyl, for example there are methyl, ethyl, propyl, isopropyl, isopropyl alkene Base, 1- acrylic, 2- acrylic, butyl, isobutyl group, sec-butyl, tert-butyl, (2- ethyl) butyl, 2- cyclobutenyl, 1,3- fourth two Alkenyl, amyl, isopentyl, 3- amyl, neopentyl, tertiary pentyl, 1- methyl amyl, 2- methyl amyl, 2- pentenyl, (3- ethyl) Amyl, hexyl, isohesyl, 5- methylhexyl, (2- ethyl) hexyl, heptyl, (3- ethyl) heptyl, octyl, nonyl, decyl, ten The aliphatic alkyls such as one alkyl, dodecyl, octadecyl；

And the group being composed of them.

M indicates hydrogen atom or alkali metal atom, preferably hydrogen atom, sodium atom or potassium atom, more preferable hydrogen atom.

As Q¹For-CO₂The compound (2) of M, for example there are the compounds for example indicated respectively by formula (2-1)~formula (2-44) And their salt.

As Q²For-CO₂The compound (2) of M, for example there are the chemical combination for example indicated respectively by formula (2-45)~formula (2-88) Object and their salt.

From the viewpoint of being readily synthesized, as compound (2), preferred compound (2-1)~compound (2-8), chemical combination Object (2-15)~compound (2-42), compound (2-45)~compound (2-52) and compound (2-59)~compound (2- 86), more preferable compound (2-1)~compound (2-4), compound (2-15)~compound (2-32), compound (2-39)~ Compound (2-42), compound (2-45)~compound (2-48), compound (2-59)~compound (2-76) and compound (2-83)~compound (2-86), wherein further preferred compound (2-1)~compound (2-4), compound (2-15)~change Close object (2-20), compound (2-27)~compound (2-28), compound (2-31)~compound (2-32), compound (2-39) ~compound (2-42), (2-45)~compound (2-48), compound (2-59)~compound (2-64), compound (2-71)~ Compound (2-72), compound (2-75)~compound (2-76) and compound (2-83)~compound (2-86).

Compound (3) is indicated by formula (3), also includes its tautomer or their salt.

In formula (3), X ' indicates the 16th race's atom ,-N (R in the periodic table of elements²⁵)-or-C (R²⁵)(R²⁶)-.As element The 16th race's atom in periodic table, for example there are oxygen atom, sulphur atom, selenium atom, tellurium atoms.From light characteristic or it is easy to manufacture in terms of Consider, as X ', preferably oxygen atom, sulphur atom ,-N (R²⁵)-or-C (R²⁵)(R²⁶The more preferable oxygen atom of)-, sulphur atom or-N (R²⁵The further preferred oxygen atom of)-, or sulphur atom, particularly preferred oxygen atom.If X ' is oxygen atom, coloring of the invention is consolidated When the property changed resin combination is made green color filter, brightness has the tendency that getting higher.

In formula (3), as R¹⁶~R²⁴In halogen atom, for example there are fluorine atom, chlorine atom, bromine atom, iodine atoms.

In formula (3), as R¹⁶~R²⁴In carbon atom number 1~20 1 valency alkyl, for example there are for example

Methyl, ethyl, propyl, isopropyl, isopropenyl, 1- acrylic, 2- acrylic, butyl, isobutyl group, sec-butyl, Tert-butyl, (2- ethyl) butyl, 2- cyclobutenyl, 1,3-butadiene base, amyl, isopentyl, 3- amyl, neopentyl, tertiary pentyl, 1- Methyl amyl, 2- methyl amyl, 2- pentenyl, (3- ethyl) amyl, hexyl, isohesyl, 5- methylhexyl, (2- ethyl) oneself The aliphatic alkyls such as base, heptyl, (3- ethyl) heptyl, octyl, nonyl, decyl, undecyl, dodecyl, octadecyl；

Phenyl, o-tolyl, tolyl, p-methylphenyl, xylyl, mesitylene base, adjacent cumenyl, isopropyl Phenyl, to aromatic hydrocarbyls such as cumenyl, benzyl, phenethyl, xenyl, 1- naphthalene, 2- naphthalene etc..

As constitute these 1 valency alkyls methylene by oxygen atom, sulphur atom ,-N (R²⁷)-, sulfonyl or carbonyl replace after Hydrogen atom contained by obtained group or 1 valency alkyl by halogen atom, cyano, nitro, carbamoyl, sulfamoyl ,- SO₃M’、-CO₂The group that M ', hydroxyl or amino obtain after replacing, for example there are for example

The aryloxy group such as phenoxy group；

The aralkoxies such as benzyloxy；

The acyloxy such as acetoxyl group, benzoyloxy；

Trifluoromethyl, perfluoro-ethyl, perfluoro propyl, perfluoroisopropyl, perfluor isopropenyl, perfluor 1- acrylic, perfluor 2- acrylic, perfluoro butyl, perfluor isobutyl group, perfluor sec-butyl, perfluoro-t-butyl, perfluor 2- cyclobutenyl, perfluor 1,3- fourth two Alkenyl, perfluoropentyl, nonafluoro-t-butyl, perfluor 3- amyl, perfluor neopentyl, perfluor tertiary pentyl, perfluor (1- methyl amyl) base, Perfluor (2- methyl amyl) base, perfluor 2- pentenyl, perfluoro hexyl, perfluor isohesyl, perfluor (5- methylhexyl) base, perfluor ((2- ethyl) hexyl) base, perfluor heptyl, perfluoro capryl, perfluor nonyl, perfluoro decyl, perfluor undecyl, perfluor dodecane The aliphatic alkyls containing fluorine atom such as base, perfluor octadecyl；

Perfluor cyclopropyl, perfluorocyclobutanearyl, perfluor cyclopenta, perfluorocyclohexyl, perfluor cyclohexenyl group, perfluor suberyl, Perfluor (1- methylcyclohexyl) base, perfluor (2- methylcyclohexyl) base, perfluor (3- methylcyclohexyl) base, perfluor (4- methyl ring Hexyl) base, perfluor (1,2- Dimethylcyclohexyl) base, perfluor (1,3- Dimethylcyclohexyl) base, perfluor (Isosorbide-5-Nitrae-dimethyleyelohexane Base) base, perfluor (2,3- Dimethylcyclohexyl) base, perfluor (2,4- Dimethylcyclohexyl) base, perfluor (2,5- dimethyleyelohexanes Base) base, perfluor (2,6- Dimethylcyclohexyl) base, perfluor (3,4- Dimethylcyclohexyl) base, perfluor (3,5- dimethyleyelohexanes Base) base, perfluor (2,2- Dimethylcyclohexyl) base, perfluor (3,3- Dimethylcyclohexyl) base, perfluor (4,4- dimethyleyelohexanes Base) base, perfluor (2,4,6- trimethylcyclohexyl) base, perfluor (2,2,6,6- tetramethyl-ring hexyl) base, perfluor (3,3,5,5- tetra- Methylcyclohexyl) alicyclic alkyl containing fluorine atom such as base；

Perfluorophenyl, perfluor (o-tolyl) base, perfluor (tolyl) base, perfluor (p-methylphenyl) base, perfluor diformazan Phenyl, perfluor mesitylene base, perfluor (adjacent cumenyl) base, perfluor (cumenyl) base, perfluor (to cumenyl) base, Perfluor benzyl, perfluor phenethyl, perfluorinated biphenyl, perfluor 1- naphthalene, perfluor 2- naphthalene, 1- trifluoromethyl, 2- fluoroform The aromatic hydrocarbyls containing fluorine atom such as base phenyl, 3- trifluoromethyl, 4- trifluoromethyl；

Perfluoromethoxy, pentafluoroethoxy, perfluor propoxyl group, perfluoroisopropoxy groups, perfluor butoxy, perfluor isobutyl oxygen Base, perfluor sec-butoxy, perfluor tert .-butoxy, perfluor amoxy, perfluor phenoxy group, perfluor benzyloxy, 2,2,2- trifluoroethoxies Base, (perfluoro-ethyl) methoxyl group, (perfluoro propyl) methoxyl group, (perfluoroisopropyl) methoxyl group, (perfluor isopropenyl) methoxyl group, (perfluor 1- acrylic) methoxyl group, (perfluor 2- acrylic) methoxyl group, (perfluoro butyl) methoxyl group, (perfluor isobutyl group) methoxy Base, (perfluor sec-butyl) methoxyl group, (perfluoro-t-butyl) methoxyl group, (perfluor 2- cyclobutenyl) methoxyl group, (perfluor 1,3-butadiene Base) methoxyl group, (perfluoropentyl) methoxyl group, (nonafluoro-t-butyl) methoxyl group, (perfluor 3- amyl) methoxyl group, (perfluor neopentyl) Methoxyl group, (perfluor tertiary pentyl) methoxyl group, (perfluor (1- methyl amyl)) methoxyl group, (perfluor (2- methyl amyl)) methoxyl group, (perfluor 2- pentenyl) methoxyl group, (perfluoro hexyl) methoxyl group, (perfluor isohesyl) methoxyl group, (perfluor (5- methylhexyl)) first Oxygroup, (perfluor ((2- ethyl) hexyl)) methoxyl group, (perfluor heptyl) methoxyl group, (perfluoro capryl) methoxyl group, (perfluor nonyl) Methoxyl group, (perfluoro decyl) methoxyl group, (perfluor undecyl) methoxyl group, (perfluorododecyl) methoxyl group, (perfluor octadecane Base) alkoxy containing fluorine atom such as methoxyl group；

As R¹⁶And R¹⁷, preferably the aliphatic alkyl of carbon atom number 1~20, carbon atom number 3~20 alicyclic alkyl And the aromatic hydrocarbyl of carbon atom number 6~20, the fat race alkyl of more preferable carbon atom number 1~10, further preferred carbon atom The aliphatic alkyl of number 1~5, the aliphatic alkyl of particularly preferred carbon atom number 2~4.

As R¹⁶And R¹⁷In aliphatic alkyl, concrete example have ethyl, butyl, hexyl, (2- ethyl) hexyl and Octyl, preferably ethyl, butyl, hexyl and (2- ethyl) hexyl, more preferable ethyl and butyl.R¹⁶And R¹⁷For these bases When group, raw material is easy to get.

Consider from easy manufacture view, preferably R¹⁸、R¹⁹、R²²、R²³、R²⁴For hydrogen atom.

R¹⁶And R¹⁸It is bonded and ring is collectively formed with the nitrogen-atoms of carbon atom and adjoining on adjacent phenyl ring, or R¹⁷And R¹⁹When being bonded and ring is collectively formed with the nitrogen-atoms of carbon atom and adjoining on adjacent phenyl ring, as *-R¹⁶- R¹⁸- * and *-R¹⁷-R¹⁹- *, for example there are *-CH₂-CH₂-*、*-CF₂-CF₂-*、*-CH₂-C(CH₂)₅- * or *-CH₂-C (CH₃)₂- * etc., preferably *-CH₂-CH₂- * or *-CH₂-C(CH₃)₂- *, particularly preferred *-CH₂-C(CH₃)₂-*.* bonding position is indicated It sets.

Consider from easy manufacture view, R²⁰Preferably hydrogen atom, hydroxyl, alkoxy, alkoxy carbonyl or acyloxy.

As R²¹, preferably hydrogen atom, the aliphatic alkyl of carbon atom number 1~6, alkoxy, alkoxy carbonyl, acyloxy or Cyano.

As R²⁵And R²⁶, preferred aliphat alkyl, alicyclic alkyl or aromatic hydrocarbyl.

R²⁵And R²⁶In aliphatic alkyl contained by hydrogen atom can be replaced by alicyclic alkyl or aromatic hydrocarbyl.

R²⁵And R²⁶In alicyclic alkyl contained by hydrogen atom can be by aliphatic alkyl, alicyclic alkyl or fragrance Race's alkyl replaces.

R²⁵And R²⁶In aromatic hydrocarbyl contained by hydrogen atom can be by aliphatic alkyl, alicyclic alkyl or fragrance Race's alkyl replaces.

As the alkali metal atom in M ', for example there are lithium atom, potassium atom, sodium atoms.It is preferred that potassium atom or sodium atom, more It is preferred that sodium atom.

As R²⁷In carbon atom number 1~20 1 valency alkyl, for example there are such as methyl, ethyl, propyl, isopropyl, isopropyls Alkenyl, 1- acrylic, 2- acrylic, butyl, isobutyl group, sec-butyl, tert-butyl, (2- ethyl) butyl, 2- cyclobutenyl, 1,3- fourth Dialkylene, amyl, isopentyl, 3- amyl, neopentyl, tertiary pentyl, 1- methyl amyl, 2- methyl amyl, 2- pentenyl, (3- second Base) amyl, hexyl, isohesyl, 5- methylhexyl, (2- ethyl) hexyl, heptyl, (3- ethyl) heptyl, octyl, nonyl, decyl, The aliphatic alkyls such as undecyl, dodecyl, octadecyl；

And the group being composed of them.

As L ' indicate group, for example there are for example respectively by formula (L ' 1)~formula (L ' 30) indicate group and these Methylene contained by group is by oxygen atom, sulphur atom ,-N (R²⁵)-, sulfonyl or carbonyl replace after obtained group or these Hydrogen atom contained by group is by halogen atom, cyano, nitro, carbamoyl, sulfamoyl ,-SO₃M’、-CO₂M ', hydroxyl or ammonia The group that base obtains after replacing.In formula (L ' 1)~formula (L ' 30), ● indicate bonding position.

The group that L ' preferred formula (L ' 1)~formula (L ' 20) or formula (L ' 29)~formula (L ' 30) indicate.It wherein, more preferably can be with Trifluoromethyl methylene with substituent group.As the preferred L ', concrete example has respectively by formula (L ' 1)~formula (L ' 17) The group of expression.Preferred formula (L ' 1)~formula (L ' 10), more preferable formula (L ' 1).By containing fluorine atom in L ', has and colouring It is not easy that the tendency of foreign matter is precipitated in hardening resin composition.

As compound (3), for example there are compounds and their salt that such as 30~table of table 125 is respectively shown in.Each table R¹⁶~R²⁶In symbol documented by column, " cHx " indicates that cyclohexyl, " Hex " indicate that n-hexyl, " pTol " are indicated to methylbenzene Base, " 2EHx " indicate that 2- ethylhexyl, " 2NPh " indicate that 2- naphthalene, " tBu " indicate that tert-butyl, " iPr " indicate isopropyl, " biPh " indicates 4- phenyl, and " FF1 " indicates that 4- trifluoromethyl, " FF2 " indicate bis- (trifluoromethyl) phenyl methyls, " FF3 " indicates perfluor cyclopenta, and " FF4 " indicates that perfluor (3,5- Dimethylcyclohexyl) base, " FF5 " indicate perfluor (4- methyl ring Hexyl) base, " FF6 " indicates that perfluorocyclohexyl, " FF7 " indicate that perfluoro-ethyl, " FF8 " indicate (perfluoro-ethyl) methoxyl group, " FF9 " Indicate that perfluor (isopropoxy) base, " FF10 " indicate that 2,2,2- trifluoro ethoxy, " FF11 " indicate perfluoromethoxy.In addition, L ' The symbol on column is corresponding with the group that above-mentioned formula (L ' 1)~formula (L ' 30) indicates respectively.

Compound (the 3-1)~compound (3-301) indicated by formula (3a-O) is illustrated in 30~table of table 43.

[table 30]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-1

Et

H

L’1

3-2

Et

H

CF₃

H

L’1

3-3

Et

H

CF₃

L’1

3-4

Et

H

Ph

H

L’1

3-5

Et

H

biPh

H

L’1

3-6

Et

H

FF1

H

L’1

3-7

Et

H

FF2

H

L’1

3-8

Et

H

FF3

H

L’1

3-9

Et

H

FF4

H

L’1

3-10

Et

H

FF5

H

L’1

3-11

Et

H

FF6

H

L’1

3-12

Et

H

FF7

H

L’1

3-13

Et

H

FF8

H

L’1

3-14

Et

H

FF9

H

L’1

3-15

Et

H

FF10

H

L’1

3-16

Et

H

FF11

H

L’1

3-17

Et

H

L’3

3-18

Et

H

L’4

3-19

Et

H

L’10

3-20

Et

H

L’12

3-21

Et

H

F

H

L’18

3-22

Et

H

L’24

3-23

Et

H

L’25

3-24

Et

H

L’26

3-25

Et

H

L’27

3-26

Et

H

L’28

3-27

Et

Me

H

L’2

3-28

Et

H

SO₃H

H

L’5

3-29

Et

H

OH

H

L’6

3-30

Et

H

PhO

H

L’7

[table 31]

[table 32]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-44

Bu

H

L’1

3-45

Bu

H

CF₃

H

L’1

3-46

Bu

H

CF₃

L’1

3-47

Bu

H

Ph

H

L’1

3-48

Bu

H

biPh

H

L’1

3-49

Bu

H

FF1

H

L’1

3-50

Bu

H

FF2

H

L’1

3-51

Bu

H

FF3

H

L’1

3-52

Bu

H

FF4

H

L’1

3-53

Bu

H

FF5

H

L’1

3-54

Bu

H

FF6

H

L’1

3-55

Bu

H

FF7

H

L’1

3-56

Bu

H

FF8

H

L’1

3-57

Bu

H

FF9

H

L’1

3-58

Bu

H

FF10

H

L’1

3-59

Bu

H

FF11

H

L’1

3-60

Bu

H

L’3

3-61

Bu

H

L’4

3-62

Bu

H

L’10

3-63

Bu

H

L’12

3-64

Bu

H

F

H

L’18

3-65

Bu

H

L’24

3-66

Bu

H

L’25

3-67

Bu

H

L’26

3-68

Bu

H

L’27

3-69

Bu

H

L’28

3-70

Bu

Me

H

L’2

3-71

Bu

H

SO₃H

H

L’5

3-72

Bu

H

OH

H

L’6

3-73

Bu

H

PhO

H

L’7

3-74

Bu

H

CO₂Ph

H

L’8

[table 33]

[table 34]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-87

Ph

H

L’1

3-88

Ph

H

CF₃

H

L’1

3-89

Ph

H

CF₃

L’1

3-90

Ph

H

Ph

H

L’1

3-91

Ph

H

biPh

H

L’1

3-92

Ph

H

FF1

H

L’1

3-93

Ph

H

FF2

H

L’1

3-94

Ph

H

FF3

H

L’1

3-95

Ph

H

FF4

H

L’1

3-96

Ph

H

FF5

H

L’1

3-97

Ph

H

FF6

H

L’1

3-98

Ph

H

FF7

H

L’1

3-99

Ph

H

FF8

H

L’1

3-100

Ph

H

FF9

H

L’1

3-101

Ph

H

FF10

H

L’1

3-102

Ph

H

FF11

H

L’1

3-103

Ph

H

L’3

3-104

Ph

H

L’4

3-105

Ph

H

L’10

3-106

Ph

H

L’12

3-107

Ph

H

F

H

L’18

3-108

Ph

H

L’24

3-109

Ph

H

L’25

3-110

Ph

H

L’26

3-111

Ph

H

L’27

3-112

Ph

H

L’28

3-113

Ph

Me

H

L’2

3-114

Ph

H

SO₃H

H

L’5

3-115

Ph

H

OH

H

L’6

3-116

Ph

H

PhO

H

L’7

[table 35]

[table 36]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-130

pTol

H

L’1

3-131

pTol

H

CF₃

H

L’1

3-132

pTol

H

CF₃

L’1

3-133

pTol

H

Ph

H

L’1

3-134

pTol

H

biPh

H

L’1

3-135

pTol

H

FF1

H

L’1

3-136

pTol

H

FF2

H

L’1

3-137

pTol

H

FF3

H

L’1

3-138

pTol

H

FF4

H

L’1

3-139

pTol

H

FF5

H

L’1

3-140

pTol

H

FF6

H

L’1

3-141

pTol

H

FF7

H

L’1

3-142

pTol

H

FF8

H

L’1

3-143

pTol

H

FF9

H

L’1

3-144

pTol

H

FF10

H

L’1

3-145

pTol

H

FF11

H

L’1

3-146

pTol

H

L’3

3-147

pTol

H

L’4

3-148

pTol

H

L’10

3-149

pTol

H

L’12

3-150

pTol

H

F

H

L’18

3-151

pTol

H

L’24

3-152

pTol

H

L’25

3-153

pTol

H

L’26

3-154

pTol

H

L’27

3-155

pTol

H

L’28

3-156

pTol

Me

H

L’2

3-157

pTol

H

SO₃H

H

L’5

3-158

pTol

H

OH

H

L’6

3-159

pTol

H

PhO

H

L’7

3-160

pTol

H

CO₂Ph

H

L’8

[table 37]

[table 38]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-173

2NPh

Ph

H

L’1

3-174

2NPh

Ph

H

CF₃

H

L’1

3-175

2NPh

Ph

H

CF₃

L’1

3-176

2NPh

Ph

H

Ph

H

L’1

3-177

2NPh

Ph

H

biPh

H

L’1

3-178

2NPh

Ph

H

FF1

H

L’1

3-179

2NPh

Ph

H

FF2

H

L’1

3-180

2NPh

Ph

H

FF3

H

L’1

3-181

2NPh

Ph

H

FF4

H

L’1

3-182

2NPh

Ph

H

FF5

H

L’1

3-183

2NPh

Ph

H

FF6

H

L’1

3-184

2NPh

Ph

H

FF7

H

L’1

3-185

2NPh

Ph

H

FF8

H

L’1

3-186

2NPh

Ph

H

FF9

H

L’1

3-187

2NPh

Ph

H

FF10

H

L’1

3-188

2NPh

Ph

H

FF11

H

L’1

3-189

2NPh

Ph

H

L’3

3-190

2NPh

Ph

H

L’4

3-191

2NPh

Ph

H

L’10

3-192

2NPh

Ph

H

L’12

3-193

2NPh

Ph

H

F

H

L’18

3-194

2NPh

Ph

H

L’24

3-195

2NPh

Ph

H

L’25

3-196

2NPh

Ph

H

L’26

3-197

2NPh

Ph

H

L’27

3-198

2NPh

Ph

H

L’28

3-199

2NPh

Ph

Me

H

L’2

3-200

2NPh

Ph

H

SO₃H

H

L’5

3-201

2NPh

Ph

H

OH

H

L’6

3-202

2NPh

Ph

H

PhO

H

L’7

3-203

2NPh

Ph

H

CO₂Ph

H

L’8

[table 39]

[table 40]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-216

Et

H

CN

H

L’1

3-217

Et

H

CN

CF₃

H

L’1

3-218

Et

H

CN

H

CF₃

L’1

3-219

Et

H

CN

Ph

H

L’1

3-220

Et

H

CN

biPh

H

L’1

3-221

Et

H

CN

FF1

H

L’1

3-222

Ft

Et

H

CN

FF2

H

L’1

3-223

Et

H

CN

FF3

H

L’1

3-224

Et

H

CN

FF4

H

L’1

3-225

Et

H

CN

FF5

H

L’1

3-226

Et

H

CN

FF6

H

L’1

3-227

Et

H

CN

FF7

H

L’1

3-228

Et

H

CN

FF8

H

L’1

3-229

Et

H

CN

FF9

H

L’1

3-230

Et

H

CN

FF10

H

L’1

3-231

Et

H

CN

FF11

H

L’1

3-232

Et

H

CN

H

L’3

3-233

Et

H

CN

H

L’4

3-234

Et

H

CN

H

L’10

3-235

Et

H

CN

H

L’12

3-236

Et

H

CN

F

H

L’18

3-237

Et

H

CN

H

L’24

3-238

Et

H

CN

H

L’25

3-239

Et

H

CN

H

L’26

3-240

Et

H

CN

H

L’27

3-241

Et

H

CN

H

L’28

3-242

Et

Me

H

CN

H

L’2

3-243

Et

H

SO₃H

H

CN

H

L’5

3-244

Et

H

OH

CN

H

L’6

3-245

Et

H

PhO

CN

H

L’7

3-246

Et

H

CN

CO₂Ph

H

L’8

[table 41]

[table 42]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-259

2EHx

H

L’1

3-260

2EHx

H

CF₃

H

L’1

3-261

2EHx

H

CF₃

L’1

3-262

2EHx

H

Ph

H

L’1

3-263

2EHx

H

biPh

H

L’1

3-264

2EHx

H

FF1

H

L’1

3-265

2EHx

H

FF2

H

L’1

3-266

2EHx

H

FF3

H

L’1

3-267

2EHx

H

FF4

H

L’1

3-268

2EHx

H

FF5

H

L’1

3-269

2EHx

H

FF6

H

L’1

3-270

2EHx

H

FF7

H

L’1

3-271

2EHx

H

FF8

H

L’1

3-272

2EHx

H

FF9

H

L’1

3-273

2EHx

H

FF10

H

L’1

3-274

2EHx

H

FF11

H

L’1

3-275

2EHx

H

L’3

3-276

2EHx

H

L’4

3-277

2EHx

H

L’10

3-278

2EHx

H

L’12

3-279

2EHx

H

F

H

L’18

3-280

2EHx

H

L’24

3-281

2EHx

H

L’25

3-282

2EHx

H

L’26

3-283

2EHx

H

L’27

3-284

2EHx

H

L’28

3-285

2EHx

Me

H

L’2

3-286

2EHx

H

SO₃H

H

L’5

3-287

2EHx

H

OH

H

L’6

3-288

2EHx

H

PhO

H

L’7

3-289

2EHx

H

CO₂Ph

H

L’8

[table 43]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-290

2EHx

H

cHx

H

L’9

3-291

2EHx

H

NBu₂

L’11

3-292

2EHx

Br

H

L’13

3-293

2EHx

H

Cl

H

L’14

3-294

2EHx

H

CO₂Me

H

L’15

3-295

2EHx

H

tBu

H

L’16

3-296

2EHx

H

CN

H

L’17

3-297

2EHx

H

NO₂

H

L’19

3-298

2EHx

H

CO₂H

L’20

3-299

2EHx

SO₂NBu₂

H

L’21

3-300

2EHx

H

CONBu₂

H

L’22

3-301

2EHx

H

MeO

H

L’23

Compound (the 3-302)~compound (3-602) indicated by formula (3a-S) is enumerated in 44~table of table 57.

[table 44]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-302

Et

H

L’1

3-303

Et

H

CF₃

H

L’1

3-304

Et

H

CF₃

L’1

3-305

Et

H

Ph

H

L’1

3-306

Et

H

biPh

H

L’1

3-307

Et

H

FF1

H

L’1

3-308

Et

H

FF2

H

L’1

3-309

Et

H

FF3

H

L’1

3-310

Et

H

FF4

H

L’1

3-311

Et

H

FF5

H

L’1

3-312

Et

H

FF6

H

L’1

3-313

Et

H

FF7

H

L’1

3-314

Et

H

FF8

H

L’1

3-315

Et

H

FF9

H

L’1

3-316

Et

H

FF10

H

L’1

3-317

Et

H

FF11

H

L’1

3-318

Et

H

L’3

3-319

Et

H

L’4

3-320

Et

H

L’10

3-321

Et

H

L’12

3-322

Et

H

F

H

L’18

3-323

Et

H

L’24

3-324

Et

H

L’25

3-325

Et

H

L’26

3-326

Et

H

L’27

3-327

Et

H

L’28

3-328

Et

Me

H

L’2

3-329

Et

H

SO₃H

H

L’5

3-330

Et

H

OH

H

L’6

3-331

Et

H

PhO

H

L’7

3-332

Et

H

CO₂Ph

H

L’8

[table 45]

[table 46]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-345

Bu

H

L’1

3-346

Bu

H

CF₃

H

L’1

3-347

Bu

H

CF₃

L’1

3-348

Bu

H

Ph

H

L’1

3-349

Bu

H

biPh

H

L’1

3-350

Bu

H

FF1

H

L’1

3-351

Bu

H

FF2

H

L’1

3-352

Bu

H

FF3

H

L’1

3-353

Bu

H

FF4

H

L’1

3-354

Bu

H

FF5

H

L’1

3-355

Bu

H

FF6

H

L’1

3-356

Bu

H

FF7

H

L’1

3-357

Bu

H

FF8

H

L’1

3-358

Bu

H

FF9

H

L’1

3-359

Bu

H

FF10

H

L’1

3-360

Bu

H

FF11

H

L’1

3-361

Bu

H

L’3

3-362

Bu

H

L’4

3-363

Bu

H

L’10

3-364

Bu

H

L’12

3-365

Bu

H

F

H

L’18

3-366

Bu

H

L’24

3-367

Bu

H

L’25

3-368

Bu

H

L’26

3-369

Bu

H

L’27

3-370

Bu

H

L’28

3-371

Bu

Me

H

L’2

3-372

Bu

H

SO₃H

H

L’5

3-373

Bu

H

OH

H

L’6

3-374

Bu

H

PhO

H

L’7

3-375

Bu

H

CO₂Ph

H

L’8

[table 47]

[table 48]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-388

Ph

H

L’1

3-389

Ph

H

CF₃

H

L’1

3-390

Ph

H

CF₃

L’1

3-391

Ph

H

Ph

H

L’1

3-392

Ph

H

biPh

H

L’1

3-393

Ph

H

FF1

H

L’1

3-394

Ph

H

FF2

H

L’1

3-395

Ph

H

FF3

H

L’1

3-396

Ph

H

FF4

H

L’1

3-397

Ph

H

FF5

H

L’1

3-398

Ph

H

FF6

H

L’1

3-399

Ph

H

FF7

H

L’1

3-400

Ph

H

FF8

H

L’1

3-401

Ph

H

FF9

H

L’1

3-402

Ph

H

FF10

H

L’1

3-403

Ph

H

FF11

H

L’1

3-404

Ph

H

L’3

3-405

Ph

H

L’4

3-406

Ph

H

L’10

3-407

Ph

H

L’12

3-408

Ph

H

F

H

L’18

3-409

Ph

H

L’24

3-410

Ph

H

L’25

3-411

Ph

H

L’26

3-412

Ph

H

L’27

3-413

Ph

H

L’28

3-414

Ph

Me

H

L’2

3-415

Ph

H

SO₃H

H

L’5

3-416

Ph

H

OH

H

L’6

3-417

Ph

H

PhO

H

L’7

3-418

Ph

H

CO₂Ph

H

L’8

[table 49]

[table 50]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-431

pTol

H

L’1

3-432

pTol

H

CF₃

H

L’1

3-433

pTol

H

CF₃

L’1

3-434

pTol

H

Ph

H

L’1

3-435

pTol

H

biPh

H

L’1

3-436

pTol

H

FF1

H

L’1

3-437

pTol

H

FF2

H

L’1

3-438

pTol

H

FF3

H

L’1

3-439

pTol

H

FF4

H

L’1

3-440

pTol

H

FF5

H

L’1

3-441

pTol

H

FF6

H

L’1

3-442

pTol

H

FF7

H

L’1

3-443

pTol

H

FF8

H

L’1

3-444

pTol

H

FF9

H

L’1

3-445

pTol

H

FF10

H

L’1

3-446

pTol

H

FF11

H

L’1

3-447

pTol

H

L’3

3-448

pTol

H

L’4

3-449

pTol

H

L’10

3-450

pTol

H

L’12

3-451

pTol

H

F

H

L’18

3-452

pTol

H

L’24

3-453

pTol

H

L’25

3-454

pTol

H

L’26

3-455

pTol

H

L’27

3-456

pTol

H

L’28

3-457

pTol

Me

H

L’2

3-458

pTol

H

SO₃H

H

L’5

3-459

pTol

H

OH

H

L’6

3-460

pTol

H

PhO

H

L’7

3-461

pTol

H

CO₂Ph

H

L’8

[table 51]

[table 52]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-474

2NPh

Ph

H

L’1

3-475

2NPh

Ph

H

CF₃

H

L’1

3-476

2NPh

Ph

H

CF₃

L’1

3-477

2NPh

Ph

H

Ph

H

L’1

3-478

2NPh

Ph

H

biPh

H

L’1

3-479

2NPh

Ph

H

FF1

H

L’1

3-480

2NPh

Ph

H

FF2

H

L’1

3-481

2NPh

Ph

H

FF3

H

L’1

3-482

2NPh

Ph

H

FF4

H

L’1

3-483

2NPh

Ph

H

FF5

H

L’1

3-484

2NPh

Ph

H

FF6

H

L’1

3-485

2NPh

Ph

H

FF7

H

L’1

3-486

2NPh

Ph

H

FF8

H

L’1

3-487

2NPh

Ph

H

FF9

H

L’1

3-488

2NPh

Ph

H

FF10

H

L’1

3-489

2NPh

Ph

H

FF11

H

L’1

3-490

2NPh

Ph

H

L’3

3-491

2NPh

Ph

H

L’4

3-492

2NPh

Ph

H

L’10

3-493

2NPh

Ph

H

L’12

3-494

2NPh

Ph

H

F

H

L’18

3-495

2NPh

Ph

H

L’24

3-496

2NPh

Ph

H

L’25

3-497

2NPh

Ph

H

L’26

3-498

2NPh

Ph

H

L’27

3-499

2NPh

Ph

H

L’28

3-500

2NPh

Ph

Me

H

L’2

3-501

2NPh

Ph

H

SO₃H

H

L’5

3-502

2NPh

Ph

H

OH

H

L’6

3-503

2NPh

Ph

H

PhO

H

L’7

3-504

2NPh

Ph

H

CO₂Ph

H

L’8

[table 53]

[table 54]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-517

Et

H

CN

H

L’1

3-518

Et

H

CN

CF₃

H

L’1

3-519

Et

H

CN

H

CF₃

L’1

3-520

Et

H

CN

Ph

H

L’1

3-521

Et

H

CN

biPh

H

L’1

3-522

Et

H

CN

FF1

H

L’1

3-523

Et

H

CN

FF2

H

L’1

3-524

Et

H

CN

FF3

H

L’1

3-525

Et

H

CN

FF4

H

L’1

3-526

Et

H

CN

FF5

H

L’1

3-527

Et

H

CN

FF6

H

L’1

3-528

Et

H

CN

FF7

H

L’1

3-529

Et

H

CN

FF8

H

L’1

3-530

Et

H

CN

FF9

H

L’1

3-531

Et

H

CN

FF10

H

L’1

3-532

Et

H

CN

FF11

H

L’1

3-533

Et

H

CN

H

L’3

3-534

Et

H

CN

H

L’4

3-535

Et

H

CN

H

L’10

3-536

Et

H

CN

H

L’12

3-537

Et

H

CN

F

H

L’18

3-538

Et

H

CN

H

L’24

3-539

Et

H

CN

H

L’25

3-540

Et

H

CN

H

L’26

3-541

Et

H

CN

H

L’27

3-542

Et

H

CN

H

L’28

3-543

Et

Me

H

CN

H

L’2

3-544

Et

H

SO₃H

H

CN

H

L’5

3-545

Et

H

OH

CN

H

L’6

3-546

Et

H

PhO

CN

H

L’7

3-547

Et

H

CN

CO₂Ph

H

L’8

[table 55]

[table 56]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-560

2EHx

H

L’1

3-561

2EHx

H

CF₃

H

L’1

3-562

2EHx

H

CF₃

L’1

3-563

2EHx

H

Ph

H

L’1

3-564

2EHx

H

biPh

H

L’1

3-565

2EHx

H

FF1

H

L’1

3-566

2EHx

H

FF2

H

L’1

3-567

2EHx

H

FF3

H

L’1

3-568

2EHx

H

FF4

H

L’1

3-569

2EHx

H

FF5

H

L’1

3-570

2EHx

H

FF6

H

L’1

3-571

2EHx

H

FF7

H

L’1

3-572

2EHx

H

FF8

H

L’1

3-573

2EHx

H

FF9

H

L’1

3-574

2EHx

H

FF10

H

L’1

3-575

2EHx

H

FF11

H

L’1

3-576

2EHx

H

L’3

3-577

2EHx

H

L’4

3-578

2EHx

H

L’10

3-579

2EHx

H

L’12

3-580

2EHx

H

F

H

L’18

3-581

2EHx

H

L’24

3-582

2EHx

H

L’25

3-583

2EHx

H

L’26

3-584

2EHx

H

L’27

3-585

2EHx

H

L’28

3-586

2EHx

Me

H

L’2

3-587

2EHx

H

SO₃H

H

L’5

3-588

2EHx

H

OH

H

L’6

3-589

2EHx

H

PhO

H

L’7

3-590

2EHx

H

CO₂Ph

H

L’8

[table 57]

Compound (the 3-603)~compound (3-903) indicated by formula (3a-N) is illustrated in 58~table of table 71.

[table 58]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-603

Et

H

Me

L’1

3-604

Et

H

CF₃

H

Me

L’1

3-605

Et

H

CF₃

Me

L’1

3-606

Et

H

Ph

H

Me

L’1

3-607

Et

H

biPh

H

Me

L’1

3-608

Et

H

FF1

H

Me

L’1

3-609

Et

H

FF2

H

Me

L’1

3-610

Et

H

FF3

H

Me

L’1

3-611

Et

H

FF4

H

Me

L’1

3-612

Et

H

FF5

H

Me

L’1

3-613

Et

H

FF6

H

Me

L’1

3-614

Et

H

FF7

H

Me

L’1

3-615

Et

H

FF8

H

Me

L’1

3-616

Et

H

FF9

H

Me

L’1

3-617

Et

H

FF10

H

Me

L’1

3-618

Et

H

FF11

H

Me

L’1

3-619

Et

H

Me

L’3

3-620

Et

H

Me

L’4

3-621

Et

H

Me

L’10

3-622

Et

H

Me

L’12

3-623

Et

H

F

H

Me

L’18

3-624

Et

H

Me

L’24

3-625

Et

H

Me

L’25

3-626

Et

H

Me

L’26

3-627

Et

H

Me

L’27

3-628

Et

H

Me

L’28

3-629

Et

Me

H

Me

L’2

3-630

Et

H

SO₃H

H

cHx

L’5

3-631

Et

H

OH

H

iPr

L’6

3-632

Et

H

PhO

H

Ph

L’7

3-633

Et

H

CO₂Ph

H

Bu

L’8

[table 59]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-634

Et

H

cHx

H

tBu

L’9

3-635

Et

H

NBu₂

Et

L’11

3-636

Et

Br

H

Me

L’13

3-637

Et

H

Cl

H

cHx

L’14

3-638

Et

H

CO₂Me

H

iPr

L’15

3-639

Et

H

tBu

H

Ph

L’16

3-640

Et

H

CN

H

Bu

L’17

3-641

Et

H

NO₂

H

tBu

L’19

3-642

Et

H

CO₂H

Et

L’20

3-643

Et

SO₂NBu₂

H

Me

L’21

3-644

Et

H

CONBu₂

H

cHx

L’22

3-645

Et

H

MeO

H

iPr

L’23

[table 60]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-646

Bu

H

Me

L’1

3-647

Bu

H

CF₃

H

Me

L’1

3-648

Bu

H

CF₃

Me

L’1

3-649

Bu

H

Ph

H

Me

L’1

3-650

Bu

H

biPh

H

Me

L’1

3-651

Bu

H

FF1

H

Me

L’1

3-652

Bu

H

FF2

H

Me

L’1

3-653

Bu

H

FF3

H

Me

L’1

3-654

Bu

H

FF4

H

Me

L’1

3-655

Bu

H

FF5

H

Me

L’1

3-656

Bu

H

FF6

H

Me

L’1

3-657

Bu

H

FF7

H

Me

L’1

3-658

Bu

H

FF8

H

Me

L’1

3-659

Bu

H

FF9

H

Me

L’1

3-660

Bu

H

FF10

H

Me

L’1

3-661

Bu

H

FF11

H

Me

L’1

3-662

Bu

H

Me

L’3

3-663

Bu

H

Me

L’4

3-664

Bu

H

Me

L’10

3-665

Bu

H

Me

L’12

3-666

Bu

H

F

H

Me

L’18

3-667

Bu

H

Me

L’24

3-668

Bu

H

Me

L’25

3-669

Bu

H

Me

L’26

3-670

Bu

H

Me

L’27

3-671

Bu

H

Me

L’28

3-672

Bu

Me

H

Me

L’2

3-673

Bu

H

SO₃H

H

cHx

L’5

3-674

Bu

H

OH

H

iPr

L’6

3-675

Bu

H

PhO

H

Ph

L’7

3-676

Bu

H

CO₂Ph

H

Bu

L’8

[table 61]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-677

Bu

H

cHx

H

tBu

L’9

3-678

Bu

H

NBu₂

Et

L’11

3-679

Bu

Br

H

Me

L’13

3-680

Bu

H

Cl

H

cHx

L’14

3-681

Bu

H

CO₂Me

H

iPr

L’15

3-682

Bu

H

tBu

H

Ph

L’16

3-683

Bu

H

CN

H

Bu

L’17

3-684

Bu

H

NO₂

H

tBu

L’19

3-685

Bu

H

CO₂H

Et

L’20

3-686

Bu

SO₂NBu₂

H

Me

L’21

3-687

Bu

H

CONBu₂

H

cHx

L’22

3-688

Bu

H

MeO

H

iPr

L’23

[table 62]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-689

Ph

H

Me

L’1

3-690

Ph

H

CF₃

H

Me

L’1

3-691

Ph

H

CF₃

Me

L’1

3-692

Ph

H

Ph

H

Me

L’1

3-693

Ph

H

biPh

H

Me

L’1

3-694

Ph

H

FF1

H

Me

L’1

3-695

Ph

H

FF2

H

Me

L’1

3-696

Ph

H

FF3

H

Me

L’1

3-697

Ph

H

FF4

H

Me

L’1

3-698

Ph

H

FF5

H

Me

L’1

3-699

Ph

H

FF6

H

Me

L’1

3-700

Ph

H

FF7

H

Me

L’1

3-701

Ph

H

FF8

H

Me

L’1

3-702

Ph

H

FF9

H

Me

L’1

3-703

Ph

H

FF10

H

Me

L’1

3-704

Ph

H

FF11

H

Me

L’1

3-705

Ph

H

Me

L’3

3-706

Ph

H

Me

L’4

3-707

Ph

H

Me

L’10

3-708

Ph

H

Me

L’12

3-709

Ph

H

F

H

Me

L’18

3-710

Ph

H

Me

L’24

3-711

Ph

H

Me

L’25

3-712

Ph

H

Me

L’26

3-713

Ph

H

Me

L’27

3-714

Ph

H

Me

L’28

3-715

Ph

Me

H

Me

L’2

3-716

Ph

H

SO₃H

H

cHx

L’5

3-717

Ph

H

OH

H

iPr

L’6

3-718

Ph

H

PhO

H

Ph

L’7

3-719

Ph

H

CO₂Ph

H

Bu

L’8

[table 63]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-720

Ph

H

cHx

H

tBu

L’9

3-721

Ph

H

NBu₂

Et

L’11

3-722

Ph

Br

H

Me

L’13

3-723

Ph

H

Cl

H

cHx

L’14

3-724

Ph

H

CO₂Me

H

iPr

L’15

3-725

Ph

H

tBu

H

Ph

L’16

3-726

Ph

H

CN

H

Bu

L’17

3-727

Ph

H

NO₂

H

tBu

L’19

3-728

Ph

H

CO₂H

Et

L’20

3-729

Ph

SO₂NBu₂

H

Me

L’21

3-730

Ph

H

CONBu₂

H

cHx

L’22

3-731

Ph

H

MeO

H

iPr

L’23

[table 64]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-732

pTol

H

Me

L’1

3-733

pTol

H

CF₃

H

Me

L’1

3-734

pTol

H

CF₃

Me

L’1

3-735

pTol

H

Ph

H

Me

L’1

3-736

pTol

H

biPh

H

Me

L’1

3-737

pTol

H

FF1

H

Me

L’1

3-738

pTol

H

FF2

H

Me

L’1

3-739

pTol

H

FF3

H

Me

L’1

3-740

pTol

H

FF4

H

Me

L’1

3-741

pTol

H

FF5

H

Me

L’1

3-742

pTol

H

FF6

H

Me

L’1

3-743

pTol

H

FF7

H

Me

L’1

3-744

pTol

H

FF8

H

Me

L’1

3-745

pTol

H

FF9

H

Me

L’1

3-746

pTol

H

FF10

H

Me

L’1

3-747

pTol

H

FF11

H

Me

L’1

3-748

pTol

H

Me

L’3

3-749

pTol

H

Me

L’4

3-750

pTol

H

Me

L’10

3-751

pTol

H

Me

L’12

3-752

pTol

H

F

H

Me

L’18

3-753

pTol

H

Me

L’24

3-754

pTol

H

Me

L’25

3-755

pTol

H

Me

L’26

3-756

pTol

H

Me

L’27

3-757

pTol

H

Me

L’28

3-758

pTol

Me

H

Me

L’2

3-759

pTol

H

SO₃H

H

cHx

L’5

3-760

pTol

H

OH

H

iPr

L’6

3-761

pTol

H

PhO

H

Ph

L’7

3-762

pTol

H

CO₂Ph

H

Bu

L’8

[table 65]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-763

pTol

H

cHx

H

tBu

L’9

3-764

pTol

H

NBu₂

Et

L’11

3-765

pTol

Br

H

Me

L’13

3-766

pTol

H

Cl

H

cHx

L’14

3-767

pTol

H

CO₂Me

H

iPr

L’15

3-768

pTol

H

tBu

H

Ph

L’16

3-769

pTol

H

CN

H

Bu

L’17

3-770

pTol

H

NO₂

H

tBu

L’19

3-771

pTol

H

CO₂H

Et

L’20

3-772

pTol

SO₂NBu₂

H

Me

L’21

3-773

pTol

H

CONBu₂

H

cHx

L’22

3-774

pTol

H

MeO

H

iPr

L’23

[table 66]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-775

2NPh

Ph

H

Me

L’1

3-776

2NPh

Ph

H

CF₃

H

Me

L’1

3-777

2NPh

Ph

H

CF₃

Me

L’1

3-778

2NPh

Ph

H

Ph

H

Me

L’1

3-779

2NPh

Ph

H

biPh

H

Me

L’1

3-780

2NPh

Ph

H

FF1

H

Me

L’1

3-781

2NPh

Ph

H

FF2

H

Me

L’1

3-782

2NPh

Ph

H

FF3

H

Me

L’1

3-783

2NPh

Ph

H

FF4

H

Me

L’1

3-784

2NPh

Ph

H

FF5

H

Me

L’1

3-785

2NPh

Ph

H

FF6

H

Me

L’1

3-786

2NPh

Ph

H

FF7

H

Me

L’1

3-787

2NPh

Ph

H

FF8

H

Me

L’1

3-788

2NPh

Ph

H

FF9

H

Me

L’1

3-789

2NPh

Ph

H

FF10

H

Me

L’1

3-790

2NPh

Ph

H

FF11

H

Me

L’1

3-791

2NPh

Ph

H

Me

L’3

3-792

2NPh

Ph

H

Me

L’4

3-793

2NPh

Ph

H

Me

L’10

3-794

2NPh

Ph

H

Me

L’12

3-795

2NPh

Ph

H

F

H

Me

L’18

3-796

2NPh

Ph

H

Me

L’24

3-797

2NPh

Ph

H

Me

L’25

3-798

2NPh

Ph

H

Me

L’26

3-799

2NPh

Ph

H

Me

L’27

3-800

2NPh

Ph

H

Me

L’28

3-801

2NPh

Ph

Me

H

Me

L’2

3-802

2NPh

Ph

H

SO₃H

H

cHx

L’5

3-803

2NPh

Ph

H

OH

H

iPr

L’6

3-804

2NPh

Ph

HH

H

PhO

H

Ph

L’7

3-805

2NPh

Ph

H

CO₂Ph

H

Bu

L’8

[table 67]

[table 68]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-818

Et

H

CN

H

Me

L’1

3-819

Et

H

CN

CF₃

H

Me

L’1

3-820

Et

H

CN

H

CF₃

Me

L’1

3-821

Et

H

CN

Ph

H

Me

L’1

3-822

Et

H

CN

biPh

H

Me

L’1

3-823

Et

H

CN

FF1

H

Me

L’1

3-824

Et

H

CN

FF2

H

Me

L’1

3-825

Et

H

CN

FF3

H

Me

L’1

3-826

Et

H

CN

FF4

H

Me

L’1

3-827

Et

H

CN

FF5

H

Me

L’1

3-828

Et

H

CN

FF6

H

Me

L’1

3-829

Et

H

CN

FF7

H

Me

L’1

3-830

Et

H

CN

FF8

H

Me

L’1

3-831

Et

H

CN

FF9

H

Me

L’1

3-832

Et

H

CN

FF10

H

Me

L’1

3-833

Et

H

CN

FF11

H

Me

L’1

3-834

Et

H

CN

H

Me

L’3

3-835

Et

H

CN

H

Me

L’4

3-836

Et

H

CN

H

Me

L’10

3-837

Et

H

CN

H

Me

L’12

3-838

Et

H

CN

F

H

Me

L’18

3-839

Et

H

CN

H

Me

L’24

3-840

Et

H

CN

H

Me

L’25

3-841

Et

H

CN

H

Me

L’26

3-842

Et

H

CN

H

Me

L’27

3-843

Et

H

CN

H

Me

L’28

3-844

Et

Me

H

CN

H

Me

L’2

3-845

Et

H

SO₃H

H

CN

H

cHx

L’5

3-846

Et

H

OH

CN

H

iPr

L’6

3-847

Et

H

PhO

CN

H

Ph

L’7

3-848

Et

H

CN

CO₂Ph

H

Bu

L’8

[table 69]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-849

Et

H

CN

H

cHx

H

tBu

L’9

3-850

Et

H

CN

H

NBu₂

Et

L’11

3-851

Et

Br

H

CN

H

Me

L’13

3-852

Et

H

Cl

H

CN

H

cHx

L’14

3-853

Et

H

CO₂Me

CN

H

iPr

L’15

3-854

Et

H

CN

H

tBu

H

Ph

L’16

3-855

Et

H

CN

H

Bu

L’17

3-856

Et

H

CN

H

NO₂

H

tBu

L’19

3-857

Et

H

CN

H

CO₂H

Et

L’20

3-858

Et

SO₂NBu₂

H

CN

H

Me

L’21

3-859

Et

H

CONBu₂

H

CN

H

cHx

L’22

3-860

Et

H

MeO

CN

H

iPr

L’23

[table 70]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-861

2EHx

H

Me

L’1

3-862

2EHx

H

CF₃

H

Me

L’1

3-863

2EHx

H

CF₃

Me

L’1

3-864

2EHx

H

Ph

H

Me

L’1

3-865

2EHx

H

biPh

H

Me

L’1

3-866

2EHx

H

FF1

H

Me

L’1

3-867

2EHx

H

FF2

H

Me

L’1

3-868

2EHx

H

FF3

H

Me

L’1

3-869

2EHx

H

FF4

H

Me

L’1

3-870

2EHx

H

FF5

H

Me

L’1

3-871

2EHx

H

FF6

H

Me

L’1

3-872

2EHx

H

FF7

H

Me

L’1

3-873

2EHx

H

FF8

H

Me

L’1

3-874

2EHx

H

FF9

H

Me

L’1

3-875

2EHx

H

FF10

H

Me

L’1

3-876

2EHx

H

FF11

H

Me

L’1

3-877

2EHx

H

Me

L’3

3-878

2EHx

H

Me

L’4

3-879

2EHx

H

Me

L’10

3-880

2EHx

H

Me

L’12

3-881

2EHx

H

F

H

Me

L’18

3-882

2EHx

H

Me

L’24

3-883

2EHx

H

Me

L’25

3-884

2EHx

H

Me

L’26

3-885

2EHx

H

Me

L’27

3-886

2EHx

H

Me

L’28

3-887

2EHx

Me

H

Me

L’2

3-888

2EHx

H

SO₃H

H

cHx

L’5

3-889

2EHx

H

OH

H

iPr

L’6

3-890

2EHx

H

PhO

H

Ph

L’7

3-891

2EHx

H

CO₂Ph

H

Bu

L’8

[table 71]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-892

2EHx

H

cHx

H

tBu

L’9

3-893

2EHx

H

NBu₂

Et

L’11

3-894

2EHx

Br

H

Me

L’13

3-895

2EHx

H

Cl

H

cHx

L’14

3-896

2EHx

H

CO₂Me

H

iPr

L’15

3-897

2EHx

H

tBu

H

Ph

L’16

3-898

2EHx

H

CN

H

Bu

L’17

3-899

2EHx

H

NO₂

H

tBu

L’19

3-900

2EHx

H

CO₂H

Et

L’20

3-901

2EHx

SO₂NBu₂

H

Me

L’21

3-902

2EHx

H

CONBu₂

H

cHx

L’22

3-903

2EHx

H

MeO

H

iPr

L’23

Compound (the 3-904)~compound (3-1204) indicated by formula (3a-C) is illustrated in 72~table of table 85.

[table 72]

[table 73]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

R²⁶

L’

3-935

Et

H

cHx

H

tBu

Ph

L’9

3-936

Et

H

NBu₂

Et

Bu

L’11

3-937

Et

Br

H

Me

tBu

L’13

3-938

Et

H

Cl

H

cHx

Et

L’14

3-939

Et

H

CO₂Me

H

iPr

Me

L’15

3-940

Et

H

tBu

H

Ph

cHx

L’16

3-941

Et

H

CN

H

Bu

iPr

L’17

3-942

Et

H

NO₂

H

tBu

Ph

L’19

3-943

Et

H

CO₂H

Et

Bu

L’20

3-944

Et

SO₂NBu₂

H

Me

tBu

L’21

3-945

Et

H

CONBu₂

H

cHx

Et

L’22

3-946

Et

H

MeO

H

iPr

Me

L’23

[table 74]

[table 75]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

R²⁶

L’

3-978

Bu

H

cHx

H

tBu

Ph

L’9

3-979

Bu

H

NBu₂

Et

Bu

L’11

3-980

Bu

Br

H

Me

tBu

L’13

3-981

Bu

H

Cl

H

cHx

Et

L’14

3-982

Bu

H

CO₂Me

H

iPr

Me

L’15

3-983

Bu

H

tBu

H

Ph

cHx

L’16

3-984

Bu

H

CN

H

Bu

iPr

L’17

3-985

Bu

H

NO₂

H

tBu

Ph

L’19

3-986

Bu

H

CO₂H

Et

Bu

L’20

3-987

Bu

SO₂NBu₂

H

Me

tBu

L’21

3-988

Bu

H

CONBu₂

H

cHx

Et

L’22

3-989

Bu

H

MeO

H

iPr

Me

L’23

[table 76]

[table 77]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

R²⁶

L’

3-1021

Ph

H

cHx

H

tBu

Ph

L’9

3-1022

Ph

H

NBu₂

Et

Bu

L’11

3-1023

Ph

Br

H

Me

tBu

L’13

3-1024

Ph

H

Cl

H

cHx

Et

L’14

3-1025

Ph

H

CO₂Me

H

iPr

Me

L’15

3-1026

Ph

H

tBu

H

Ph

cHx

L’16

3-1027

Ph

H

CN

H

Bu

iPr

L’17

3-1028

Ph

H

NO₂

H

tBu

Ph

L’19

3-1029

Ph

H

CO₂H

Et

Bu

L’20

3-1030

Ph

SO₂NBu₂

H

Me

tBu

L’21

3-1031

Ph

H

CONBu₂

H

cHx

Et

L’22

3-1032

Ph

H

MeO

H

iPr

Me

L’23

[table 78]

[table 79]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-1064

pTol

H

cHx

H

tBu

Ph

L’9

3-1065

pTol

H

NBu₂

Et

Bu

L’11

3-1066

pTol

Br

H

Me

tBu

L’13

3-1067

pTol

H

Cl

H

cHx

Et

L’14

3-1068

pTol

H

CO₂Me

H

iPr

Me

L’15

3-1069

pTol

H

tBu

H

Ph

cHx

L’16

3-1070

pTol

H

CN

H

Bu

iPr

L’17

3-1071

pTol

H

NO₂

H

tBu

Ph

L’19

3-1072

pTol

H

CO₂H

Et

Bu

L’20

3-1073

pTol

SO₂NBu₂

H

Me

tBu

L’21

3-1074

pTol

H

CONBu₂

H

cHx

Et

L’22

3-1075

pTol

H

MeO

H

iPr

Me

L’23

[table 80]

[table 81]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-1107

2NPh

Ph

H

cHx

H

tBu

Ph

L’9

3-1108

2NPh

Ph

H

NBu₂

Et

Bu

L’11

3-1109

2NPh

Ph

Br

H

Me

tBu

L’13

3-1110

2NPh

Ph

H

Cl

H

cHx

Et

L’14

3-1111

2NPh

Ph

H

CO₂Me

H

iPr

Me

L’15

3-1112

2NPh

Ph

H

tBu

H

Ph

cHx

L’16

3-1113

2NPh

Ph

H

CN

H

Bu

iPr

L’17

3-1114

2NPh

Ph

H

NO₂

H

tBu

Ph

L’19

3-1115

2NPh

Ph

H

CO₂H

Et

Bu

L’20

3-1116

2NPh

Ph

SO₂NBu₂

H

Me

tBu

L’21

3-1117

2NPh

Ph

H

CONBu₂

H

cHx

Et

L’22

3-1118

2NPh

Ph

H

MeO

H

iPr

Me

L’23

[table 82]

[table 83]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-1150

Et

H

CN

H

cHx

H

tBu

Ph

L’9

3-1151

Et

H

CN

H

NBu₂

Et

Bu

L’11

3-1152

Et

Br

H

CN

H

Me

tBu

L’13

3-1153

Et

H

Cl

H

CN

H

cHx

Et

L’14

3-1154

Et

H

CO₂Me

CN

H

iPr

Me

L’15

3-1155

Et

H

CN

H

tBu

H

Ph

cHx

L’16

3-1156

Et

H

CN

H

Bu

iPr

L’17

3-1157

Et

H

CN

H

NO₂

H

tBu

Ph

L’19

3-1158

Et

H

CN

H

CO₂H

Et

Bu

L’20

3-1159

Et

SO₂NBu₂

H

CN

H

Me

tBu

L’21

3-1160

Et

H

CONBu₂

H

CN

H

cHx

Et

L’22

3-1161

Et

H

MeO

CN

H

iPr

Me

L’23

[table 84]

[table 85]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-1193

2EHx

H

cHx

H

tBu

Ph

L’9

3-1194

2EHx

H

NBu₂

Et

Bu

L’11

3-1195

2EHx

Br

H

Me

tBu

L’13

3-1196

2EHx

H

Cl

H

cHx

Et

L’14

3-1197

2EHx

H

CO₂Me

H

iPr

Me

L’15

3-1198

2EHx

H

tBu

H

Ph

cHx

L’16

3-1199

2EHx

H

CN

H

Bu

iPr

L’17

3-1200

2EHx

H

NO₂

H

tBu

Ph

L’19

3-1201

2EHx

H

CO₂H

Et

Bu

L’20

3-1202

2EHx

SO₂NBu₂

H

Me

tBu

L’21

3-1203

2EHx

H

CONBu₂

H

cHx

Et

L’22

3-1204

2EHx

H

MeO

H

iPr

Me

L’23

Compound (the 3-1205)~compound (3-1247) indicated by formula (3b-O) is illustrated in table 86~87.

[table 86]

[table 87]

Compound

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-1236

CO₂Me

H

L’9

3-1237

H

tBu

H

L’11

3-1238

H

CN

H

L’13

3-1239

H

NO₂

H

L’14

3-1240

H

CO₂H

L’15

3-1241

MeO

H

L’16

3-1242

H

Me

H

L’17

3-1243

H

Br

H

L’19

3-1244

H

SO₃H

H

L’20

3-1245

H

Cl

L’21

3-1246

CONBu₂

H

L’22

3-1247

H

SO₂NBu₂

H

L’23

Compound (the 3-1248)~compound (3-1290) indicated by formula (3b-S) is illustrated in table 88~89.

[table 88]

[table 89]

Compound

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-1279

CO₂Me

H

L’9

3-1280

H

tBu

H

L’11

3-1281

H

CN

H

L’13

3-1282

H

NO₂

H

L’14

3-1283

H

CO₂H

L’15

3-1284

MeO

H

L’16

3-1285

H

Me

H

L’17

3-1286

H

Br

H

L’19

3-1287

H

SO₃H

H

L’20

3-1288

H

Cl

L’21

3-1289

CONBu₂

H

L’22

3-1290

H

SO₂NBu₂

H

L’23

Compound (3-1291)~compound (3-1333) of formula (3b-N) expression is illustrated in table 90~91.

[table 90]

Compound

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-1291

H

Me

L’1

3-1292

H

CF3

H

Me

L’1

3-1293

H

CF₃

Me

L’1

3-1294

H

Ph

H

Me

L’1

3-1295

H

biPh

H

Me

L’1

3-1296

H

FF1

H

Me

L’1

3-1297

H

FF2

H

Me

L’1

3-1298

H

FF3

H

Me

L’1

3-1299

H

FF4

H

Me

L’1

3-1300

H

FF5

H

Me

L’1

3-1301

H

FF6

H

Me

L’1

3-1302

H

FF7

H

Me

L’1

3-1303

H

FF8

H

Me

L’1

3-1304

H

FF9

H

Me

L’1

3-1305

H

FF10

H

Me

L’1

3-1306

H

FF11

H

Me

L’1

3-1307

H

Me

L’3

3-1308

H

Me

L’4

3-1309

H

Me

L’10

3-1310

H

Me

L’12

3-1311

H

F

H

Me

L’18

3-1312

H

Me

L’24

3-1313

H

Me

L’25

3-1314

H

Me

L’26

3-1315

H

Me

L’27

3-1316

H

Me

L’28

3-1317

OH

H

Me

L’2

3-1318

H

PhO

H

cHx

L’5

3-1319

H

CO₂Ph

H

iPr

L’6

3-1320

H

cHx

H

Ph

L’7

3-1321

H

NBu₂

Bu

L’8

[table 91]

Compound (the 3-1334)~compound (3-1376) indicated by formula (3b-C) is illustrated in table 92~93.

[table 92]

[table 93]

Compound

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

R²⁶

L’

3-1365

CO₂Me

H

tBu

Ph

L’9

3-1366

H

tBu

H

Et

Bu

L’11

3-1367

H

CN

H

Me

tBu

L’13

3-1368

H

NO₂

H

cHx

Et

L’14

3-1369

H

CO₂H

iPr

Me

L’15

3-1370

MeO

H

Ph

cHx

L’16

3-1371

H

Me

H

Bu

iPr

L’17

3-1372

H

Br

H

tBu

Ph

L’19

3-1373

H

SO₃H

H

Et

Bu

L’20

3-1374

H

Cl

Me

tBu

L’21

3-1375

CONBu₂

H

cHx

Et

L’22

3-1376

H

SO₂NBu₂

H

iPr

Me

L’23

Compound (the 3-1377)~compound (3-1419) indicated by formula (3c-O) is illustrated in table 94~95.

[table 94]

[table 95]

Compound

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-1408

CO₂Me

H

L’9

3-1409

H

tBu

H

L’11

3-1410

H

CN

H

L’13

3-1411

H

NO₂

H

L’14

3-1412

H

CO₂H

L’15

3-1413

MeO

H

L’16

3-1414

H

Me

H

L’17

3-1415

H

Br

H

L’19

3-1416

H

SO₃H

H

L’20

3-1417

H

Cl

L’21

3-1418

CONBu₂

H

L’22

3-1419

H

SO₂NBu₂

H

L’23

Compound (the 3-1420)~compound (3-1462) indicated by formula (3c-S) is illustrated in table 96~97.

[table 96]

[table 97]

Compound

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-1451

CO₂Me

H

L’9

3-1452

H

tBu

H

L’11

3-1453

H

CN

H

L’13

3-1454

H

NO₂

H

L’14

3-1455

H

CO₂H

L’15

3-1456

MeO

H

L’16

3-1457

H

Me

H

L’17

3-1458

H

Br

H

L’19

3-1459

H

SO₃H

H

L’20

3-1460

H

Cl

L’21

3-1461

CONBu₂

H

L’22

3-1462

H

SO₂NBu₂

H

L’23

Compound (the 3-1463)~compound (3-1505) indicated by formula (3c-N) is illustrated in table 98~99.

[table 98]

Compound

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-1463

H

Me

L’1

3-1464

H

CF₃

H

Me

L’1

3-1465

H

CF₃

Me

L’1

3-1466

H

Ph

H

Me

L’1

3-1467

H

biPh

H

Me

L’1

3-1468

H

FF1

H

Me

L’1

3-1469

H

FF2

H

Me

L’1

3-1470

H

FF3

H

Me

L’1

3-1471

H

FF4

H

Me

L’1

3-1472

H

FF5

H

Me

L’1

3-1473

H

FF6

H

Me

L’1

3-1474

H

FF7

H

Me

L’1

3-1475

H

FF8

H

Me

L’1

3-1476

H

FF9

H

Me

L’1

3-1477

H

FF10

H

Me

L’1

3-1478

H

FF11

H

Me

L’1

3-1479

H

Me

L’3

3-1480

H

Me

L’4

3-1481

H

Me

L’10

3-1482

H

Me

L’12

3-1483

H

F

H

Me

L’18

3-1484

H

Me

L’24

3-1485

H

Me

L’25

3-1486

H

Me

L’26

3-1487

H

Me

L’27

3-1488

H

Me

L’28

3-1489

OH

H

Me

L’2

3-1490

H

PhO

H

cHx

L’5

3-1491

H

CO₂Ph

H

iPr

L’6

3-1492

H

cHx

H

Ph

L’7

3-1493

H

NBu₂

Bu

L’8

[table 99]

Compound

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-1494

CO₂Me

H

tBu

L’9

3-1495

H

tBu

H

Et

L’11

3-1496

H

CN

H

Me

L’13

3-1497

H

NO₂

H

cHx

L’14

3-1498

H

CO₂H

iPr

L’15

3-1499

MeO

H

Ph

L’16

3-1500

H

Me

H

Bu

L’17

3-1501

H

Br

H

tBu

L’19

3-1502

H

SO₃H

H

Et

L’20

3-1503

H

Cl

Me

L’21

3-1504

CONBu₂

H

cHx

L’22

3-1505

H

SO₂NBu₂

H

iPr

L’23

Compound (the 3-1506)~compound (3-1548) indicated by formula (3c-C) is illustrated in table 100~101.

[table 100]

Compound

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

R²⁶

L’

3-1506

H

Me

L’1

3-1507

H

CF₃

H

Me

L’1

3-1508

H

CF₃

Me

L’1

3-1509

H

Ph

H

Me

L’1

3-1510

H

biPh

H

Me

L’1

3-1511

H

FF1

H

Me

L’1

3-1512

H

FF2

H

Me

L’1

3-1513

H

FF3

H

Me

L’1

3-1514

H

FF4

H

Me

L’1

3-1515

H

FF5

H

Me

L’1

3-1516

H

FF6

H

Me

L’1

3-1517

H

FF7

H

Me

L’1

3-1518

H

FF8

H

Me

L’1

3-1519

H

FF9

H

Me

L’1

3-1520

H

FF10

H

Me

L’1

3-1521

H

FF11

H

Me

L’1

3-1522

H

Me

L’3

3-1523

H

Me

L’4

3-1524

H

Me

L’10

3-1525

H

Me

L’12

3-1526

H

F

H

Me

L’18

3-1527

H

Me

L’24

3-1528

H

Me

L’25

3-1529

H

Me

L’26

3-1530

H

Me

L’27

3-1531

H

Me

L’28

3-1532

OH

H

Me

cHx

L’2

3-1533

H

PhO

H

cHx

iPr

L’5

3-1534

H

CO₂Ph

H

iPr

Me

L’6

3-1535

H

cHx

H

Ph

cHx

L’7

3-1536

H

NBu₂

Bu

iPr

L’8

[table 101]

Compound (the 3-1549)~compound (3-1652) indicated by formula (3a-O) is illustrated in table 102~105.

[table 102]

[table 103]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-1579

2EHx

Et

H

CO₂Ph

H

L’8

3-1580

2EHx

Et

H

cHx

H

L’9

3-1581

2EHx

Et

H

NBu₂

L’11

3-1582

2EHx

Et

Br

H

L’13

3-1583

2EHx

Et

H

Cl

H

L’14

3-1584

2EHx

Et

H

CO₂Me

H

L’15

3-1585

2EHx

Et

H

tBu

H

L’16

3-1586

2EHx

Et

H

CN

H

L’17

3-1587

2EHx

Et

H

NO₂

H

L’19

3-1588

2EHx

Et

H

CO₂H

L’20

3-1589

2EHx

Et

SO₂NBu₂

H

L’21

3-1590

2EHx

Et

H

CONBu₂

H

L’22

3-1591

2EHx

Et

H

MeO

H

L’23

3-1592

2EHx

Hex

H

L’1

3-1593

2EHx

Hex

H

CF₃

H

L’1

3-1594

2EHx

Hex

H

CF₃

L’1

3-1595

2EHx

Hex

H

Ph

H

L’1

3-1596

2EHx

Hex

H

biPh

H

L’1

3-1597

2EHx

Hex

H

FF1

H

L’1

3-1598

2EHx

Hex

H

FF2

H

L’1

3-1599

2EHx

Hex

H

FF3

H

L’1

3-1600

2EHx

Hex

H

FF4

H

L’1

3-1601

2EHx

Hex

H

FF5

H

L’1

3-1602

2EHx

Hex

H

FF6

H

L’1

3-1603

2EHx

Hex

H

FF7

H

L’1

3-1604

2EHx

Hex

H

FF8

H

L’1

3-1605

2EHx

Hex

H

FF9

H

L’1

3-1606

2EHx

Hex

H

FF10

H

L’1

3-1607

2EHx

Hex

H

FF11

H

L’1

3-1608

2EHx

Hex

H

L’3

[table 104]

[table 105]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-1639

2NPh

Ph

H

L’29

3-1640

Et

H

CN

H

L’29

3-1641

2EHx

H

L’29

3-1642

2EHx

Et

H

L’29

3-1643

2EHx

Hex

H

L’29

3-1644

Et

H

L’30

3-1645

Bu

H

L’30

3-1646

Ph

H

L’30

3-1647

pTol

H

L’30

3-1648

2NPh

Ph

H

L’30

3-1649

Et

H

CN

H

L’30

3-1650

2EHx

H

L’30

3-1651

2EHx

Et

H

L’30

3-1652

2EHx

Hex

H

L’30

Compound (the 3-1653)~compound (3-1656) indicated by formula (3b-O) is illustrated in table 106.

[table 106]

Compound

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-1653

H

L’29

3-1654

H

CN

H

L’29

3-1655

H

L’30

3-1656

H

CN

H

L’30

Compound (the 3-1657)~compound (3-1660) indicated by formula (3c-O) is illustrated in table 107.

[table 107]

Compound

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-1657

H

L’29

3-1658

H

CN

H

L’29

3-1659

H

L’30

3-1660

H

CN

H

L’30

Compound (the 3-1661)~compound (3-1764) indicated by formula (3a-S) is illustrated in table 108~111.

[table 108]

[table 109]

[table 110]

[table 111]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-1751

2NPh

Ph

H

L’29

3-1752

Et

H

CN

H

L’29

3-1753

2EHx

H

L’29

3-1754

2EHx

Et

H

L’29

3-1755

2EHx

Hex

H

L’29

3-1756

Et

H

L’30

3-1757

Bu

H

L’30

3-1758

Ph

H

L’30

3-1759

pTol

H

L’30

3-1760

2NPh

Ph

H

L’30

3-1761

Et

H

CN

H

L’30

3-1762

2EHx

H

L’30

3-1763

2EHx

Et

H

L’30

3-1764

2EHx

Hex

H

L’30

Compound (the 3-1765)~compound (3-1768) indicated by formula (3b-S) is illustrated in table 112.

[table 112]

Compound

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-1765

H

L’29

3-1766

H

CN

H

L’29

3-1767

H

L’30

3-1768

H

CN

H

L’30

Compound (the 3-1769)~compound (3-1772) indicated by formula (3c-S) is illustrated in table 113.

[table 113]

Compound

R²⁰

R²¹

R²²

R²³

R²⁴

L’

3-1769

H

L’29

3-1770

H

CN

H

L’29

3-1771

H

L’30

3-1772

H

CN

H

L’30

Compound (the 3-1773)~compound (3-1876) indicated by formula (3a-N) is illustrated in table 114~117.

[table 114]

[table 115]

[table 116]

[table 117]

Compound

R¹⁶

R¹⁷

R¹⁸

R¹⁹

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-1863

2NPh

Ph

H

Me

L’29

3-1864

Et

H

CN

H

Me

L’29

3-1865

2EHx

H

Me

L’29

3-1866

2EHx

Et

H

Me

L’29

3-1867

2EHx

Hex

H

Me

L’29

3-1868

Et

H

Me

L’30

3-1869

Bu

H

Me

L’30

3-1870

Ph

H

Me

L’30

3-1871

pTol

H

Me

L’30

3-1872

2NPh

Ph

H

Me

L’30

3-1873

Et

H

CN

H

Me

L’30

3-1874

2EHx

H

Me

L’30

3-1875

2EHx

Et

H

Me

L’30

3-1876

2EHx

Hex

H

Me

L’30

Compound (the 3-1877)~compound (3-1880) indicated by formula (3b-N) is illustrated in table 118.

[table 118]

Compound

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-1877

H

Me

L’29

3-1878

H

CN

H

Me

L’29

3-1879

H

Me

L’30

3-1880

H

CN

H

Me

L’30

Compound (the 3-1881)~compound (3-1884) indicated by formula (3c-N) is illustrated in table 119.

[table 119]

Compound

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

L’

3-1881

H

Me

L’29

3-1882

H

CN

H

Me

L’29

3-1883

H

Me

L’30

3-1884

H

CN

H

Me

L’30

Compound (the 3-1885)~compound (3-1988) indicated by formula (3a-C) is illustrated in table 120~123.

[table 120]

[table 121]

[table 122]

[table 123]

Compound (the 3-1989)~compound (3-1992) indicated by formula (3b-C) is illustrated in table 124.

[table 124]

Compound

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

R²⁶

L’

3-1989

H

Me

L’29

3-1990

H

CN

H

Me

L’29

3-1991

H

Me

L’30

3-1992

H

CN

H

Me

L’30

Compound (the 3-1993)~compound (3-1996) indicated by formula (3c-C) is illustrated in table 125.

[table 125]

Compound

R²⁰

R²¹

R²²

R²³

R²⁴

R²⁵

R²⁶

L’

3-1993

H

Me

L’29

3-1994

H

CN

H

Me

L’29

3-1995

H

Me

L’30

3-1996

H

CN

H

Me

L’30

From raw material it is chiral from the viewpoint of, preferred compound (3-1), compound (3-44), compound (3-87), compound (3-130), compound (3-173), compound (3-216), compound (3-259), compound (3-302), compound (3- 345), compound (3-388), compound (3-431), compound (3-474), compound (3-517), compound (3-560), change Close object (3-603), compound (3-646), compound (3-689), compound (3-732), compound (3-775), compound (3- 818), compound (3-861), compound (3-904), compound (3-947), compound (3-990), compound (3-1033), Compound (3-1076), compound (3-1162), compound (3-1205), compound (3-1248), is changed compound (3-1119) Close object (3-1291), compound (3-1334), compound (3-1377), compound (3-1420), compound (3-1463), chemical combination Object (3-1506), compound (3-1549) and compound (3-1592).Wherein, more preferable compound (3-1), compound (3- 44), compound (3-87), compound (3-130), compound (3-173), compound (3-216), compound (3-259), chemical combination Object (3-1205), compound (3-1377), compound (3-1549) and compound (3-1592), further preferred compound (3-1), compound (3-44), compound (3-259), compound (3-1205), compound (3-1377), compound (3-1549) And compound (3-1592).

Compound (4) or compound (5) are indicated by formula (4) or formula (5), also include its tautomer or their salt.

In formula (4) and formula (5), X " indicates the 16th race's atom ,-N (R in the periodic table of elements³⁴)-or-C (R³⁴) (R³⁵)-.As the 16th race's atom in the periodic table of elements, for example there are oxygen atom, sulphur atom, selenium atom, tellurium atoms.From light characteristic Or it is easy to manufacture from the aspect of, as X ", preferably oxygen atom, sulphur atom ,-N (R³⁴)-or-C (R³⁴)(R³⁵The more preferable oxygen in)-, wherein Atom.

In formula (4) and formula (5), as R²⁸~R⁴¹In halogen atom for example there are fluorine atom, chlorine atom, bromine atom, iodine are former Son.

In formula (4) and formula (5), as R²⁸~R³²In carbon atom number 1~20 1 valency alkyl, for example there are for example

Methyl, ethyl, propyl, isopropyl, isopropenyl, 1- acrylic, 2- acrylic, butyl, isobutyl group, sec-butyl, Tert-butyl, 2- cyclobutenyl, 1,3-butadiene base, amyl, isopentyl, 3- amyl, neopentyl, tertiary pentyl, 1- methyl amyl, 2- first Base amyl, 2- pentenyl, hexyl, isohesyl, 5- methylhexyl, (2- ethyl) hexyl, heptyl, octyl, nonyl, decyl, 11 Aliphatic alkyl until the carbon atom numbers such as alkyl, dodecyl, octadecyl 20；

The alicyclic alkyls such as cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cyclohexenyl group, suberyl；

Phenyl, o-tolyl, tolyl, p-methylphenyl, xylyl, mesitylene base, adjacent cumenyl, isopropyl Phenyl, to aromatic hydrocarbyls such as cumenyl, benzyl, phenethyl, xenyl, 1- naphthalene, 2- naphthalenes.

As constitute these 1 valency alkyls methylene by oxygen atom, sulphur atom ,-N (R⁴²)-, sulfonyl or carbonyl replace after Hydrogen atom contained by obtained group or 1 valency alkyl is by halogen atom, cyano, nitro, carbamoyl, sulfamoyl, sulphur The group that base, carboxyl, hydroxyl, imidazoles -1- base or amino obtain after replacing, for example there are for example

Methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, penta oxygen The alkoxies such as base, phenoxy group, benzyloxy；

The acyloxy such as acetoxyl group, benzoyloxy；

And the group being composed of them.

As R²⁸And R²⁹, preferred aliphat alkyl, alicyclic alkyl or aromatic hydrocarbyl.

R²⁸And R²⁹In aliphatic alkyl contained by hydrogen atom can be replaced by alicyclic alkyl or aromatic hydrocarbyl.

R²⁸And R²⁹In alicyclic alkyl contained by hydrogen atom can be by aliphatic alkyl, alicyclic alkyl or fragrance Race's alkyl replaces.

R²⁸And R²⁹In aromatic hydrocarbyl contained by hydrogen atom can be by aliphatic alkyl, alicyclic alkyl or fragrance Race's alkyl replaces.

Consider from easy manufacture view, R³²It is preferred that hydrogen atom, hydroxyl, alkoxy, alkoxy carbonyl or acyloxy.

As R³³, preferably for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl group, sec-butyl, tert-butyl, amyl, The aliphatic alkyl of the carbon atom numbers such as isopentyl, neopentyl, tertiary pentyl 1~6；Methoxyl group, ethyoxyl, propoxyl group, isopropoxy, The ethers such as butoxy, isobutoxy, tert-butoxy, amoxy, phenoxy group, benzyloxy；Methoxycarbonyl, ethoxy carbonyl, third The ester groups such as Epoxide carbonyl, acetoxyl group, benzoyloxy or cyano.

As R³⁴~R³⁵, preferred aliphat alkyl, alicyclic alkyl, aromatic hydrocarbyl or the hydrocarbon being composed of them Base.

R³⁶~R⁴¹In any one be-SO₃M".M " indicates alkali metal atom, preferably sodium atom or potassium atom.

As compound (4), for example there are such as 126~table of table, 145 compound represented and their salt.In each table, " cHx " indicates that cyclohexyl, " pTol " indicate that p-methylphenyl, " 2EHx " indicate that 2- ethylhexyl, " 2NPh " indicate 2- naphthalene, " tBu " indicates that tert-butyl, " iPr " indicate isopropyl.

Compound (the 4-1)~compound (4-70) indicated by formula (4a-O) is illustrated in 126~table of table 128.

[table 126]

Compound

R²⁸

R²⁹

R³⁰

R³¹

R³²

R³³

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

4-1

Et

H

SO₃H

H

4-2

Et

H

SO₃H

H

4-3

Et

H

SO₃H

H

4-4

Et

H

SO₃H

H

4-5

Et

H

SO₃H

H

4-6

Et

H

SO₃H

4-7

Et

H

SO₃H

H

SO₃H

H

4-8

Bu

H

SO₃H

H

4-9

Bu

H

SO₃H

H

4-10

Bu

H

SO₃H

H

4-11

Bu

H

SO₃H

H

4-12

Bu

H

SO₃H

H

4-13

Bu

H

SO₃H

4-14

Bu

H

SO₃H

H

SO₃H

H

4-15

Ph

H

SO₃H

H

4-16

Ph

H

SO₃H

H

4-17

Ph

H

SO₃H

H

4-18

Ph

H

SO₃H

H

4-19

Ph

H

SO₃H

H

4-20

Ph

H

SO₃H

4-21

Ph

H

SO₃H

H

SO₃H

H

4-22

pTol

H

SO₃H

H

4-23

pTol

H

SO₃H

H

4-24

pTol

H

SO₃H

H

4-25

pTol

H

SO₃H

H

4-26

pTol

H

SO₃H

H

4-27

pTol

H

SO₃H

4-28

pTol

H

SO₃H

H

SO₃H

H

4-29

2NPh

Ph

H

SO₃H

H

4-30

2NPh

Ph

H

SO₃H

H

[table 127]

[table 128]

Compound

R²⁸

R²⁹

R³⁰

R³¹

R³²

R³³

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

4-61

Bu

2NPh

H

SO₃H

MeO

H

PhO

H

SO₃H

H

4-62

Ph

Et

H

NBu₂

H

CO₂Ph

H

SO₃H

4-63

pTol

Ph

H

NO₂

H

SO₃H

H

SO₃H

Me

4-64

2NPh

pTol

H

Br

SO₃H

H

Et

H

4-65

Et

Bu

H

SO₂NBu₂

H

SO₃H

H

4Pr

H

4-66

2EHx

Et

H

Cl

H

cHx

SO₃H

H

4-67

Bu

2NPh

H

CONBu₂

SO₃Na

H

SO₃H

H

4-68

Ph

Et

SO₃H

H

CN

F

H

SO₃H

H

4-69

pTol

Ph

H

MeO

H

CO₂H

H

SO₃H

4-70

2NPh

pTol

F

H

CN

H

SO₃H

H

SO₃H

H

Compound (the 4-71)~compound (4-140) indicated by formula (4a-S) is illustrated in 129~table of table 131.

[table 129]

[table 130]

[table 131]

Compound

R²⁸

R²⁹

R³⁰

R³¹

R³²

R³³

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

4-131

Bu

2NPh

H

SO₃H

MeO

H

PhO

H

SO₃H

H

4-132

Ph

Et

H

NBu₂

H

CO₂Ph

H

SO₃H

4-133

pTol

Ph

H

NO₂

H

SO₃H

H

SO₃H

Me

4-134

2NPh

pTol

H

Br

SO₃H

H

Et

H

4-135

Et

Bu

H

SO₂NBu₂

H

SO₃H

H

4Pr

H

4-136

2EHx

Et

H

Cl

H

cHx

SO₃H

H

4-137

Bu

2NPh

H

CONBu₂

SO₃H

H

SO₃H

H

4-138

Ph

Et

SO₃H

H

CN

F

H

SO₃H

H

4-139

pTol

Ph

H

MeO

H

CO₂H

H

SO₃Na

4-140

2NPh

pTol

F

H

CN

H

SO₃H

H

SO₃H

H

Compound (the 4-141)~compound (4-210) indicated by formula (4a-N) is illustrated in 132~table of table 134.

[table 132]

[table 133]

Compound

R²⁸

R²⁹

R³⁰

R³¹

R³²

R³³

R³⁴

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

4-171

2NPh

Ph

H

4Pr

H

SO₃H

H

4-172

2NPh

Ph

H

Ph

H

S_OH

H

4-173

2NPh

Ph

H

Bu

H

SO₃H

H

4-174

2NPh

Ph

H

tBu

H

SO₃H

4-175

2NPh

Ph

H

Et

H

SO₃H

H

SO₃H

H

4-176

Et

H

CN

Me

SO₃H

H

4-177

Et

H

CN

cHx

H

SO₃H

H

4-178

Et

H

CN

4Pr

H

SO₃H

H

4-179

Et

H

CN

Ph

H

SO₃H

H

4-180

Et

H

CN

Bu

H

SO₃H

H

4-181

Et

H

CN

tBu

H

SO₃H

4-182

Et

H

CN

Et

H

SO₃H

H

SO₃H

H

4-183

2EHx

H

Me

SO₃H

H

4-184

2EHx

H

cHx

H

SO₃H

H

4-185

2EHx

H

4Pr

H

SO₃H

H

4-186

2EHx

H

Ph

H

SO₃H

H

4-187

2EHx

H

Bu

H

SO₃H

H

4-188

2EHx

H

tBu

H

SO₃H

4-189

2FHx

2EHx

H

Et

H

SO₃H

H

SO₃H

H

4-190

Ph

Et

H

Ph

tBu

SO₃H

H

OH

H

4-191

pTol

Ph

H

CO₂Ph

Et

H

SO₃H

H

NBu₂

H

4-192

2NPh

pTol

H

PhO

Me

H

tBu

SO₃H

H

4-193

Et

Bu

H

4Pr

cHx

CO₂H

H

SO₃H

H

4-194

2EHx

Et

H

CO₂Me

SO₃H

4Pr

H

SO₃H

H

4-195

Bu

2NPh

H

NO₂

H

Me

Ph

H

SO₃H

4-196

Ph

Et

CONBu₂

H

Et

Bu

H

SO₃H

H

SO₃H

H

4-197

pTol

Ph

H

SO₂NBu₂

H

CO₂Me

Bu

SO₃H

H

4-198

2NPh

pTol

H

Cl

tBu

H

SO₃H

H

4-199

Et

Bu

H

cHx

Et

Br

H

SO₃H

H

4-200

2EHx

Et

H

OH

Me

H

Ph

H

SO₃H

H

[table 134]

Compound (the 4-211)~compound (4-280) indicated by formula (4a-C) is illustrated in 135~table of table 137.

[table 135]

Compound

R²⁸

R²⁹

R³⁰

R³¹

R³²

R³³

R³⁴

R³⁵

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

4-211

Et

H

Me

SO₃H

H

4-212

Et

H

cHx

H

SO₃H

H

4-213

Et

H

4Pr

H

SO₃H

H

4-214

Et

H

Ph

H

SO₃H

H

4-215

Et

H

Bu

H

SO₃H

H

4-216

Et

H

tBu

H

SO₃H

4-217

Et

H

Et

H

SO₃H

H

SO₃H

H

4-218

Bu

H

Me

SO₃H

H

4-219

Bu

H

cHx

H

SO₃H

H

4-220

Bu

H

4Pr

H

SO₃H

H

4-221

Bu

H

Ph

H

SO₃H

H

4-222

Bu

H

Bu

H

SO₃H

H

4-223

Bu

H

tBu

H

SO₃H

4-224

Bu

H

Et

H

SO₃H

H

SO₃H

H

4-225

Ph

H

Me

SO₃H

H

4-226

Ph

H

cHx

H

SO₃H

H

4-227

Ph

H

4Pr

H

SO₃H

H

4-228

Ph

H

Ph

H

SO₃H

H

4-229

Ph

H

Bu

H

SO₃H

H

4-230

Ph

H

tBu

H

SO₃H

4-231

Ph

H

Et

H

SO₃H

H

SO₃H

H

4-232

pTol

H

Me

SO₃H

H

4-233

pTol

H

cHx

H

SO₃H

H

4-234

pTol

H

4Pr

H

SO₃H

H

4-235

pTol

H

Ph

H

SO₃H

H

4-236

pTol

H

Bu

H

SO₃H

H

4-237

pTol

H

tBu

H

SO₃H

4-238

pTol

H

Et

H

SO₃H

H

SO₃H

H

4-239

2NPh

Ph

H

Me

SO₃H

H

4-240

2NPh

Ph

H

cHx

H

SO₃H

H

[table 136]

Compound

R²⁸

R²⁹

R³⁰

R³¹

R³²

R³³

R³⁴

R³⁵

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

4-241

2NPh

Ph

H

4Pr

H

SO₃H

H

4-242

2NPh

Ph

H

Ph

H

SO₃H

H

4-243

2NPh

Ph

H

Bu

H

SO₃H

H

4-244

2NPh

Ph

H

tBu

H

SO₃H

4-245

2NPh

Ph

H

Et

H

SO₃H

H

SO₃H

H

4-246

Et

H

CN

Me

SO₃H

H

4-247

Et

H

CN

cHx

H

SO₃H

H

4-248

Et

H

CN

4Pr

H

SO₃H

H

4-249

Et

H

CN

Ph

H

SO₃H

H

4-250

Et

H

CN

Bu

H

SO₃H

H

4-251

Et

H

CN

tBu

H

SO₃H

4-252

Et

H

CN

Et

H

SO₃H

H

SO₃H

H

4-253

2EHx

2FHx

H

Me

MHe

SO₃H

H

4-254

2EHx

H

cHx

H

SO₃H

H

4-255

2EHx

H

4Pr

H

SO₃H

H

4-256

2EHx

H

Ph

H

SO₃H

H

4-257

2EHx

H

Bu

H

SO₃H

H

4-258

2EHx

H

tBu

H

SO₃H

4-259

2EHx

H

Et

H

SO₃H

H

SO₃H

H

4-260

Ph

Et

H

Ph

tBu

Bu

SO₃H

H

OH

H

4-261

pTol

Ph

H

CO₂Ph

Et

tBu

H

SO₃H

H

NBu₂

H

4-262

2NPh

pTol

H

PhO

Me

tBu

H

tBu

SO₃H

H

4-263

Et

Bu

H

4Pr

cHx

Et

CO₂H

H

SO₃H

H

4-264

2EHx

Et

H

CO₂Me

SO₃H

4Pr

Me

H

SO₃H

H

4-265

Bu

2NPh

H

NO₂

H

Me

Ph

cHx

H

SO₃H

4-266

Ph

Et

CONBu₂

H

Et

Bu

4Pr

H

SO₃H

H

SO₃H

H

4-267

pTol

Ph

H

SO₂NBu₂

H

CO₂Me

Bu

Ph

SO₃H

H

4-268

2NPh

pTol

H

Cl

tBu

Bu

H

SO₃H

H

4-269

Et

Bu

H

cHx

Et

Bu

Br

H

SO₃H

H

4-270

2EHx

Et

H

OH

Me

tBu

H

Ph

H

SO₃H

H

[table 137]

Compound

R²⁸

R²⁹

R³⁰

R³¹

R³²

R³³

R³⁴

R³⁵

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

4-271

Bu

2NPh

H

SO₃H

MeO

cHx

Et

H

PhO

H

SO₃H

H

4-272

Ph

Et

H

NBu₂

4-Pr

Me

H

CO₂Ph

H

SO₃H

4-273

pTol

Ph

H

NO₂

Ph

cHx

H

SO₃H

H

SO₃H

Me

4-274

2NPh

pTol

H

Br

Et

4-Pr

SO₃H

H

Et

H

4-275

Et

Bu

H

SO₂NBu₂

Me

Ph

H

SO₃H

H

4-Pr

H

4-276

2EHx

Et

H

Cl

cHx

Et

H

cHx

SO₃Na

H

4-277

Bu

2NPh

H

CONBu₂

4-Pr

Me

SO₃H

H

SO₃H

H

4-278

Ph

Et

SO₃H

H

CN

F

Ph

cHx

H

SO₃H

H

4-279

pTol

Ph

H

MeO

H

CO₂H

Bu

4-Pr

H

SO₃H

4-280

2NPh

pTol

F

H

CN

tBu

Ph

H

SO₃H

H

SO₃H

H

Compound (the 4-281)~compound (4-308) indicated by formula (4b-O) is illustrated in table 138.

[table 138]

Compound (the 4-309)~compound (4-336) indicated by formula (4b-S) is illustrated in table 139.

[table 139]

Compound (the 4-337)~compound (4-364) indicated by formula (4b-N) is illustrated in table 140.

[table 140]

Compound (the 4-365)~compound (4-392) indicated by formula (4b-C) is illustrated in table 141.

[table 141]

Compound (the 4-393)~compound (4-420) indicated by formula (4c-O) is illustrated in table 142.

[table 142]

Compound (the 4-421)~compound (4-448) indicated by formula (4c-S) is illustrated in table 143.

[table 143]

Compound (the 4-449)~compound (4-476) indicated by formula (4c-N) is illustrated in table 144.

[table 144]

Compound (the 4-477)~compound (4-504) indicated by formula (4c-C) is illustrated in table 145.

[table 145]

Compound

R³²

R³³

R³⁴

R³⁵

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

4-477

H

Me

SO₃H

H

4-478

H

cHx

H

SO₃H

H

4-479

H

4Pr

H

SO₃H

H

4-480

H

Ph

H

SO₃H

H

4-481

H

Bu

H

SO₃H

H

4-482

H

tBu

H

SO₃H

4-483

H

Et

H

SO₃H

H

SO₃H

H

4-484

H

Ph

tBu

Bu

SO₃H

H

OH

H

4-485

H

CO₂Ph

Et

tBu

H

SO₃H

H

NBu₂

H

4-486

H

PhO

Me

tBu

H

SO₃H

tBu

H

4-487

H

4Pr

cHx

Et

CO₂H

H

SO₃H

H

4-488

CO₂Me

SO₃H

4Pr

Me

H

SO₃H

H

4-489

H

Me

Ph

cHx

H

NO₂

H

SO₃H

4-490

H

Et

Bu

4Pr

H

CONBu₂

SO₃H

H

SO₃H

H

4-491

H

CO₂Me

Bu

Ph

SO₃H

H

SO₂NBu₂

H

4-492

H

tBu

Bu

H

SO₃H

H

Cl

4-493

H

cHx

Et

Bu

H

SO₃H

H

Br

H

4-494

H

OH

Me

tBu

H

SO₃H

H

Ph

4-495

H

MeO

cHx

Et

H

PhO

H

SO₃H

H

4-496

H

NBu₂

4Pr

Me

H

CO₂Ph

H

SO₃H

4-497

H

NO₂

Ph

cHx

Me

H

SO₃H

H

SO₃H

H

4-498

Et

Br

Et

4Pr

SO₃H

H

4-499

H

SO₂NBu₂

Me

Ph

H

SO₃Na

H

4Pr

H

4-500

H

Cl

cHx

Et

H

SO₃H

H

cHx

4-501

SO₃H

CONBu₂

4Pr

Me

H

SO₃H

H

4-502

H

F

Ph

cHx

CN

H

SO₃H

H

4-503

H

CO₂H

Bu

4Pr

H

MeO

H

SO₃H

4-504

F

CN

tBu

Ph

H

SO₃H

H

SO₃H

H

As compound (5), for example there are such as 146~table of table, 165 compound represented and their salt.In each table,

" cHx " indicates that cyclohexyl, " pTol " indicate that p-methylphenyl, " 2EHx " indicate that 2- ethylhexyl, " 2NPh " indicate 2- naphthalene, " tBu " indicate that tert-butyl, " iPr " indicate isopropyl.

Compound (the 5-1)~compound (5-70) indicated by formula (5a-O) is illustrated in 146~table of table 148.

[table 146]

Compound

R²⁸

R²⁹

R³⁰

R³¹

R³²

R³³

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

5-1

Et

H

SO₃H

H

5-2

Et

H

SO₃H

H

5-3

Et

H

SO₃H

H

5-4

Et

H

SO₃H

H

5-5

Et

H

SO₃H

H

5-6

Et

H

SO₃H

5-7

Et

H

SO₃H

H

SO₃H

H

5-8

Bu

H

SO₃H

H

5-9

Bu

H

SO₃H

H

5-10

Bu

H

SO₃H

H

5-11

Bu

H

SO₃H

H

5-12

Bu

H

SO₃H

H

5-13

Bu

H

SO₃H

5-14

Bu

H

SO₃H

H

SO₃H

H

5-15

Ph

H

SO₃H

H

5-16

Ph

H

SO₃H

H

5-17

Ph

H

SO₃H

H

5-18

Ph

H

SO₃H

H

5-19

Ph

H

SO₃H

H

5-20

Ph

H

SO₃H

5-21

Ph

H

SO₃H

H

SO₃H

H

5-22

pTol

H

SO₃H

H

5-23

pTol

H

SO₃H

H

5-24

pTol

H

SO₃H

H

5-25

pTol

H

SO₃H

H

5-26

pTol

H

SO₃H

H

5-27

pTol

H

SO₃H

5-28

pTol

H

SO₃H

H

SO₃H

H

5-29

2NPh

Ph

H

SO₃H

H

5-30

2NPh

Ph

H

SO₃H

H

[table 147]

[table 148]

Compound

R²⁸

R²⁹

R³⁰

R³¹

R³²

R³³

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

5-61

Bu

2NPh

H

SO₃H

MeO

H

PhO

H

SO₃H

H

5-62

Ph

Et

H

NBu₂

H

CO₂Ph

H

SO₃H

5-63

pTol

Ph

H

NO₂

H

SO₃H

H

SO₃H

Me

5-64

2NPh

pTol

H

Br

SO₃H

H

Et

H

5-65

Et

Bu

H

SO₂NBu₂

H

SO₃H

H

iPr

H

5-66

2EHx

Et

H

Cl

H

cHx

SO₃Na

H

5-67

Bu

2NPh

H

CONBu₂

SO₃H

H

SO₃H

H

5-68

Ph

Et

SO₃H

H

CN

F

H

SO₃H

H

5-69

pTol

Ph

H

MeO

H

CO₂H

H

SO₃H

5-70

2NPh

pTol

F

H

CN

H

SO₃H

H

SO₃H

H

Compound (the 5-71)~compound (5-140) indicated by formula (5a-S) is illustrated in 149~table of table 151.

[table 149]

Compound

R²⁸

R²⁹

R³⁰

R³¹

R³²

R³³

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

5-71

Et

H

SO₃H

H

5-72

Et

H

SO₃H

H

5-73

Et

H

SO₃H

H

5-74

Et

H

SO₃H

H

5-75

Et

H

SO₃H

H

5-76

Et

H

SO₃H

5-77

Et

H

SO₃H

H

SO₃H

H

5-78

Bu

H

SO₃H

H

5-79

Bu

H

SO₃H

H

5-80

Bu

H

SO₃H

H

5-81

Bu

H

SO₃H

H

5-82

Bu

H

SO₃H

H

5-83

Bu

H

SO₃H

5-84

Bu

H

SO₃H

H

SO₃H

H

5-85

Ph

H

SO₃H

H

5-86

Ph

H

SO₃H

H

5-87

Ph

H

SO₃H

H

5-88

Ph

H

SO₃H

H

5-89

Ph

H

SO₃H

H

5-90

Ph

H

SO₃H

5-91

Ph

H

SO₃H

H

SO₃H

H

5-92

pTol

H

SO₃H

H

5-93

pTol

H

SO₃H

H

5-94

pTol

H

SO₃H

H

5-95

pTol

H

SO₃H

H

5-96

pTol

H

SO₃H

H

5-97

pTol

H

SO₃H

5-98

pTol

H

SO₃H

H

SO₃H

H

5-99

2NPh

Ph

H

SO₃H

H

5-100

2NPh

Ph

H

SO₃H

H

[table 150]

[table 151]

Compound

R²⁸

R²⁹

R³⁰

R³¹

R³²

R³³

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

5-131

Bu

2NPh

H

SO₃H

MeO

H

PhO

H

SO₃H

H

5-132

Ph

Et

H

NBu₂

H

CO₂Ph

H

SO₃H

5-133

pTol

Ph

H

NO₂

H

SO₃H

H

SO₃H

Me

5-134

2NPh

pTol

H

Br

SO₃H

H

Et

H

5-135

Et

Bu

H

SO₂NBu₂

H

SO₃H

H

iPr

H

5-136

2EHx

Et

H

Cl

H

cHx

SO₃H

H

5-137

Bu

2NPh

H

CONBu₂

SO₃H

H

SO₃Na

H

5-138

Ph

Et

SO₃H

H

CN

F

H

SO₃H

H

5-139

pTol

Ph

H

MeO

H

CO₂H

H

SO₃H

5-140

2NPh

pTol

F

H

CN

H

SO₃H

H

SO₃H

H

Compound (the 5-141)~compound (5-210) indicated by formula (5a-N) is illustrated in 152~table of table 154.

[table 152]

Compound

R²⁸

R²⁹

R³⁰

R³¹

R³²

R³³

R³⁴

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

5-141

Et

H

Me

SO₃H

H

5-142

Et

H

cHx

H

SO₃H

H

5-143

Et

H

iPr

H

SO₃H

H

5-144

Et

H

Ph

H

SO₃H

H

5-145

Et

H

Bu

H

SO₃H

H

5-146

Et

H

tBu

H

SO₃H

5-147

Et

H

Et

H

SO₃H

H

SO₃H

H

5-148

Bu

H

Me

SO₃H

H

5-149

Bu

H

cHx

H

SO₃H

H

5-150

Bu

H

iPr

H

SO₃H

H

5-151

Bu

H

Ph

H

SO₃H

H

5-152

Bu

H

Bu

H

SO₃H

H

5-153

Bu

H

tBu

H

SO₃H

5-154

Bu

H

Et

H

SO₃H

H

SO₃H

H

5-155

Ph

H

Me

SO₃H

H

5-156

Ph

H

cHx

H

SO₃H

H

5-157

Ph

H

iPr

H

SO₃H

H

5-158

Ph

H

Ph

H

SO₃H

H

5-159

Ph

H

Bu

H

SO₃H

H

5-160

Ph

H

tBu

H

SO₃H

5-161

Ph

H

Et

H

SO₃H

H

SO₃H

H

5-162

pTol

H

Me

SO₃H

H

5-163

pTol

H

cHx

H

SO₃H

H

5-164

pTol

H

iPr

H

SO₃H

H

5-165

pTol

H

Ph

H

SO₃H

H

5-166

pTol

H

Bu

H

SO₃H

H

5-167

pTol

H

tBu

H

SO₃H

5-168

pTol

H

Et

H

SO₃H

H

SO₃H

H

5-169

2NPh

Ph

H

Me

SO₃H

H

5-170

2NPh

Ph

H

cHx

H

SO₃H

H

[table 153]

[table 154]

Compound

R²⁸

R²⁹

R³⁰

R³¹

R³²

R³³

R³⁴

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

5-201

Bu

2NPh

H

SO₃H

MeO

cHx

H

PhO

H

SO₃H

H

5-202

Ph

Et

H

NBu₂

iPr

H

CO₂Ph

H

SO₃H

5-203

pTol

Ph

H

NO₂

Ph

H

SO₃H

H

SO₃H

Me

5-204

2NPh

pTol

H

Br

Et

SO₃H

H

Et

H

5-205

Et

Bu

H

SO₂NBu₂

Me

H

SO₃H

H

iPr

H

5-206

2EHx

Et

H

Cl

cHx

H

cHx

SO₃H

H

5-207

Bu

2NPh

H

CONBu₂

iPr

SO₃H

H

SO₃H

H

5-208

Ph

Et

SO₃H

H

CN

F

Ph

H

SO₃Na

H

5-209

pTol

Ph

H

MeO

H

CO₂H

Bu

H

SO₃H

5-210

2NPh

pTol

F

H

CN

tBu

H

SO₃H

H

SO₃H

H

Compound (5-211)~compound (5-280 indicated by formula (5a-C) is illustrated in 155~table of table 157.

[table 155]

[table 156]

Compound

R²⁸

R²⁹

R³⁰

R³¹

R³²

R³³

R³⁴

R³⁵

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

5-241

2NPh

Ph

H

iPr

H

SO₃H

H

5-242

2NPh

Ph

H

Ph

H

SO₃H

H

5-243

2NPh

Ph

H

Bu

H

SO₃H

H

5-244

2NPh

Ph

H

tBu

H

SO₃H

5-245

2NPh

Ph

H

Et

H

SO₃H

H

SO₃H

H

5-246

Et

H

CN

Me

SO₃H

H

5-247

Et

H

CN

cHx

H

SO₃H

H

5-248

Et

H

CN

iPr

H

SO₃H

H

5-249

Et

H

CN

Ph

H

SO₃H

H

5-250

Et

H

CN

Bu

H

SO₃H

H

5-251

Et

H

CN

tBu

H

SO₃H

5-252

Et

H

CN

Et

H

SO₃H

H

SO₃H

H

5-253

2EHx

H

Me

SO₃H

H

5-254

2EHx

H

cHx

H

SO₃H

H

5-255

2EHx

H

iPr

H

SO₃H

H

5-256

2EHx

H

Ph

H

SO₃H

H

5-257

2EHx

H

Bu

H

SO₃H

H

5-258

2EHx

H

tBu

H

SO₃H

5-259

2EHx

H

Et

H

SO₃H

H

SO₃H

H

5-260

Ph

Et

H

Ph

tBu

Bu

SO₃H

H

OH

H

5-261

pTol

Ph

H

CO₂Ph

Et

tBu

H

SO₃H

H

NBu₂

H

5-262

2NPh

pTol

H

PhO

Me

tBu

H

tBu

SO₃H

H

5-263

Et

Bu

H

iPr

cHx

Et

CO₂H

H

SO₃H

H

5-264

2EHx

Et

H

CO₂Me

SO₃H

iPr

Me

H

SO₃H

H

5-265

Bu

2NPh

H

NO₂

H

Me

Ph

cHx

H

SO₃H

5-266

Ph

Et

CONBu₂

H

Et

Bu

iPr

H

SO₃H

H

SO₃H

H

5-267

pTol

Ph

H

SO₂NBu₂

H

CO₂Me

Bu

Ph

SO₃H

H

5-268

2NPh

pTol

H

Cl

tBu

Bu

H

SO₃H

H

5-269

Et

Bu

H

cHx

Et

Bu

Br

H

SO₃H

H

5-270

2EHx

Et

H

OH

Me

tBu

H

Ph

H

SO₃H

H

[table 157]

Compound (the 5-281)~compound (5-308) indicated by formula (5b-O) is illustrated in table 158.

[table 158]

Compound

R³²

R³³

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

5-281

H

SO₃H

H

5-282

H

SO₃H

H

5-283

H

SO₃H

H

5-284

H

SO₃H

H

5-285

H

SO₃H

H

5-286

H

SO₃H

5-287

H

SO₃H

H

SO₃H

H

5-288

H

Ph

SO₃H

H

OH

H

5-289

H

CO₂Ph

H

SO₃H

H

NBu₂

H

5-290

H

PhO

H

SO₃H

tBu

H

5-291

H

iPr

CO₂H

H

SO₃H

H

5-292

CO₂Me

SO₃H

H

SO₃H

H

5-293

H

Me

H

NO₂

H

SO₃H

5-294

H

Et

H

CONBu₂

SO₃H

H

SO₃H

H

5-295

H

CO₂Me

SO₃H

H

SO₂NBu₂

H

5-296

H

tBu

H

SO₃H

H

Cl

5-297

H

cHx

H

SO₃H

H

Br

H

5-298

H

OH

H

SO₃H

H

Ph

5-299

H

MeO

H

PhO

H

SO₃H

H

5-300

H

NBu₂

H

CO₂Ph

H

SO₃H

5-301

H

NO₂

Me

H

SO₃H

H

SO₃H

H

5-302

Et

Br

SO₃Na

H

5-303

H

SO₂NBu₂

H

SO₃H

H

iPr

H

5-304

H

Cl

H

SO₃H

H

cHx

5-305

SO3H

CONBu₂

H

SO₃H

H

5-306

H

F

CN

H

SO₃H

H

5-307

H

CO₂H

H

MeO

H

SO₃H

5-308

F

CN

H

SO₃H

H

SO₃H

H

Compound (the 5-309)~compound (5-336) indicated by formula (5b-S) is illustrated in table 159.

[table 159]

Compound

R³²

R³³

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

5-309

H

SO₃H

H

5-310

H

SO₃H

H

5-311

H

SO₃H

H

5-312

H

SO₃H

H

5-313

H

SO₃H

H

5-314

H

SO₃H

5-315

H

SO₃H

H

SO₃H

H

5-316

H

Ph

SO₃H

H

OH

H

5-317

H

CO₂Ph

H

SO₃H

H

NBu₂

H

5-318

H

PhO

H

SO₃H

tBu

H

5-319

H

iPr

CO₂H

H

SO₃H

H

5-320

CO₂Me

SO₃H

H

SO₃H

H

5-321

H

Me

H

NO₂

H

SO₃H

5-322

H

Et

H

CONBu₂

SO₃H

H

SO₃H

H

5-323

H

CO₂Me

SO₃H

H

SO₂NBu₂

H

5-324

H

tBu

H

SO₃H

H

Cl

5-325

H

cHx

H

SO₃H

H

Br

H

5-326

H

OH

H

SO₃H

H

Ph

5-327

H

MeO

H

PhO

H

SO₃H

H

5-328

H

NBu₂

H

CO₂Ph

H

SO₃H

5-329

H

NO₂

Me

H

SO₃H

H

SO₃H

H

5-330

Et

Br

SO₃H

H

5-331

H

SO₂NBu₂

H

SO₃Na

H

iPr

H

5-332

H

Cl

H

SO₃H

H

cHx

5-333

SO₃H

CONBu₂

H

SO₃H

H

5-334

H

F

CN

H

SO₃H

H

5-335

H

CO₂H

H

MeO

H

SO₃H

5-336

F

CN

H

SO₃H

H

SO₃H

H

Compound (the 5-337)~compound (5-364) indicated by formula (5b-N) is illustrated in table 160.

[table 160]

Compound

R³²

R³³

R³⁴

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

5-337

H

Me

SO₃H

H

5-338

H

cHx

H

SO₃H

H

5-339

H

iPr

H

SO₃H

H

5-340

H

Ph

H

SO₃H

H

5-341

H

Bu

H

SO₃H

H

5-342

H

tBu

H

SO₃H

5-343

H

Et

H

SO₃H

H

SO₃H

H

5-344

H

Ph

tBu

SO₃H

H

OH

H

5-345

H

CO₂Ph

Et

H

SO₃H

H

NBu₂

H

5-346

H

PhO

Me

H

SO₃H

tBu

H

5-347

H

iPr

cHx

CO₂H

H

SO₃H

H

5-348

CO₂Me

SO₃H

iPr

H

SO₃H

H

5-349

H

Me

Ph

H

NO₂

H

SO₃H

5-350

H

Et

Bu

H

CONBu₂

SO₃H

H

SO₃H

H

5-351

H

CO₂Me

Bu

SO₃H

H

SO₂NBu₂

H

5-352

H

tBu

H

SO₃H

H

Cl

5-353

H

cHx

Et

H

SO₃H

H

Br

H

5-354

H

OH

Me

H

SO₃H

H

Ph

5-355

H

MeO

cHx

H

PhO

H

SO₃H

H

5-356

H

NBu₂

iPr

H

CO₂Ph

H

SO₃H

5-357

H

NO₂

Ph

Me

H

SO₃H

H

SO₃H

H

5-358

Et

Br

Et

SO₃H

H

5-359

H

SO₂NBu₂

Me

H

SO₃H

H

iPr

H

5-360

H

Cl

cHx

H

SO₃Na

H

cHx

5-361

SO₃H

CONBu₂

iPr

H

SO₃H

H

5-362

H

F

Ph

CN

H

SO₃H

H

5-363

H

CO₂H

Bu

H

MeO

H

SO₃H

5-364

F

CN

tBu

H

SO₃H

H

SO₃H

H

Compound (the 5-365)~compound (5-392) indicated by formula (5b-C) is illustrated in table 161.

[table 161]

Compound

R³²

R³³

R³⁴

R³⁵

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

5-365

H

Me

SO₃H

H

5-366

H

cHx

H

SO₃H

H

5-367

H

iPr

H

SO₃H

H

5-368

H

Ph

H

SO₃H

H

5-369

H

Bu

H

SO₃H

H

5-370

H

tBu

H

SO₃H

5-371

H

Et

H

SO₃H

H

SO₃H

H

5-372

H

Ph

tBu

Bu

SO₃H

H

OH

H

5-373

H

CO₂Ph

Et

tBu

H

SO₃H

H

NBu₂

H

5-374

H

PhO

Me

tBu

H

SO₃H

tBu

H

5-375

H

iPr

cHx

Et

CO₂H

H

SO₃H

H

5-376

CO₂Me

SO₃H

iPr

Me

H

SO₃H

H

5-377

H

Me

Ph

cHx

H

NO₂

H

SO₃H

5-378

H

Et

Bu

iPr

H

CONBu₂

SO₃H

H

SO₃H

H

5-379

H

CO₂Me

Bu

Ph

SO₃H

H

SO₂NBu₂

H

5-380

H

tBu

Bu

H

SO₃H

H

Cl

5-381

H

cHx

Et

Bu

H

SO₃H

H

Br

H

5-382

H

OH

Me

tBu

H

SO₃H

H

Ph

5-383

H

MeO

cHx

Et

H

PhO

H

SO₃H

H

5-384

H

NBu₂

iPr

Me

H

CO₂Ph

H

SO₃H

5-385

H

NO₂

Ph

cHx

Me

H

SO₃H

H

SO₃H

H

5-386

Et

Br

Et

iPr

SO₃H

H

5-387

H

SO₂NBu₂

Me

Ph

H

SO₃H

H

iPr

H

5-388

H

Cl

cHx

Et

H

SO₃H

H

cHx

5-389

SO₃H

CONBu₂

iPr

Me

H

SO₃Na

H

5-390

H

F

Ph

cHx

CN

H

SO₃H

H

5-391

H

CO₂H

Bu

iPr

H

MeO

H

SO₃H

5-392

F

CN

tBu

Ph

H

SO₃H

H

SO₃H

H

Compound (the 5-393)~compound (5-420) indicated by formula (5c-O) is illustrated in table 162.

[table 162]

Compound

R³²

R³³

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

5-393

H

SO₃H

H

5-394

H

SO₃H

H

5-395

H

SO₃H

H

5-396

H

SO₃H

H

5-397

H

SO₃H

H

5-398

H

SO₃H

5-399

H

SO₃H

H

SO₃H

H

5-400

H

Ph

SO₃H

H

OH

H

5-401

H

CO₂Ph

H

SO₃H

H

NBu₂

H

5-402

H

PhO

H

SO₃H

tBu

H

5-403

H

iPr

CO₂H

H

SO₃H

H

5-404

CO₂Me

SO₃H

H

SO₃H

H

5-405

H

Me

H

NO₂

H

SO₃H

5-406

H

Et

H

CONBu₂

SO₃H

H

SO₃H

H

5-407

H

CO₂Me

SO₃H

H

SO₂NBu₂

H

5-408

H

tBu

H

SO₃H

H

Cl

5-409

H

cHx

H

SO₃H

H

Br

H

5-410

H

OH

H

SO₃H

H

Ph

5-411

H

MeO

H

PhO

H

SO₃H

H

5-412

H

NBu₂

H

CO₂Ph

H

SO₃H

5-413

H

NO₂

Me

H

SO₃H

H

SO₃H

H

5-414

Et

Br

SO₃H

H

5-415

H

SO₂NBu₂

H

SO₃H

H

iPr

H

5-416

H

Cl

H

SO₃H

H

cHx

5-417

SO₃H

CONBu₂

H

SO₃H

H

5-418

H

F

CN

H

SO₃Na

H

5-419

H

CO₂H

H

MeO

H

SO₃H

5-420

F

CN

H

SO₃H

H

SO₃H

H

Compound (the 5-421)~compound (5-448) indicated by formula (5c-S) is illustrated in table 163.

[table 163]

Compound

R³²

R³³

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

5-421

H

SO₃H

H

5-422

H

SO₃H

H

5-423

H

SO₃H

H

5-424

H

SO₃H

H

5-425

H

SO₃H

H

5-426

H

SO₃H

5-427

H

SO₃H

H

SO₃H

H

5-428

H

Ph

SO₃H

H

OH

H

5-429

H

CO₂Ph

H

SO₃H

H

NBu₂

H

5-430

H

PhO

H

SO₃H

tBu

H

5-431

H

iPr

CO₂H

H

SO₃H

H

5-432

CO₂Me

SO₃H

H

SO₃H

H

5-433

H

Me

H

NO₂

H

SO₃H

5-434

H

Et

H

CONBu₂

SO₃H

H

SO₃H

H

5-435

H

CO₂Me

SO₃H

H

SO₂NBu₂

H

5-436

H

tBu

H

SO₃H

H

Cl

5-437

H

cHx

H

SO₃H

H

Br

H

5-438

H

OH

H

SO₃H

H

Ph

5-439

H

MeO

H

PhO

H

SO₃H

H

5-440

H

NBu₂

H

CO₂Ph

H

SO₃H

5-441

H

NO₂

Me

H

SO₃H

H

SO₃H

H

5-442

Et

Br

SO₃H

H

5-443

H

SO₂NBu₂

H

SO₃H

H

iPr

H

5-444

H

Cl

H

SO₃H

H

cHx

5-445

SO₃H

CONBu₂

H

SO₃H

H

5-446

H

F

CN

H

SO₃H

H

5-447

H

CO₂H

H

MeO

H

SO₃Na

5-448

F

CN

H

SO₃H

H

SO₃H

H

Compound (the 5-449)~compound (5-476) indicated by formula (5c-N) is illustrated in table 164.

[table 164]

Compound

R³²

R³³

R³⁴

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

5-449

H

Me

SO₃H

H

5-450

H

cHx

H

SO₃H

H

5-451

H

iPr

H

SO₃H

H

5-452

H

Ph

H

SO₃H

H

5-453

H

Bu

H

SO₃H

H

5-454

H

tBu

H

SO₃H

5-455

H

Et

H

SO₃H

H

SO₃H

H

5-456

H

Ph

tBu

SO₃H

H

OH

H

5-457

H

CO₂Ph

Et

H

SO₃H

H

NBu₂

H

5-458

H

PhO

Me

H

SO₃H

tBu

H

5-459

H

iPr

cHx

CO₂H

H

SO₃H

H

5-460

CO₂Me

SO₃H

iPr

H

SO₃H

H

5-461

H

Me

Ph

H

NO₂

H

SO₃H

5-462

H

Et

Bu

H

CONBu₂

SO₃H

H

SO₃H

H

5-463

H

CO₂Me

Bu

SO₃H

H

SO₂NBu₂

H

5-464

H

tBu

H

SO₃H

H

Cl

5-465

H

cHx

Et

H

SO₃H

H

Br

H

5-466

H

OH

Me

H

SO₃H

H

Ph

5-467

H

MeO

cHx

H

PhO

H

SO₃H

H

5-468

H

NBu₂

iPr

H

CO₂Ph

H

SO₃H

5-469

H

NO₂

Ph

Me

H

SO₃H

H

SO₃H

H

5-470

Et

Br

Et

SO₃Na

H

5-471

H

SO₂NBu₂

Me

H

SO₃H

H

iPr

H

5-472

H

Cl

cHx

H

SO₃H

H

cHx

5-473

SO3H

CONBu₂

iPr

H

SO₃H

H

5-474

H

F

Ph

CN

H

SO₃H

H

5-475

H

CO₂H

Bu

H

MeO

H

SO₃H

5-476

F

CN

tBu

H

SO₃H

H

SO₃H

H

Compound (the 5-477)~compound (5-504) indicated by formula (5c-C) is illustrated in table 165.

[table 165]

Compound

R³²

R³³

R³⁴

R³⁵

R³⁶

R³⁷

R³⁸

R³⁹

R⁴⁰

R⁴¹

5-477

H

Me

SO₃H

H

5-478

H

cHx

H

SO₃H

H

5-479

H

iPr

H

SO₃H

H

5-480

H

Ph

H

SO₃H

H

5-481

H

Bu

H

SO₃H

H

5-482

H

tBu

H

SO₃H

5-483

H

Et

H

SO₃H

H

SO₃H

H

5-484

H

Ph

tBu

Bu

SO₃H

H

OH

H

5-485

H

CO₂Ph

Et

tBu

H

SO₃H

H

NBu₂

H

5-486

H

PhO

Me

tBu

H

SO₃H

tBu

H

5-487

H

iPr

cHx

Et

CO₂H

H

SO₃H

H

5-488

CO₂Me

SO₃H

iPr

Me

H

SO₃H

H

5-489

H

Me

Ph

cHx

H

NO₂

H

SO₃H

5-490

H

Et

Bu

iPr

H

CONBu₂

SO₃H

H

SO3H

H

5-491

H

CO₂Me

Bu

Ph

SO₃H

H

SO₂NBu₂

H

5-492

H

tBu

Bu

H

SO₃H

H

Cl

5-493

H

cHx

Et

Bu

H

SO₃H

H

Br

H

5-494

H

OH

Me

tBu

H

SO₃H

H

Ph

5-495

H

MeO

cHx

Et

H

PhO

H

SO₃H

H

5-496

H

NBu₂

iPr

Me

H

CO₂Ph

H

SO₃H

5-497

H

NO₂

Ph

cHx

Me

H

SO₃H

H

SO₃H

H

5-498

Et

Br

Et

iPr

SO₃H

H

5-499

H

SO₂NBu₂

Me

Ph

H

SO₃Na

H

iPr

H

5-500

H

Cl

cHx

Et

H

SO₃H

H

cHx

5-501

SO₃H

CONBu₂

iPr

Me

H

SO₃H

H

5-502

H

F

Ph

cHx

CN

H

SO₃H

H

5-503

H

CO₂H

Bu

iPr

H

MeO

H

SO₃H

5-504

F

CN

tBu

Ph

H

SO₃H

H

SO₃H

H

From raw material it is chiral from the viewpoint of, as compound (4), preferred compound (4-1)~compound (4-49) is changed Close object (4-71)~compound (4-119), compound (4-141)~compound (4-189), compound (4-211)~compound (4-259), compound (4-281)~compound (4-287), compound (4-309)~compound (4-315), compound (4- 337)~compound (4-343), compound (4-365)~compound (4-371), compound (4-393)~compound (4- 399), compound (4-421)~compound (4-427), compound (4-449)~compound (4-455) and compound (4- 477)~compound (4-483), wherein more preferable compound (4-1)~compound (4-14), compound (4-281)~chemical combination Object (4-287) and compound (4-393)~compound (4-399), wherein further preferred compound (4-5), compound (4-12), compound (4-285) and compound (4-397).

From raw material it is chiral from the viewpoint of, as compound (5), preferred compound (5-1)~compound (5-49) is changed Close object (5-71)~compound (5-119), compound (5-141)~compound (5-189), compound (5-211)~compound (5-259), compound (5-281)~compound (5-287), compound (5-309)~compound (5-315), compound (5- 337)~compound (5-343), compound (5-365)~compound (5-371), compound (5-393)~compound (5- 399), compound (5-421)~compound (5-427), compound (5-449)~compound (5-455) and compound (5- 477)~compound (5-483), wherein more preferable compound (5-1)~compound (5-14), compound (5-281)~chemical combination Object (5-287) and compound (5-393)~compound (5-399), wherein even more preferably compound (5-5), compound (5-12), compound (5-285) and compound (5-397).

As the manufacturing method of the compound of the present invention (1), can enumerate for example based on Dyes and Pigments (dye Material and pigment) (2008), the method that the method recorded in 77,556-558. is manufactured.Specifically, compound (1) can be with The compound and cyan-acetic ester of the compound, formula (pp2) expression that are indicated by formula (pp1) are in benzoic acid and solvent In the presence of carry out cyclization, to be manufactured.Preferably 0 DEG C~200 DEG C of reaction temperature, more preferable 100 DEG C~150 DEG C.Instead Preferably 1 hour~24 hours, more preferable 8 hours~18 hours, further preferred 8 hours~16 hours between seasonable.As described Solvent, for example there are methanol, ethyl alcohol, 2- propyl alcohol, n-butyl alcohol, 1- amylalcohol, 1- octanol or N-Methyl pyrrolidones etc., preferably 1- penta Alcohol.

[in formula (pp1) and formula (pp2), R¹~R⁵、R⁷~R⁹, AA, X and L respectively indicate meaning same as described above Think.]

It manufactures in compound (1), 1 mole of compound indicated relative to formula (pp2), the compound that formula (pp1) indicates Preferably 1 mole~10 moles of usage amount, more preferable 1 mole~2 moles, further preferred 1 mole.

It manufactures in compound (1), 1 mole of compound indicated relative to formula (pp2), the usage amount of cyan-acetic ester is excellent Select 1 mole~10 moles, more preferable 1 mole~2 moles, further preferred 1 mole.

It manufactures in compound (1), 1 mole of compound indicated relative to formula (pp2), the usage amount of benzoic acid is usually 0.3 mole~3 moles, preferably 0.3~0.6 mole, more preferable 0.3~0.4 mole.

In addition, compound (1 ') in compound (1) can be indicated by the compound that is indicated by formula (pp1), formula (pp3) Compound and cyan-acetic ester cyclization is carried out in the presence of benzoic acid and solvent, to be manufactured.Reaction temperature Preferably 0 DEG C~200 DEG C, more preferable 100 DEG C~150 DEG C of degree.Reaction time preferably 1 hour~24 hours, more preferable 8 hours~18 Hour, further preferred 8 hours~16 hours.As the solvent, for example there are methanol, ethyl alcohol, 2- propyl alcohol, n-butyl alcohol, 1- penta Alcohol, 1- octanol or N-Methyl pyrrolidone etc., preferably 1- amylalcohol.

[in formula (pp3), R⁷~R⁹, X and L indicate the meaning same as described above.]

It manufactures in compound (1 '), 1 mole of compound indicated relative to formula (pp3), the compound that formula (pp1) indicates Usage amount is usually 2 moles or more 20 moles hereinafter, it is preferred that 2~4 moles, further preferred 2 moles.

It manufactures in compound (1 '), 1 mole of compound indicated relative to formula (pp3), the usage amount of cyan-acetic ester Usually 2 moles~20 moles, preferably 2~4 moles, more preferable 2 moles.

It manufactures in compound (1 '), 1 mole of compound indicated relative to formula (pp3), the usage amount of benzoic acid is usually 0.6 mole~6 moles, preferably 0.6~1.2 mole, more preferable 0.6~0.7 mole.

To the method for obtaining the compound of the present invention (1) or compound (1 ') as target compound by reaction mixture There is no particular limitation, can use well known various methods.It is preferred that such as column chromatography；Suitably adjust reaction mixture Temperature and make crystallization be precipitated, filter to take the crystallization method；Or compound (1) or change are added to using by reaction mixture The method in the solvent that object (1 ') will not dissolve is closed, crystallization is precipitated, filters to take to obtain the crystallization.The crystallization filtered to take preferably is used Water, acetonitrile, methanol, ethyl alcohol, 2- propyl alcohol, n-butyl alcohol, 1- amylalcohol, 1- octanol, tetrahydrofuran, acetone, acetic acid, ethyl acetate, oneself Alkane, toluene or their mixed liquor equal solvent are cleaned, and are then dried.In addition it is also possible to as desired by following The known methods such as method, column chromatography or recrystallization, are further purified, the method be dissolved in acetonitrile, Methanol, ethyl alcohol, 2- propyl alcohol, n-butyl alcohol, 1- amylalcohol, 1- octanol, tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, toluene, In chloroform or their mixed liquor equal solvent, after being cleaned with sodium hydrate aqueous solution, the method that is dried.

Compound (2) can be based on such as Dyes and Pigments (2008), method described in 77,556-558. into Row manufacture.

Specifically, compound (2) can pass through the compound for the compound, formula (pp ' 2) expression that formula (pp ' 1) is indicated And cyan-acetic ester carries out cyclization, in the presence of benzoic acid and solvent to be manufactured.Reaction temperature is preferred It is 0 DEG C~200 DEG C, more preferably 100 DEG C~150 DEG C.Reaction time is preferably 1 hour~24 hours, more preferably 8 hours~ 16 hours.As the solvent, for example there are methanol, ethyl alcohol, 2- propyl alcohol, n-butyl alcohol, 1- amylalcohol, 1- octanol or N- crassitudes Ketone etc., preferably 1- amylalcohol.

[in formula (pp ' 1) and formula (pp ' 2), R¹¹~R¹⁴、Q¹And Q²Respectively indicate the meaning same as described above.]

It manufactures in compound (2), 1 mole of compound indicated relative to formula (pp ' 2), the compound that formula (pp ' 1) indicates Usage amount be preferably 1 mole~10 moles, more preferably 1 mole~4 moles, further preferably 1 mole~3 moles, into One step is more preferably 1 mole.

It manufactures in compound (2), 1 mole of compound indicated relative to formula (pp ' 2), the usage amount of cyan-acetic ester It is preferably 1 mole~10 moles, more preferably 1 mole~4 moles, further preferably 1 mole~3 moles, further more excellent It is selected as 1 mole.

It manufactures in compound (2), 1 mole of compound indicated relative to formula (pp ' 2), the usage amount of benzoic acid is preferably It is 0.1 mole~3 moles, more preferably 0.3 mole~3 moles, further preferably 0.3 mole~1.2 moles, further more excellent It is selected as 0.3~0.4 mole.

To the method by reaction mixture acquirement target compound compound (2), there is no particular limitation, can be using public affairs The various methods known.It is preferred that such as column chromatography；The method of appropriate adjustment reaction mixture temperature；Or it uses reaction mixture The method being added in the solvent that compound (2) will not dissolve is precipitated crystallization, filters to take to obtain the crystallization.That filters to take should Water, acetonitrile, methanol, ethyl alcohol, 2- propyl alcohol, n-butyl alcohol, 1- amylalcohol, 1- octanol, tetrahydrofuran, acetone, acetic acid, second are preferably used in crystallization Acetoacetic ester, hexane, toluene, n,N-Dimethylformamide, N-Methyl pyrrolidone, chloroform or their mixed liquor equal solvent carry out Cleaning or recrystallization, then be dried.In addition it is also possible to as needed using the known methods such as column chromatography or recrystallization into The further purification of row.

Compound (3) can be manufactured for example, by method as follows.Firstly, the chemical combination that formula (pp " 1) indicates Object and diethyl malonate reaction, obtain the compound of formula (pp " 2) expression.Then, formula (pp " 2) indicate compound, Phosphoryl chloride phosphorus oxychloride and n,N-Dimethylformamide reaction, obtain the compound of formula (pp " 3) expression.Finally, passing through formula (pp " 3) table The compound reaction that the compound and formula (pp " 4) shown indicates, obtains compound (3).Formula (pp " 1) indicate compound and The compound that formula (pp " 4) indicates can use commercially available product respectively, and the object manufactured by any known method also can be used Matter.

[in formula (pp " 1), formula (pp " 2), formula (pp " 3) and formula (pp " 4), R¹⁶~R²⁴, X ' and L ' respectively indicate with The above-mentioned identical meaning.]

In the compound that manufacture formula (pp " 2) indicates, 1 mole of compound indicated relative to formula (pp " 1), malonic acid diethyl Preferably 1 mole or more 10 moles of the usage amount of ester hereinafter, more preferable 1~3 mole.

The manufacture for the compound that formula (pp " 2) indicates is preferably there are triethylamine, tri-n-butylamine, pyrrolidines, piperidines, pyrazines etc. Implement under conditions of the organic bases such as amine or pyridine, wherein more preferably implementing under conditions of there are piperidines.Furthermore it is preferred that existing Implement under conditions of solvent, as the solvent, preferably alcohol, tetrahydrofuran, acetone, the methyl-isobutyl of carbon atom number 1~10 Ketone, acetic acid, glacial acetic acid, ethyl acetate, acetonitrile, water, hexane, toluene, chloroform, n,N-Dimethylformamide, N, N- dimethyl second Amide, N-Methyl pyrrolidone, wherein more preferable ethyl alcohol.Preferably -5 DEG C~140 DEG C of reaction temperature, wherein more preferable 10 DEG C~ 100℃。

In the manufacture for the compound that formula (pp " 3) indicates, 1 mole of compound indicated relative to formula (pp " 2), phosphoryl chloride phosphorus oxychloride Preferably 1 mole or more 10 moles of usage amount hereinafter, more preferable 1~5 mole.

In the manufacture for the compound that formula (pp " 3) indicates, 1 mole of compound, N indicated relative to formula (pp " 2), N- diformazan Preferably 1 mole or more 10 moles of the usage amount of base formamide hereinafter, more preferable 1~5 mole.

The manufacture for the compound that formula (pp " 3) indicates preferably is implemented under conditions of there are solvent, excellent as the solvent Select the alcohol of carbon atom number 1~10, tetrahydrofuran, acetone, methyl iso-butyl ketone (MIBK), acetic acid, glacial acetic acid, ethyl acetate, acetonitrile, water, Hexane, toluene, chloroform, n,N-Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone, wherein more preferable N, Dinethylformamide.Preferably -5 DEG C~100 DEG C of reaction temperature, wherein more preferably -5 DEG C~60 DEG C.

In the manufacture of compound (3), 1 mole of compound indicated relative to formula (pp " 4), the chemical combination that formula (pp " 3) indicates Preferably 2 moles or more 20 moles of the usage amount of object hereinafter, more preferable 2~3 moles.

The manufacture of compound (3) is preferably implemented under conditions of there are organic bases such as sodium acetate, potassium acetate or lithium acetates, In more preferably implement under conditions of there are sodium acetate.Furthermore it is preferred that implementing under conditions of there are solvent, as described molten Agent, it is preferable to use the alcohol of carbon atom number 1~10, tetrahydrofuran, acetone, methyl iso-butyl ketone (MIBK), acetic acid, glacial acetic acid, ethyl acetate, Acetonitrile, water, hexane, toluene, chloroform, n,N-Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone, wherein The more preferable acetic acid of ice.Preferably 0 DEG C~140 DEG C of reaction temperature, wherein more preferable 70 DEG C~110 DEG C.

To the method by reaction mixture acquirement target compound compound (3), there is no particular limitation, can be using public affairs The various methods known.Such as column chromatography can be enumerated；Or water is added in the reactive mixture, crystallization is precipitated, filters to take The method of the crystallization.The crystallization filtered to take can be pungent with water, acetonitrile, methanol, ethyl alcohol, 2- propyl alcohol, n-butyl alcohol, 1- amylalcohol, 1- Alcohol, tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, toluene, methylene chloride, chloroform, tetrachloromethane or their mixed liquor Equal solvent is cleaned, then is dried.Furthermore, it is possible to be allowed to be dissolved in acetonitrile, methanol, ethyl alcohol, 2- propyl alcohol, 1- as needed Butanol, 1- amylalcohol, 1- octanol, tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, toluene, methylene chloride, chloroform, four chloromethanes In alkane or their mixed liquor equal solvent, after being cleaned with sodium hydrate aqueous solution, it is dried, it can also be by using column chromatography Method well known to method or recrystallization etc. is further purified.

The compound of the present invention (3) can be based on such as Dyes and Pigments (2008), side described in 77,556. Method is manufactured.Specifically, the compound and cyanogen for the compound, formula (pp " 4) expression that formula (pp " 1) is indicated can be passed through Ethyl carries out cyclization, in the presence of benzoic acid and solvent to be manufactured.Reaction temperature is preferably 0 DEG C~ 200 DEG C, more preferably 100 DEG C~150 DEG C.Reaction time is preferably 1 hour~24 hours, and more preferably 8 hours~18 hours, Especially it is more preferably 8 hours~16 hours.As the solvent, for example there are methanol, ethyl alcohol, 2- propyl alcohol, n-butyl alcohol, 1- amylalcohol, 1- octanol or N-Methyl pyrrolidone etc., preferably 1- amylalcohol.

It manufactures in compound (3), 1 mole of compound indicated relative to formula (pp " 4), the compound that formula (pp " 1) indicates Usage amount be usually 2 moles or more 20 moles hereinafter, preferably 2~4 moles, especially preferably 2 moles.

It manufactures in compound (3), 1 mole of compound indicated relative to formula (pp " 4), the usage amount of cyan-acetic ester It is preferably generally 2 moles~20 moles, preferably 2~4 moles, especially preferably 2 moles.

It manufactures in compound (3), 1 mole of compound indicated relative to formula (pp " 4), the usage amount of benzoic acid is usually 0.6 mole~6 moles, preferably 0.6 mole~1.2 moles, especially preferably 0.6 mole~0.7 mole.

To the method by reaction mixture acquirement target compound the compound of the present invention (3), there is no particular limitation, can To use well known various methods.It is preferred that such as column chromatography；Appropriate adjustment reaction mixture temperature, and crystallization is precipitated, mistake The method that leaching obtains the crystallization；Or using the method being added to reaction mixture in the solvent that compound (3) will not dissolve, make Crystallization is precipitated, and filters to take to obtain the crystallization.The crystallization filtered to take preferably use water, acetonitrile, methanol, ethyl alcohol, 2- propyl alcohol, n-butyl alcohol, 1- amylalcohol, 1- octanol, tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, toluene or their mixture equal solvent cleaning, Re-dry.Furthermore, it is possible to be carried out as desired by method well known to following methods, column chromatography or recrystallization etc. further Purification, the method be allowed to be dissolved in acetonitrile, methanol, ethyl alcohol, 2- propyl alcohol, n-butyl alcohol, 1- amylalcohol, 1- octanol, tetrahydrofuran, In acetone, acetic acid, ethyl acetate, hexane, toluene, chloroform or their mixed liquor equal solvent, carried out with sodium hydrate aqueous solution After cleaning, the method that is dried.

As the compound of the present invention (4) or the manufacturing method of compound (5), there can be exemplified for example based on Dyes and Pigments (2008), the method that method described in 77,556-558. is manufactured.

As the manufacturing method of compound (4), following method can be enumerated: specifically, being indicated by formula (pp " ' 1) Compound, formula (pp " ' 2) indicate compound and cyan-acetic ester in the presence of benzoic acid and solvent, carry out ring Change reaction, to be manufactured.Preferably 0 DEG C~200 DEG C of reaction temperature, more preferable 100 DEG C~150 DEG C.Reaction time preferably 1 hour ~24 hours, more preferable 8 hours~16 hours.As the solvent, for example there are methanol, ethyl alcohol, 2- propyl alcohol, n-butyl alcohol, 1- penta Alcohol, 1- octanol or N-Methyl pyrrolidone etc., preferably 1- amylalcohol.

[in formula (pp " ' 1) and formula (pp " ' 2), R²⁸~R³²、R³⁶~R⁴¹And X " respectively indicates meaning same as described above Think.]

In the manufacture of compound (4), 1 mole of compound indicated relative to formula (pp " ' 2), the change that formula (pp " ' 1) indicates Preferably 1 mole~10 moles of usage amount for closing object, more preferable 1 mole~4 moles, further preferred 1 mole~3 moles, into one Walk more preferable 1 mole.

In the manufacture of compound (4), 1 mole of compound indicated relative to formula (pp " ' 2), the use of cyan-acetic ester Preferably 1 mole~10 moles of amount, more preferable 1 mole~4 moles, further preferred 1 mole~3 moles, even more preferably 1 rubs You.

In the manufacture of compound (4), 1 mole of compound indicated relative to formula (pp " ' 2), the usage amount of benzoic acid is preferred 0.1 mole~3 moles, more preferable 0.3 mole~3 moles, further preferred 0.3 mole~1.2 moles, even more preferably 0.3~0.4 mole.

As the manufacturing method of the compounds of this invention (5), following method can be enumerated: specifically, passing through formula (pp " ' 1) indicate compound, formula (pp " ' 3) indicate compound and cyan-acetic ester in the presence of benzoic acid and solvent, into Row cyclization, to be manufactured.Preferably 0 DEG C~200 DEG C of reaction temperature, more preferable 100 DEG C~150 DEG C.Reaction time preferably 1 Hour~24 hours, more preferable 8 hours~16 hours.As the solvent, for example there are methanol, ethyl alcohol, 2- propyl alcohol, n-butyl alcohol, 1- amylalcohol, 1- octanol or N-Methyl pyrrolidone etc., preferably 1- amylalcohol.

[in formula (pp " ' 3), R³⁶~R⁴¹And X " respectively indicates the meaning same as described above.]

In the manufacture of compound (5), 1 mole of compound indicated relative to formula (pp " ' 3), the change that formula (pp " ' 1) indicates Preferably 1 mole~10 moles of usage amount for closing object, more preferable 1 mole~4 moles, further preferred 1 mole~3 moles, into one Walk more preferable 1 mole.

In the manufacture of compound (5), 1 mole of compound indicated relative to formula (pp " ' 3), the use of cyan-acetic ester Preferably 1 mole~10 moles of amount, more preferable 1 mole~4 moles, further preferred 1 mole~3 moles, even more preferably 1 rubs You.

In the manufacture of compound (5), 1 mole of compound indicated relative to formula (pp " ' 3), the usage amount of benzoic acid is preferred 0.1 mole~3 moles, more preferable 0.3 mole~3 moles, further preferred 0.3 mole~1.2 moles, even more preferably 0.3~0.4 mole.

To the no spy of the method for obtaining target compound the compound of the present invention (4) or compound (5) by reaction mixture Other restriction can use well known various methods.It is preferred that such as column chromatography；Appropriate adjustment reaction mixture temperature makes to tie Partial crystallization goes out, filter to take the crystallization method；Or reaction mixture is added to compound (4) for use or compound (5) will not Method in the solvent of dissolution is precipitated crystallization, filters to take to obtain the crystallization.Water, acetonitrile, first are preferably used in the crystallization filtered to take Alcohol, ethyl alcohol, 2- propyl alcohol, n-butyl alcohol, 1- amylalcohol, 1- octanol, tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, toluene or it Mixed liquor equal solvent cleaned, then be dried.

Furthermore, it is possible to be carried out as desired by method well known to following methods, column chromatography or recrystallization etc. further Purification, the method is to be allowed to be dissolved in acetonitrile, methanol, ethyl alcohol, 2- propyl alcohol, n-butyl alcohol, 1- amylalcohol, 1- octanol, tetrahydro furan Mutter, in acetone, acetic acid, ethyl acetate, hexane, toluene, chloroform or their mixed liquor equal solvent, with sodium hydrate aqueous solution into It goes after cleaning, the method being dried.

Compound with cumarin skeleton contains compound (1), compound (1 '), compound (2), compound (3), compound (4) or compound (5) etc. have the compound of cumarin skeleton as effective component.It is adjacent with oxa- naphthalene The compound of ketone skeleton can only by compound (1), compound (1 '), compound (2), compound (3), compound (4) or Compound (5) is constituted, and can also contain aftermentioned dyestuff.Compound with cumarin skeleton contains preferably 70~100 The tool such as compound (1), compound (1 '), compound (2), compound (3), compound (4) or compound (5) of quality % ratio There is the compound of cumarin skeleton.

The compound with cumarin skeleton in the present invention is as display devices such as liquid crystal display devices Dyestuff contained by the photosensitive composition of colour filter is useful.

In colorant (A), in addition to containing compound (1), compound (1 '), compound (2), compound (3), compound (4) or compound (5) etc. with the compound of cumarin skeleton except, can also be further containing being different from compound (1), compound (1 '), compound (2), compound (3), compound (4) or compound (5) etc. have cumarin skeleton The dyestuff and/or pigment of compound.

Have as compound (1), compound (1 '), compound (2), compound (3), compound (4) or compound (5) etc. There is the dyestuff other than the compound of cumarin skeleton, for example there are in Colour Index (Colour Index) (The Society OfDyers and Colourists is published) in be sorted in solvent (Solvent), acid (Acid), alkaline (Basic), living Property (reactive), directly (Direct), dispersion (Disperse) or restore the dyestuff etc. of (Vat).More specifically citing just like The dyestuff of lower Colour Index (C.I.) number, but it is not limited to these.

C.I. solvent yellow 25,79,81,82,83,89；

C.I. Indian yellow 7,23,25,42,65,76；

C.I. active yellow 2,76,116；

C.I. direct Huang 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. Viride Nitens 1；

C.I. vat green 1 etc..

It is preferred that colorant (A) containing compound (1), compound (1 '), compound (2), compound (3), compound (4) or Compound (5) etc. has the compound of cumarin skeleton, and contains pigment (P).

As the pigment (P) that can contain in colorant (A), there is no particular limitation, and well known pigment can be used, and lifts Example, which has, to be for example sorted in pigment in Colour Index (The Society ofDyers and Colourists publication) Pigment.

As pigment, for example there are such as C.I. pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86, 93, the Huangs such as 94,109,110,117,125,128,137,138,139,147,148,150,153,154,166,173,194,214 Color pigment；

C.I. the orange pigments such as pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71,73；

C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,209,215, 216, the red pigments such as 224,242,254,255,264,265；

C.I. the blue pigments such as pigment blue 15,15:3,15:4,15:6,60；C.I. pigment violet 1,19,23,29,32,36, 38 equal violet pigments；

C.I. the viridine greens such as pigment Green 7,36,58；

C.I. the browns such as pigment brown 23,25；

C.I. black pigments such as pigment black 1,7 etc..

Pigment (P) preferred phthalocyanine color, is more preferably selected from and is made of halogenated copper phthalocyanine pigment and halogenated ZnPc pigment At least one of group, further preferably selected from by chloro copper phthalocyanine, bromo copper phthalocyanine and bromo ZnPc At least one of the group of pigment composition, even more preferably in the group being made of C.I. pigment Green 7,36 and 58 extremely Few one kind.The pigment is suitble to use in green pigment, by containing the pigment, is easy to carry out the best of projection spectrum Change, the light resistance and chemical resistance of colour filter become good.

Pigment, which can according to need, to be handled as follows: rosin processing；Using having imported acidic-group or basic group Pigment derivative etc. surface treatment；The grafting that surface of pigments carries out is handled by high-molecular compound etc.；Pass through sulfuric acid The micronized of the progress such as micronized method is handled；Or the cleaning treatment of impurity is removed by organic solvent or water etc.；It is handed over by ion It changes method and removes removing processing of ionic impurity etc..The partial size of preferred pigments is respectively uniform.

It, can be by being allowed to carry out decentralized processing containing pigment dispersing agent, to be made in equably for pigment It is scattered in the dispersible pigment dispersion of the state in pigment dispersing agent solution.Pigment can separately carry out decentralized processing, can also To mix a variety of carry out decentralized processings.

As the pigment dispersing agent, for example there are such as cationic system, anionic system, nonionic system, both sexes, Polyester, Pigment dispersing agents such as polyamine system, acrylic acid series etc..These pigment dispersing agents can be used alone, and can also be made with two or more combination With.As pigment dispersing agent, for example there are trade name KP (SHIN-ETSU HANTOTAI's chemical industry (strain) system), mono- レ Application of Off ロ (common prosperity society chemistry (strain) system), mono- ス of ソ Le スパ (ゼネカ (strain) system), EFKA (CIBA society system), (the monosodium glutamate Off アイ Application テ of アジスパ mono- Network ノ (strain) system), Disperbyk (mono- society's system of ビ Star Network ケミ) etc..

When using pigment dispersing agent, relative to 100 mass parts of pigment, usage amount preferably 100 below the mass, more preferably It is more than 5 mass parts that 50 below the mass.The usage amount of pigment dispersing agent has in above range and obtains more uniform dispersity Dispersible pigment dispersion tendency.

In addition to containing compound (1), compound (1 '), compound (2), compound (3), compound (4) in colorant (A) Or compound (5) etc. have cumarin skeleton compound except, also containing different from compound (1), compound (1 '), Compound (2), compound (3), compound (4) or compound (5) etc. have cumarin skeleton compound dyestuff with And/or when pigment, relative to the total amount of colorant (A), compound (1), compound (2), compound (3), is changed compound (1 ') Closing object (4) or compound (5) etc. has containing ratio preferably 1 mass % or more, 100 matter of compound of cumarin skeleton % is measured hereinafter, more preferable 1 mass % or more, 65 mass % is hereinafter, further preferred 2 mass % or more, 60 mass % or less.

Relative to the total amount of colorant (A), compound (1), compound (1 '), compound (2), compound (3), compound (4) or containing ratio preferably 1 matter of the compound and C.I. pigment Yellow 12 9 with cumarin skeleton such as compound (5) 100 mass % of % or more is measured hereinafter, more preferable 1 mass % or more, 65 mass % is hereinafter, 60 matter of further preferred 2 mass % or more Measure % or less.

When containing pigment (P), relative to the total amount of colorant (A), containing ratio preferably 1 mass % or more, 99 mass % with Under, more preferable 35 mass % or more, 99 mass % is hereinafter, even more preferably 40 mass % or more, 98 mass % or less.

Relative to the total amount of solid component, the containing ratio of colorant (A) preferably 1 mass % or more, 70 mass % is hereinafter, more It is preferred that 5 mass % or more, 70 mass % hereinafter, further preferred 5 mass % or more, 60 mass % hereinafter, even more preferably 5 matter Measure % or more 50 mass % or less.The containing ratio of colorant (A) can obtain desired light splitting or color is dense in the range Degree.

In this specification, " total amount of solid component " refer to removed from colored curable resin composition of the invention it is molten Ingredient total amount after agent (E).The total amount of solid component and content relative to its each ingredient can be for example, by liquid phase colors Analysis method known in spectrometry or gas chromatography etc. is measured.

To resin (B), there is no particular limitation, preferably alkali soluble resin, more preferably has from from by unsaturation The addition polymers of at least one structural unit selected in the group of carboxylic acid and unsaturated carboxylic acid anhydrides composition.As such resin For example there are resin below [K1]~[K6] etc..

Resin [K1] be selected from least one of the group that is made of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides (a) (with Under, sometimes referred to as " (a) ") with carbon atom number 2~4 cyclic annular ether structure and ethylene unsaturated bond monomer (b) (with Under, sometimes referred to as " (b) ") copolymer；

Resin [K2] (a), (b), the monomer (c) (be only rather than (a) and (b)) that can be copolymerized with (a) are (hereinafter, sometimes Referred to as " (c) ") copolymer；

The copolymer of resin [K3] (a) and (c)；

Resin obtained by resin [K4] (a) is reacted with the copolymer of (c) with (b)；

Resin obtained by resin [K5] (b) is reacted with the copolymer of (c) with (a)；

Resin [K6] (b) is reacted with the copolymer of (c) with (a), further with resin obtained by carboxylic acid anhydride reactant.

As (a), concrete example have such as acrylic acid, methacrylic acid, butenoic acid, it is o-, m-, to vinyl benzoic acid Unsaturated monocarboxylic class；

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3- vinylphthalic acid, 4- vinyl neighbour benzene two Formic acid, 3,4,5,6- tetrahydrophthalic acids, 1,2,3,6- tetrahydrophthalic acids, dimethyl tetrahydro phthalic acid, 1,4- The unsaturated dicarboxylics class such as cyclohexene dicarboxylic acid；

Methyl -5- norbornene -2,3- dicarboxylic acids, bicyclic [the 2.2.1] -2- heptene of 5- carboxyl, 5,6- dicarboxyl are bicyclic [2.2.1] -2- heptene, 5- carboxyl -5- methyl bicycle [2.2.1] -2- heptene, 5- carboxyl -5- ethyl bicyclic [2.2.1] -2- heptan Alkene, 5- carboxyl -6- methyl bicycle [2.2.1] -2- heptene, bicyclic [the 2.2.1] -2- heptene of 5- carboxyl -6- ethyl etc. contain carboxyl Bicyclic unsaturated compound class；

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3- vinylphthalic acid acid anhydride, 4- vinylphthalic acid acid anhydride, 3,4,5,6- tetrabydrophthalic anhydrides, 1,2,3,6- tetrabydrophthalic anhydrides, dimethyl tetrahydro phthalic anhydride, 5,6- The unsaturated dicarboxylics class acid anhydrides such as bicyclic [the 2.2.1] -2- heptene acid anhydrides of dicarboxyl；

Mono succinate (2- (methyl) acryloyl-oxyethyl) ester, phthalic acid list (2- (methyl) acryloxy second Base) etc. 2 yuan or more of polybasic carboxylic acid single ((methyl) acryloxyalkyl) esters of unsaturation；

Unsaturated acrylic compounds etc. in the same molecule of α-(methylol) acrylic acid etc containing hydroxyl and carboxyl.

Wherein, from terms of copolyreaction or from the aspect of dissolubility in aqueous alkali of obtained resin, preferably third Olefin(e) acid, methacrylic acid, maleic anhydride etc..

(b) refer to the cyclic annular ether structure with such as carbon atom number 2~4 (such as selected from by oxirane ring, oxa- ring fourth At least one of the group of alkane and tetrahydrofuran ring composition) and ethylene unsaturated bond polymerizable compound.(b) preferred tool There are the cyclic ether of carbon atom number 2~4 and the monomer of (methyl) acryloxy.

In addition, " (methyl) acrylic acid " is indicated selected from the group being made of acrylic acid and methacrylic acid in this specification At least one of.The statements such as " (methyl) acryloyl group " and " (methyl) acrylate " the also meaning having the same.

As (b), for example there are the monomers (b1) for example with epoxy ethyl and ethylene unsaturated bond (hereinafter, sometimes referred to as For " (b1) "), the monomer (b2) with oxetanylmethoxy and ethylene unsaturated bond (hereinafter, sometimes referred to as " (b2) "), have Tetrahydrofuran base and the monomer (b3) (hereinafter, sometimes referred to as " (b3) ") of ethylene unsaturated bond etc..

As (b1), structure obtained by being at least partially epoxidized for example there are the unsaturated aliphatic hydrocarbon for example with straight chain or containing branch Monomer (b1-1) (hereinafter, sometimes referred to as " (b1-1) "), be at least partially epoxidized with alicyclic unsaturated hydrocarbon obtained by structure list Body (b1-2) (hereinafter, sometimes referred to as " (b1-2) ").

As (b1-1), for example there are (methyl) glycidyl acrylate, (methyl) propenoic acid beta-methylglycidyl esters, (methyl) propenoic acid beta-ethyl glycidyl ester, glycidyl vinyl ether, adjacent vinylbenzyl glycidyl base ether, second Alkenyl benzyl glycidyl ether, to vinylbenzyl glycidyl base ether, Alpha-Methyl neighbour's vinylbenzyl glycidyl base ether, Alpha-Methyl-vinylbenzyl glycidyl base ether, Alpha-Methyl-are bis- to vinylbenzyl glycidyl base ether, 2,3- (to shrink sweet Oil base oxygroup methyl) styrene, bis- (glycidyl oxy methyl) styrene of 2,4-, bis- (the glycidyl oxygroup first of 2,5- Base) styrene, bis- (glycidyl oxy methyl) styrene of 2,6-, 2,3,4- tri- (glycidyl oxy methyl) benzene second Alkene, 2,3,5- tri- (glycidyl oxy methyl) styrene, 2,3,6- tri- (glycidyl oxy methyl) styrene, 3,4, 5- tri- (glycidyl oxy methyl) styrene, 2,4,6- tri- (glycidyl oxy methyl) styrene etc..

As (b1-2), for example there are-vinylcyclohexene oxides, 1,2- epoxy -4- vinyl cyclohexane, (methyl) propylene 3,4- of acid epoxycyclohexanecarboxylate, (methyl) acrylic acid 3, the compound and formula that 4- epoxycyclohexanecarboxylate, formula (I) indicate (II) compound etc. indicated.

[in formula (I) and formula (II),^aAnd R^bThe alkyl of hydrogen atom or carbon atom number 1~4 is indicated, contained by the alkyl Hydrogen atom can be optionally substituted by a hydroxyl group.

X^aAnd X^bIndicate singly-bound ,-R^c-、*-R^c-O-、*-R^c- S- or *-R^c-NH-。

R^cIndicate the alkylidene of carbon atom number 1~6.

* the bonding position with O is indicated.]

As the alkyl of carbon atom number 1~4, for example there are methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, uncles Butyl etc..

Alkyl after being optionally substituted by a hydroxyl group as hydrogen atom, for example there are methylol, 1- hydroxyethyl, 2- hydroxyethyl, 1- hydroxyls Base propyl, 2- hydroxypropyl, 3- hydroxypropyl, 1- hydroxyl -1- Methylethyl, 2- hydroxyl -1- Methylethyl, 1- hydroxybutyl, 2- hydroxybutyl, 3- hydroxybutyl, 4- hydroxybutyl etc..

As R^aAnd R^b, for example there are hydrogen atom, methyl, methylol, 1- hydroxyethyl, 2- hydroxyethyl, preferably hydrogen is former Son, methyl.

As alkylidene, methylene, ethylidene, 1,2- propylidene, 1,3- propylidene, Isosorbide-5-Nitrae-butylidene, 1,5- pentylidene, 1,6- hexylidene etc..

As X^aAnd X^b, for example there are singly-bound, methylene, ethylidene, *-CH₂- O- and *-CH₂CH₂- O-, preferably singly Key, *-CH₂CH₂-O-.* the bonding position with O is indicated.

As the compound that formula (I) is indicated, for example there are the compounds etc. that any one is indicated by formula (I-1)~formula (I-15). Wherein, the change that preferred formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11)~formula (I-15) indicate Close object, the compound that more preferable formula (I-1), formula (I-7), formula (I-9) or formula (I-15) indicate.

As the compound that formula (II) is indicated, for example there are the compounds that any one is indicated by formula (II-1)~formula (II-15) Deng.Wherein, preferred formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11)~formula (II- 15) compound indicated, the compound that more preferable formula (II-1), formula (II-7), formula (II-9) or formula (II-15) indicate.

The compound that the compound and formula (II) that formula (I) indicates indicate can use individually, can also be by formula (I) The compound that the compound of expression is indicated with formula (II) is used in combination.And when with them, compound and formula (II) table that formula (I) indicates The containing ratio of the compound shown by mole on the basis of, preferably 5: 95~95: 5, more preferable 10: 90~90: 10, further preferably 20: 80~80: 20.

As (b2), preferably with the monomer of oxetanylmethoxy and (methyl) acryloxy.As (b2), for example there are 3- Methyl -3- methacryloxymethyl oxetanes, 3- methyl -3- acryloyloxymethyl oxetanes, 3- ethyl - 3- methacryloxymethyl oxetanes, 3- ethyl -3- acryloyloxymethyl oxetanes, 3- methyl -3- first Base acryloyl-oxyethyl oxetanes, 3- methyl -3- acryloyl-oxyethyl oxetanes, 3- ethyl -3- methyl-prop Alkene trimethylammonium oxetanes, 3- ethyl -3- acryloyl-oxyethyl oxetanes etc..

As (b3), preferably with the monomer of tetrahydrofuran base and (methyl) acryloxy.As (b3), concrete example There are tetrahydrofurfuryl acrylate (such as one ト V#150 of ビス U, Osaka Organic Chemical Industry (strain) system), methacrylic acid tetrahydro Furfuryl group ester etc..

As (b), in terms of the reliabilities such as heat resistance, the chemical resistance that can further increase the colour filter obtained Consider, preferably (b1).Further from the aspect of the excellent storage stability of colored curable resin composition, more preferably (b1-2)。

As (c), for example there are such as (methyl) methyl acrylate, (methyl) ethyl acrylate, the positive fourths of (methyl) acrylic acid Ester, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid Dodecyl ester, (methyl) lauryl acrylate, (methyl) octadecyl acrylate, (methyl) acrylic acid ring pentyl ester, (first Base) cyclohexyl acrylate, (methyl) acrylic acid 2- methyl cyclohexyl, (methyl) acrylic acid tricyclic [5.2.1.0^2,6] silane -8- base Ester (in this technical field, usual entitled " (methyl) dicyclopentyl acrylate ".In addition, being sometimes referred to as " (methyl) propylene Sour tricyclodecyl ester "), (methyl) acrylic acid tricyclic [5.2.1.0^2,6] decene -8- base ester (in this technical field, trivial name For " (methyl) acrylic acid dicyclopentenyl base ester "), (methyl) acrylic acid bicyclopentyl oxygroup ethyl ester, (methyl) isobomyl acrylate Ester, (methyl) adamantyl acrylate, (methyl) allyl acrylate, (methyl) acrylic acid propargyl ester, (methyl) third (methyl) esters of acrylic acid such as olefin(e) acid phenylester, (methyl) acrylic acid naphthalene ester, (methyl) benzyl acrylate；

(methyl) third containing hydroxyl such as (methyl) acrylic acid 2- hydroxyethyl ester, (methyl) acrylic acid 2- hydroxy-propyl ester Olefin(e) acid esters；

The dicarboxylic diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate；

Bicyclic [2.2.1] -2- heptene, 5- methyl bicycle [2.2.1] -2- heptene, bicyclic [the 2.2.1] -2- heptene of 5- ethyl, Bicyclic [the 2.2.1] -2- heptene of 5- hydroxyl, bicyclic [the 2.2.1] -2- heptene of 5- methylol, 5- (2 '-hydroxyethyl) are bicyclic Bicyclic [the 2.2.1] -2- heptene of [2.2.1] -2- heptene, 5- methoxyl group, bicyclic [the 2.2.1] -2- heptene of 5- ethyoxyl, 5,6- dihydroxy Bicyclic [the 2.2.1] -2- heptene of base, bicyclic [the 2.2.1] -2- heptene of 5,6- bis- (methylol), 5,6- bis- (2 '-hydroxyethyl) are bicyclic Bicyclic [the 2.2.1] -2- heptene of [2.2.1] -2- heptene, 5,6- dimethoxy, bicyclic [the 2.2.1] -2- heptene of 5,6- diethoxy, Bicyclic [the 2.2.1] -2- heptene of 5- hydroxy-5-methyl base, bicyclic [the 2.2.1] -2- heptene of 5- hydroxyl -5- ethyl, 5- methylol -5- first Bicyclic [the 2.2.1] -2- heptene of base, bicyclic [the 2.2.1] -2- heptene of 5- tert-butoxycarbonyl, 5- cyclohexyl Epoxide carbonyl are bicyclic Bicyclic [the 2.2.1] -2- heptene of [2.2.1] -2- heptene, 5- phenyloxycarbonyl, 5,6- bis- (tert-butoxycarbonyls) are bicyclic The bicyclic unsaturated compound classes such as [2.2.1] -2- heptene, 5,6- bis- (cyclohexyl Epoxide carbonyls) bicyclic [2.2.1] -2- heptene；

N-phenylmaleimide, N- N-cyclohexylmaleimide, N- benzyl maleimide, N- succinimide -3- Maleimidobenzoyl ester, N- succinimide -4- malimidobutanoate, N- succinimide -6- maleimide The dicarbonyl imides such as capronate, N- succinimide -3- maleimidopropionic acid ester, N- (9- acridinyl) maleimide spread out Biological species；

Styrene, α-methylstyrene, m-methyl styrene, p-methylstyrene, vinyltoluene, to methoxybenzene second Alkene, acrylonitrile, methacrylonitrile, vinyl chloride, dichloroethylene, acrylamide, Methacrylamide, vinyl acetate, 1,3- fourth Diene, isoprene, 2,3- dimethyl -1,3-butadiene etc..

Wherein, from the aspect of copolyreaction and heat resistance, optimization styrene, vinyltoluene, (methyl) propylene Sour benzyl ester, (methyl) acrylic acid tricyclic [5.2.1.0^2,6] decane -8- base ester, N-phenylmaleimide, N- cyclohexyl Malaysia Acid imide, N- benzyl maleimide, bicyclic [2.2.1] -2- heptene.

In resin [K1], ratio of each structural unit in all structural units for constituting resin [K1], preferably

From the structural unit of (a)；2~60 moles of %

From the structural unit of (b)；40~98 moles of %,

More preferably

From the structural unit of (a)；10~50 moles of %

From the structural unit of (b)；50~90 moles of %.

When the ratio of the structural unit of resin [K1] within the above range when, with colored curable resin composition guarantor Deposit stability, formed pattern when developability and acquisition pattern excellent solvent resistance tendency.

Resin [K1] can refer to such as document " experimental method of Polymer Synthesizing " (height point is closed into experiment method) (great Jin Long Hang Zhe publishing house (strain) chemistry is with distribution in people the 1st edition the 1st brush on March 1st, 1972) documented by remember in method and the document The citation of load is manufactured.

Specifically, it can be listed below method, by (a) of specified amount and (b), the loadings reaction such as polymerization initiator and solvent holds In device, such as by being made deoxidizing atmosphere, being heated and kept the temperature while agitating by nitrogen displacement oxygen.In addition, used herein Polymerization initiator and solvent etc. be not particularly limited, substance usually used in the field can be used.For example, polymerization initiator can It enumerates, azo-compound (2,2 '-azodiisobutyronitriles, 2,2 '-azos two (2,4- methyl pentane nitrile) etc.) or organic peroxy Object (benzoyl peroxide etc.), as long as each monomer can be dissolved, can be enumerated as colored curable resin group as solvent Close the aftermentioned solvent etc. of the solvent (E) of object.In addition, the copolymer obtained can be directly using the solution after reaction, it is possible to use dense Solution after contracting or dilution, it is possible to use the solid (powder) taken out by the methods of reprecipitation.When particularly as the polymerization Solvent can be directly by the solution after reaction by using the solvent contained in colored curable resin composition of the invention For modulating colored curable resin composition of the invention, thus manufacturing process can be simplified.

In resin [K2], ratio of each structural unit in all structural units for constituting resin [K2], preferably

From the structural unit of (a)；2~45 moles of %

From the structural unit of (b)；2~95 moles of %

From the structural unit of (c)；1~65 mole of %,

More preferably

From the structural unit of (a)；5~40 moles of %

From the structural unit of (b)；5~80 moles of %

From the structural unit of (c)；5~60 moles of %.

When the ratio of the structural unit of resin [K2] within the above range when, with colored curable resin composition guarantor The solvent resistance of pattern of developability and acquisition when depositing stability, forming pattern, heat resistance and mechanical strength are inclined To.

Resin [K2] can take method identical with method documented by the manufacturing method for example as resin [K1] come into Row manufacture.

In resin [K3], ratio of each structural unit in all structural units for constituting resin [K3], preferably

From the structural unit of (a)；2~60 moles of %

From the structural unit of (c)；40~98 moles of %,

More preferably

From the structural unit of (a)；10~50 moles of %

From the structural unit of (c)；50~90 moles of %.

Resin [K3] can take method identical with method documented by the manufacturing method for example as resin [K1] come into Row manufacture.

Manufacture can be performed as follows in resin [K4]: obtaining the copolymer of (a) and (c), make carbon atom number 2 possessed by (b) Carboxylic acid possessed by~4 cyclic ether and (a) and/or carboxylic acid anhydrides carry out addition.

Firstly, according to the copolymerization for manufacturing (a) Yu (c) in the same manner with method documented by the manufacturing method as resin [K1] Object.At this point, it is preferred that ratio cited by the ratio and resin [K3] of each structural unit is identical.

Then, make the cyclic ether of carbon atom number 2~4 possessed by (b) and the carboxylic acid from (a) in above-mentioned copolymer And/or a part reaction of carboxylic acid anhydrides.

After the copolymer of manufacture (a) and (c), the atmosphere in flask is and then replaced as air by nitrogen, by (b), The catalysts (such as three (dimethylaminomethyl) phenol etc.) and polymerization inhibitor of carboxylic acid or carboxylic acid anhydrides and cyclic ether are (such as right Benzenediol etc.) etc. be added in flask, by being reacted 1~10 hour at such as 60~130 DEG C, can get resin [K4].

(b) usage amount is relative to 100 moles of (a), and preferably 5~80 moles, 10~75 moles more preferable.By in this model In enclosing, the pattern of storage stability with colored curable resin composition, developability when forming pattern and acquisition The tendency that solvent resistance, heat resistance, mechanical strength and the balance of sensitivity improve.Reactivity height, unreacted based on cyclic ether (b) be not easy the point of remaining, (b), preferably (b1) used in resin [K4], further preferred (b1-1).

Relative to (a), (b) and 100 mass parts of total amount (c), the usage amount of above-mentioned catalysts preferably 0.001~5 Mass parts.The usage amount of above-mentioned polymerization inhibitor is relative to (a), (b) and 100 mass parts of total amount (c), preferably 0.001~5 mass Part.

The reaction conditions such as loading method, reaction temperature and time are contemplated that manufacturing equipment or the calorific value that polymerization generates Deng being suitably adjusted.In addition, as polymerizing condition, it is contemplated that the calorific value etc. generated to manufacturing equipment or polymerization, suitably Ground adjusts loading method or reaction temperature.

As the first stage of resin [K5], method identical with the manufacturing method of above-mentioned resin [K1] can be taken, is obtained (b) with the copolymer of (c).Ibid, the copolymer of acquisition can be directly using the solution after reaction, it is possible to use concentration or dilution Solution afterwards, it is possible to use the solid (powder) taken out by the methods of reprecipitation.

The ratio of structural unit from (b) and (c), relative to the total of all structural units for constituting above-mentioned copolymer Molal quantity, it is preferred respectively

From the structural unit of (b)；5~95 moles of %

From the structural unit of (c)；5~95 moles of %,

More preferably

From the structural unit of (b)；10~90 moles of %

From the structural unit of (c)；10~90 moles of %.

Further, with the manufacturing method of resin [K4] under the same conditions, by making carboxylic acid or carboxylic acid possessed by (a) Acid anhydride, the possessed cyclic ether from (b) of copolymer with (b) and (c) are reacted, be can get resin [K5].

Relative to 100 moles of (b), preferably 5~80 moles of usage amount with (a) of above-mentioned copolymer reaction.Based on ring-type The reactivity of ether is high, unreacted (b) is not easy remaining, and (b) used in resin [K5] is preferred (b1), further preferred (b1- 1)。

Resin [K6] be resin [K5] further with resin obtained by carboxylic acid anhydride reactant.

Make cyclic ether and carboxylic acid or carboxylic acid anhydrides reacts hydroxyl generated, with carboxylic acid anhydride reactant.

Carboxylic acid anhydrides can be enumerated, maleic anhydride, citraconic anhydride, itaconic anhydride, 3- vinylphthalic acid acid anhydride, 4- vinyl Phthalic anhydride, 3,4,5,6- tetrabydrophthalic anhydrides, 1,2,3,6- tetrabydrophthalic anhydrides, dimethyl tetrahydro neighbour's benzene Bicyclic [2.2.1] -2- heptene acid anhydrides of dicarboxylic acid anhydride, 5,6- dicarboxyl etc..Usage amount 1 of the usage amount of carboxylic acid anhydrides relative to (a) Mole, preferably 0.5~1 mole.

As resin (B), concrete example has (methyl) acrylic acid 3, and 4- epoxycyclohexyl-methyl ester/(methyl) acrylic acid is total Polymers, (methyl) acrylic acid 3,4- epoxy tricyclic [5.2.1.0^2.6] resins [K1] such as decyl ester/(methyl) acrylic copolymer； (methyl) glycidyl acrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, the contracting of (methyl) acrylic acid Water glyceryl ester/styrene/(methyl) acrylic copolymer, (methyl) acrylic acid 3,4- epoxy tricyclic [5.2.1.0^2.6] decyl Ester/(methyl) acrylic acid/N- N-cyclohexylmaleimide copolymer, (methyl) acrylic acid 3,4- epoxy tricyclic [5.2.1.0^2.6] Decyl ester/(methyl) acrylic acid/vinyl toluene copolymer, 3- methyl -3- (methyl) acryloyloxymethyl oxetanes/ The resins such as (methyl) acrylic/styrene copolymer [K2]；(methyl) benzyl acrylate/(methyl) acrylic copolymer, benzene Ethylene/(methyl) acrylic copolymer, (methyl) benzyl acrylate/(methyl) acrylic acid tricyclodecyl ester/(methyl) propylene The resins such as acid copolymer [K3]；(methyl) benzyl acrylate/(methyl) acrylic copolymer shrinks sweet with (methyl) acrylic acid Resin that oil base ester addition obtains, (methyl) acrylic acid tricyclodecyl ester/styrene/(methyl) acrylic copolymer and (methyl) Resin that glycidyl acrylate addition obtains, (methyl) acrylic acid tricyclodecyl ester/(methyl) benzyl acrylate/ The resins [K4] such as the resin that (methyl) acrylic copolymer and (methyl) glycidyl acrylate addition obtain；(methyl) third Resin obtained by olefin(e) acid tricyclodecyl ester/(methyl) glycidyl acrylate copolymer is reacted with (methyl) acrylic acid, (methyl) acrylic acid tricyclodecyl ester/styrene/(methyl) glycidyl acrylate copolymer and (methyl) acrylic acid The resins such as resin obtained by reaction [K5]；(methyl) acrylic acid tricyclodecyl ester/(methyl) glycidyl acrylate is total to Resin obtained by polymers is reacted with (methyl) acrylic acid, the resins such as resin obtained by further being reacted with tetrabydrophthalic anhydride [K6] etc..

Resin (B) is preferably selected from one of the group being made of resin [K1], resin [K2] and resin [K3], more preferably Selected from one of the group being made of resin [K2] and resin [K3].When for these resins, colored curable resin composition Developability it is excellent.

From the viewpoint of from the adhesiveness of colored pattern and substrate, further preferred resin [K2].

The weight average molecular weight of the polystyrene conversion of resin (B) is usually 3,000~100,000, preferably 5,000~50, 000, more preferable 5,000~35,000, further preferred 5,000~30,000, even more preferably 6,000~30,000.When Molecular weight within the above range when, have and improve hardness of film, residual film ratio is also high, unexposed portion dissolubility in developer solution Well, the tendency that the resolution of colored pattern is improved.

Molecular weight distribution [weight average molecular weight (Mw)/number-average molecular weight (Mn)] は, preferably 1.1~6 of resin (B), it is more excellent Select 1.2~4 In あ Ru.

The acid value of resin (B) is usually 20~170mg-KOH/g, preferably 30~170mg-KOH/g, more preferable 40~ 170mg-KOH/g, further preferred 50~170mg-KOH/g, even more preferably 50~150mg-KOH/g, particularly preferred 60 ~150mg-KOH/g, particularly preferred 60~135mg-KOH/g, most preferably 70~135mg-KOH/g.Acid value herein is conduct The value that the amount (mg) of potassium hydroxide needed for neutralizing 1g resin is measured, can be dripped by using potassium hydroxide aqueous solution It is fixed to acquire.

Relative to the total amount of solid component, the content of resin (B) preferably 7~65 mass %, more preferable 10~60 mass %, Further preferred 13~60 mass %, even more preferably 17~55 mass %.When resin (B) content within the above range When, there is colored pattern easy to form, the tendency that furthermore resolution of colored pattern and residual film ratio are improved.

For example there are the living radicals and/or acid that are generated by polymerization initiator (D) to gather for polymerizable compound (C) The compound of conjunction, such as the compound etc. of the ethylene unsaturated bond with polymerism, preferably (methyl) acrylate compounds.

As the polymerizable compound with 1 ethylene unsaturated bond, for example there are such as nonyl phenyl carbitol propylene Acid esters, acrylic acid 2- hydroxyl -3- phenoxy propyl ester, 2- ethylhexyl carbitol acrylate, acrylic acid 2- hydroxyethyl ester, N-vinyl pyrrolidone etc. and above-mentioned (a), (b) and (c).

As the polymerizable compound with 2 ethylene unsaturated bonds, for example there are such as 1,6- hexylene glycols two (methyl) Acrylate, ethylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) propylene Acid esters, bis- (acryloyl-oxyethyl) ethers of bisphenol-A, 3- methyl pentanediol two (methyl) acrylate etc..

Wherein, polymerizable compound (C) is preferably with the polymerizable compound of 3 ethylene unsaturated bonds.As in this way Polymerizable compound, for example there are such as trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylic acid Ester, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) propylene Acid esters, tripentaerythritol eight (methyl) acrylate, tripentaerythritol seven (methyl) acrylate, tetrapentaerythritol ten (methyl) Acrylate, tetrapentaerythritol nine (methyl) acrylate, three (2- (methyl) acryloyl-oxyethyl) isocyanuric acid esters, second two Alcohol is modified pentaerythrite four (methyl) acrylate, glycol-modified dipentaerythritol six (methyl) acrylate, propylene glycol and changes Property pentaerythrite four (methyl) acrylate, propylene glycol modified ジ pentaerythrite six (methyl) acrylate, caprolactone modification season Penta tetrol four (methyl) acrylate, caprolactone modification dipentaerythritol six (methyl) acrylate etc..

Wherein, preferably dipentaerythritol five (methyl) acrylate and dipentaerythritol six (methyl) acrylate.

The weight average molecular weight of polymerizable compound (C) preferably 150 or more 2,900 hereinafter, more preferable 150 or more 1,500 with Under, further preferred 150 or more 800 hereinafter, even more preferably 190 or more 700 or less.

Relative to the total amount of solid component, the content of polymerizable compound (C) is usually 5~65 mass %, and preferably 7~65 Quality %, more preferable 10~60 mass %, further preferred 13~60 mass %, even more preferably 17~55 mass %.

In addition, the content ratio (resin (B): polymerizable compound (C)) of resin (B) and polymerizable compound (C) are with quality On the basis of, preferably 20: 80~80: 20, more preferable 35: 65~80: 20.

When the content of polymerizable compound (C) within the above range when, with colored pattern formation when residual film ratio and filter The tendency that the chemical resistance of color device is improved.

Polymerization initiator (D) starts the chemical combination of polymerization as long as living radical, acid etc. can be generated by light or heat effect Object is not particularly limited, and well known polymerization initiator can be used.

As polymerization initiator (D), for example there are O- acyl group oxime compound, benzene alkyl ketone compound, double imidazole compounds, three Piperazine compound and acylphosphine oxide compound etc..

The O- acyl group oxime compound is the compound with part-structure shown in formula (d1).Hereinafter, * indicates bonding position It sets.

As the O- acyl group oxime compound, for example there are such as N- benzoyloxy -1- (4- phenylsulfartyl phenyl) -1- fourths Ketone -2- imines, N- benzoyloxy -1- (4- phenylsulfartyl phenyl) -1- octanone -2- imines, N- benzoyloxy -1- (4- benzene Base sulfenyl phenyl) -3- cyclopenta -1- acetone -2- imines, N- acetoxyl group -1- [9- ethyl -6- (2- methyl benzoyl) - 9H- carbazole -3- base] ethane -1- imines, N- acetoxyl group -1- [9- ethyl -6- { 2- methyl -4- (3,3- dimethyl -2,4- bis- Oxocyclopentyl methyl oxygroup) benzoyl } -9H- carbazole -3- base] ethane -1- imines, N- acetoxyl group -1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -3- cyclopenta propane -1- imines, N- benzoyloxy -1- [9- ethyl -6- (2- methyl benzoyl) -9H- carbazole -3- base] -3- cyclopenta -1- acetone -2- imines etc..Also gorgeous good solid (イ Le can be used ガキユア) OXE01, OXE02 (above, BASF society system), the commercially available products such as N-1919 (ADEKA society system).Wherein, O- acyl group oximate Object is closed to be preferably selected from by N- benzoyloxy-1- (4- phenylsulfartyl phenyl)-1- butanone-2-imines, N- benzoyloxy-1- (4- phenylsulfartyl phenyl) -1- octanone -2- imines and N- benzoyloxy -1- (4- phenylsulfartyl phenyl) -3- cyclopenta -1- At least one kind of, more preferable N- benzoyloxy -1- (4- phenylsulfartyl phenyl) -1- octanone-in the group of acetone -2- imines composition 2- imines.

The benzene alkyl ketone compound is the chemical combination with part-structure shown in part-structure shown in formula (d2) or formula (d3) Object.In these part-structures, phenyl ring can have substituent group.

Compound with part-structure shown in formula (d2) can be enumerated, such as 2- methyl -2- morpholino -1- (4- methyl mercapto Phenyl) -1- acetone, 2- dimethylamino -1- (4- morpholinyl phenyl) -2- benzyl -1- butanone, 2- (dimethylamino) -2- [(4- Aminomethyl phenyl) methyl] -1- [4- (4- morpholinyl) phenyl] -1- butanone etc..Can also be used it is gorgeous it is good it is solid 369,907 and 379 (more than BASF society system) etc. commercially available products.

Compound with part-structure shown in formula (d3) can be enumerated, such as 2- hydroxy-2-methyl -1- phenyl-propane -1- Ketone, 2- hydroxy-2-methyl -1- (4- (2- hydroxyl-oxethyl) phenyl) -1- acetone, 1- hydroxycyclohexylphenylketone, 2- hydroxyl -2- Methyl-1-(4- isopropenyl phenyl)-1- acetone oligomer, α, α-diethoxy acetophenone, benzyl dimethyl ketal etc..

Consider from sensitivity, benzene alkyl ketone compound, preferably the compound with part-structure shown in formula (d2).It is described double Imidazolium compounds is the compound that such as formula (d5) indicates.

[in formula (d5), R⁵¹~R⁵⁶Expression can have the aryl of the carbon atom number 6~10 of substituent group.]

For example there are such as phenyl, toluyl, xylyl, ethylphenyl and naphthalenes for the aryl of carbon atom number 6~10 Deng preferred phenyl.

As substituent group, for example there are such as halogen atom, alkoxies of carbon atom number 1~4 etc..Halogen atom is that for example fluorine is former Son, chlorine atom, bromine atom, iodine atom etc., preferably chlorine atom.For example there are such as methoxyl groups, second for the alkoxy of carbon atom number 1~4 Oxygroup, propoxyl group, butoxy etc., preferably methoxyl group.

As double imidazole compound, for example there are such as 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl double imidazoles, 2,2 '-bis- (2,3- ジ chlorphenyl) -4,4 ', 5,5 '-tetraphenyl double imidazoles (such as JPH06-75372-A, JPH06-75373-A Equal references.), 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-tetraphenyl double imidazoles, 2,2 '-bis- (2- chlorphenyls) -4,4 ', 5, The double imidazoles of 5 '-four (alkoxyl phenyls), 2, the double imidazoles of 2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (dialkoxy phenyl), 2, 2 '-bis- (2- chlorphenyls) -4,4 ', 5,5 '-four (tri-alkoxy phenyl) double imidazoles are (for example, see JPS48-38403-B, JPS62- 174204-A etc.), 4,4 ' 5, the imidazolium compounds that the phenyl of 5 '-positions is replaced by carbonylic alkoxy is (for example, see JPH07- 10913-A etc.) etc..Wherein, preferably following formula indicate compound and their mixture.

As the triaizine compounds, for example there are bis- (the trichloromethyl) -6- (4- methoxyphenyl) -1,3,5- of such as 2,4- Triazine, 2,4- bis- (trichloromethyl) -6- (4- methoxyl group naphthalene) -1,3,5-triazines, bis- (the trichloromethyl) -6- piperonyls-of 2,4- Bis- (trichloromethyl) -6- (4- the methoxyl-styrene) -1,3,5-triazines of 1,3,5-triazines, 2,4-, 2,4- bis- (trichloromethyls) - 6- (2- (5- methylfuran -2- base) vinyl) -1,3,5-triazines, bis- (the trichloromethyl) -6- of 2,4- (2- (furans -2- base) second Alkenyl) -1,3,5-triazines, bis- (the trichloromethyl) -6- of 2,4- (2- (4- diethylamino -2- aminomethyl phenyl) vinyl) -1,3, Bis- (the trichloromethyl) -6- of 5- triazine, 2,4- (2- (3,4- Dimethoxyphenyl) vinyl) -1,3,5-triazines etc..

As the acylphosphine oxide compound, for example there are 2,4,6-trimethylbenzoyldiphenylphosphine oxide etc..

Further, as polymerization initiator (D), for example there are benzoin, benzoin methyl ether, benzoin ethyl ether, benzene The benzoins compound such as acyloin isopropyl ether, benzoin isobutyl ether；Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4- benzene Base benzophenone, 4- benzoyl -4 '-dimethyl diphenyl sulfide, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, The benzophenone cpds such as 2,4,6- tri-methyl benzophenones；The naphtoquinone compounds such as 9,10- phenanthrenequione, 2- ethyl hydrazine, camphorquinone； 10- butyl -2- chloro-acridine ketone, benzil, phenylglyoxalates methyl esters, titanocenes compound etc..These compounds preferably with it is aftermentioned Polymerization trigger auxiliary agent (D1) (especially amine) be applied in combination.

Polymerization initiator (D) preferably comprise selected from benzene alkyl ketone compound, triaizine compounds, acylphosphine oxide compound, At least one kind of polymerization initiator in the group of O- acyl group oxime compound and double imidazole compound composition, further preferably O- acyl group The polymerization initiator of oxime compound.

Relative to 100 mass parts of total amount of resin (B) and polymerizable compound (C), the content of polymerization initiator (D) is excellent Select 0.1~40 mass parts, more preferable 0.1~30 mass parts, further preferred 1~30 mass parts, even more preferably 1~20 matter Measure part.

Polymerization trigger auxiliary agent (D1) is the polymerization for promoting to be caused by polymerization initiator the photopolymerizable compound of polymerization Compound or sensitizer.When comprising polymerization trigger auxiliary agent (D1), usually it is applied in combination with polymerization initiator (D).

Polymerization trigger auxiliary agent (D1) can be enumerated, amine compounds, alkoxy anthracene compound, thioxanthone compounds and carboxylic acid chemical combination Object etc..

The amine compounds can be enumerated, triethanolamine, methyl diethanolamine, triisopropanolamine, 4- dimethylamino benzene first Sour methyl esters, ethyl 4-dimethylaminobenzoate, 4- dimethylaminobenzoic acid isopentyl ester, benzoic acid 2- dimethylaminoethyl Ester, 4- dimethylaminobenzoic acid 2- ethylhexyl, N, N- dimethyl-p-toluidine, 4,4 '-two (dimethylamino) hexichol first Ketone (common name Michler's keton), 4,4 '-two (diethylamino) benzophenone, 4,4 '-two (ethylmethylamino) benzophenone etc., In preferably 4,4 '-two (diethylamino) benzophenone.It can also be used EAB-F (hodogaya chemical industry (strain) system) etc. commercially available Product.

The alkoxy anthracene compound can be enumerated, 9,10- dimethoxy anthracenes, 2-ethyl-9,10-dimethoxypyrene, 9,10- Diethoxy anthracene, 2- ethyl -9,10- diethoxy anthracene, 9,10- dibutoxy anthracene, 2- ethyl -9,10- dibutoxy anthracene etc..

As the thioxanthone compounds, for example there are 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- diethyl thiophenes Ton ketone, 2,4-, bis- clopenthixal ketone, the chloro- 4- propoxythioxanthone of 1- etc..

As the carboxylic acid compound, for example there are thiophenyl acetic acid, methylphenyl-sulfanyl acetic acid, ethylthiophenyl acetic acid, first Base ethylthiophenyl acetic acid, dimethyl benzene ethyl thioglycollic acid, Methoxv-phenylsulfanvl acetic acid, dimethoxyphenylthio acetic acid, chlorobenzene sulphur Guanidine-acetic acid, dichloro-benzenes ethyl thioglycollic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio acetic acid, N- naphthalene glycine, naphthalene oxygen Guanidine-acetic acid etc..

When using these polymerization trigger auxiliary agent (D1), content is total relative to resin (B) and polymerizable compound (C) Measure 100 mass parts, preferably 0.1~30 mass parts, more preferable 1~20 mass parts.When the amount of polymerization trigger auxiliary agent (D1) is in the model When enclosing interior, have and colored pattern is further formed with high sensitivity, improves the tendency of colour filter productivity.

Solvent (E) is not particularly limited, and solvent usually used in the field can be used.For example there are such as ester solvent (molecules The interior solvent containing-COO-, without-O-), ether solvents (intramolecular contains-O-, the solvent without-COO-), ether-ether solvent (point Contain the solvent of-COO- and-O- in sub), ketone solvent (intramolecular contains-CO-, the solvent without-COO-), alcoholic solvent (molecule It is interior containing OH, without the solvent of-O- ,-CO- and-COO-), aromatic hydrocarbon solvents, amide solvent, dimethyl sulfoxide etc..

Ester solvent can be enumerated, methyl lactate, ethyl lactate, butyl lactate, 2- hydroxy-isobutyric alkanoic acid methyl esters, ethyl acetate, N-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyric acid fourth Ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, adnoral acetate and Gamma-butyrolacton etc..

Ether solvents can be enumerated, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol only son Base ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Single ethylether, propylene glycol monopropyl ether, glycol monobutyl ether, 3- methoxyl group-n-butyl alcohol, 3- methoxyl group -3- methyl butanol, four Hydrogen furans, oxinane, Isosorbide-5-Nitrae-dioxanes, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Methylethyl Ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methyl anisole etc..

As ether-ether solvent, for example there are methoxy menthyl acetate, ethyl methoxyacetate, methoxyacetic acid butyl esters, ethoxy Acetic acid methyl ester, ethoxy ethyl acetate, 3- methoxy methyl propionate, 3- methoxypropionate, 3- ethoxypropanoate, 3- ethoxyl ethyl propionate, 2- methoxy methyl propionate, 2- methoxypropionate, 2- methoxy propyl propyl propionate, 2- ethyoxyl Methyl propionate, 2- ethoxyl ethyl propionate, 2- methoxyl group -2 Methylpropionic acid methyl esters, 2- ethyoxyl -2 Methylpropionic acid ethyl ester, 3- Methoxybutyl acetic acid esters, 3- methyl -3- methoxybutyl acetic acid esters, propylene glycol monomethyl ether, propylene glycol list ethyl Ether acetic acid ester, propylene glycol monopropyl ether acetic acid esters, ethylene glycol single methyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, diethyl Glycol list monoethyl ether acetate, diethylene glycol monobutyl ether acetic acid esters, dipropylene glycol methyl ether acetic acid esters etc..

As ketone solvent, for example there are 4- hydroxy-4-methyl-2-pentanone, acetone, 2- butanone, 2-HEPTANONE, 3- heptanone, 4- heptan Ketone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone, isophorone etc..

As alcoholic solvent, for example there are methanol, ethyl alcohol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerol Deng.

As aromatic hydrocarbon solvents, for example there are the Ga such as benzene,toluene,xylene, mesitylene.

As amide solvent, for example there are n,N-Dimethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidones Deng.

These solvents may be used alone, two or more kinds can also be used.

Wherein, preferably propylene glycol monomethyl ether, ethyl lactate, propylene glycol monomethyl ether, 3- ethoxy-propionic acid second Ester, ethylene glycol single methyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3- methoxyl group fourth Yl acetate, 3- methoxyl group-n-butyl alcohol, 4- hydroxy-4-methyl-2-pentanone, n,N-Dimethylformamide and N- methylpyrrole Alkanone, more preferable propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether Acetic acid esters, ethyl lactate, 3- methoxybutyl acetic acid esters, 3- methoxyl group-n-butyl alcohol, 3- ethoxyl ethyl propionate and N- methyl Pyrrolidones.

The content of solvent (E), relative to the total amount of colored curable resin composition, preferably 70~95 mass % are more excellent Select 75~92 mass %, further preferred 75~90 mass %.In other words, the solid component of colored curable resin composition is excellent Select 5~30 mass %, more preferable 8~25 mass %, further preferred 10~25 mass %.

When the content of solvent (E) within the above range when, have coating when flatness improve, in addition, formed colour filter When the colour saturation sufficiently tendency that makes display characteristic improve.

Colored curable resin composition of the invention can contain levelling agent (F).

Levelling agent (F) can be enumerated, silicone-based surfactant, fluorine system surfactant and the silicone-based table with fluorine atom Face activating agent etc..They can have polymerizable group in side chain.

Silicone-based surfactant can be enumerated, and intramolecular has the surfactant etc. of siloxanes key.It can specifically enumerate, TORAY silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: eastern レ One ニ Application グ (strain) of ダウ U system), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (SHIN-ETSU HANTOTAI's chemical industry (strain) system), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (mono- マ Application スマテリア Le ズジヤパ Application contract commercial firm system of モメ Application テイ Block パ Off オ) etc..

Above-mentioned fluorine system surfactant can be enumerated, and intramolecular has the surfactant etc. of fluoro carbochain.It can specifically arrange Lift Off ロラ mono- De (registered trademark) FC430, FC431 (Sumitomo 3M (strain) system), メガ Off ア Star Network (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (DIC (strain) system), エ Off ト Star プ (registered trademark) EF301, EF303, EF351, EF352 (Mitsubishi's マテリア Le electronics is melted into (strain) system), mono- Off ロ Application (registered trademark) of サ S381, S382, SC101, SC105 (Asahi Glass (strain) system) and E5844 ((strain) ダイキ Application Off アイ Application ケミカ Le research It is made) etc..

The above-mentioned silicone-based surfactant with fluorine atom can be enumerated, and intramolecular has siloxanes key and fluoro carbochain Surfactant etc..メガ Off ア Star Network (registered trademark) R08, BL20, F475, F477 and F443 (DIC can specifically be enumerated (strain) system) etc..

The content of levelling agent (F), relative to the total amount of colored curable resin composition, preferably 0.001 mass % or more 0.2 mass % hereinafter, more preferable 0.002 mass % or more, 0.1 mass % hereinafter, further preferred 0.005 mass % or more 0.07 mass % or less.The content of levelling agent (F) within the above range when, the flatness of colour filter can be made to improve.

Colored curable resin composition of the invention can contain filler as needed, other high-molecular compounds, glue Close the additives well-known in the art such as promotor, antioxidant, light stabilizer, chain-transferring agent.

Colored curable resin composition of the invention can be by mixing such as colorant (A), resin (B), polymerism Compound (C), polymerization initiator (D) and solvent used as needed (E), levelling agent (F), polymerization trigger auxiliary agent (D1) with And other compositions are prepared.

When pigment contains pigment (P), pigment is mixed in advance with some or all of solvent (E) preferably, uses pearl Grinding machine etc. is allowed to disperse, until the average grain diameter of pigment becomes 0.2 μm of degree below.At this point, can also mix as needed State part or all of pigment dispersing agent, resin (B).Can by mixed in the dispersible pigment dispersion so obtained it is remaining at Point, defined concentration is made, thus prepares target coloration hardening resin composition.

It is preferred that in advance by compound (1), compound (1 '), compound (2), compound (3), compound (4) or compound (5) etc. the compound with cumarin skeleton is dissolved in part or all of solvent (E), is configured to solution.It is preferred that will The filter in 0.01~1 μm or so of aperture of the solution is filtered.

It is preferred that the filter in 0.01~10 μm or so of aperture of mixed colored curable resin composition was carried out Filter.

As the method by colored curable resin composition manufacture colored pattern of the invention, photoetching process, spray can be enumerated The method of the use of ink and water, print process etc..Wherein preferred photoetching process.Photoetching process is that above-mentioned colored curable resin composition is coated on substrate, is led to It crosses drying and forms coloring compositions nitride layer, the method that the composition layer is exposed via photomask, is developed.In photoetching process, lead to It crosses in exposure without using photomask, and/or without development, the coloring film of said combination nitride layer solidfied material can be formed. The colored pattern or coloring film being thusly-formed are colour filter of the invention.

The pattern film thickness of production is not particularly limited, and can be suitably adjusted according to purpose or purposes etc., such as 0.1~30 μm, preferably 0.1~20 μm, further preferred 0.5~6 μm.

The soda lime glass of quartz glass, borosilicate glass, aluminosilicate glass, surface covering silica can be used in substrate The equal resin plates such as glass plates or polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, above-mentioned base Aluminium, silver, silver/copper/palldium alloy film etc. are formd on plate.Other color-filter layer, resin layer, crystal can be formed on these substrates Pipe, circuit etc..

By photoetching process formed each color pixel can known or usual device and under the conditions of carry out.Such as it can be performed as follows Production.

Firstly, colored curable resin composition is coated on substrate, it is dry by heat drying (preliminary drying) and/or decompression The volatile ingredients such as dry removing solvent are allowed to drying, obtain smooth coloring compositions nitride layer.

Coating method can be enumerated, spin-coating method, slot coated method, slit & method of spin coating etc..

Preferably 30~120 DEG C, more preferable 50~110 DEG C of temperature when being thermally dried.In addition, heating time preferably 10 Second~60 minutes, more preferable 30 seconds~30 minutes.

When being dried under reduced pressure, carried out preferably under the pressure of 50~150Pa, under 20~25 DEG C of temperature range.

The film thickness of coloring compositions nitride layer is not particularly limited, and can be properly selected according to the film thickness of target colour filter.

Then, coloring compositions nitride layer is exposed via photomask to form it into target coloration pattern.The photomask On pattern be not particularly limited, can according to intended applications use pattern.

Exposure light source used, the preferably light source of the light of generation 250~450nm wavelength.Such as it can be to the light less than 350nm Ended using the optical filter by the end of the wavelength region, the light near 436nm, near 408nm, near 365nm is used The bandpass filter for selecting the wavelength region carries out selective taking-up.It can specifically enumerate, mercury lamp, light emitting diode, halogenation gold Belong to lamp, halogen lamp etc..

In order to integrally can equably irradiate parallel rays to plane of exposure, or keep photomask and coloring compositions nitride layer correctly right Position is, it is preferable to use the exposure devices such as mask aligner, step-by-step exposure machine.

Developed by contacting the coloring compositions nitride layer after exposing with developer solution, color-patch map can be formed on substrate Case.By development, the unexposed portion of coloring compositions nitride layer can be made to be dissolved in developer solution to remove.

The water of the developer solution preferably alkali compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide Solution.Concentration in the aqueous solution of these alkali compounds, preferably 0.01~10 mass %, more preferable 0.02~5 mass %.Into One step, developer solution can also contain surfactant.

Any one of paddling process, infusion process and spray-on process etc. can be used in developing method.Further, when development, substrate It can be tilted with any angle.

It is preferably washed after development.

Further, it is dried after preferably being carried out to the colored pattern film of acquisition.Preferably 150~250 DEG C of temperature of baking afterwards, it is more excellent Select 160~235 DEG C.It dries the time preferably 1~120 minute, more preferable 10~60 minutes afterwards.

According to the present invention, it is possible to provide the colored curable resin composition of the especially colour filter of high brightness can be manufactured. The colour filter is suitable for display device (such as liquid crystal display device, organic el device, Electronic Paper etc.) and solid-state image pickup member Colour filter in part etc..

Embodiment

Next embodiment is enumerated, more specific description is carried out to the present invention.Example in " % " and " part " as long as no It illustrates, as quality % and mass parts.

In synthesis example below, the structure NMR (JMM-ECA-500 of compound；Japan Electronics (strain) system) or mass spectrum point Analysis (1200 type of LC:Agilent system, MASS:Agilent LC/MSDD6130 type) is confirmed.

The measurement of the weight average molecular weight (Mw) and number-average molecular weight (Mn) of the polystyrene conversion of resin is existed by GPC method It is carried out under the following conditions.

Device；HLC-8120GPC (eastern ソ mono- (strain) system)

Chromatographic column；TSK-GELG2000HXL

Chromatogram column temperature；40℃

Solvent；THF

Flow velocity；1.0mL/min

Test solution solid component concentration；0.001~0.01 mass %

Injection rate；50μL

Detector；RI

Standard substance is used in correction；TSK STANDARD POLYSTYRENE

F-40、F-4、F-288、A-2500、A-500

(eastern ソ mono- (strain) system)

The ratio between weight average molecular weight and number-average molecular weight that polystyrene obtained above is converted (Mw/Mn) are used as molecule Amount distribution.

Synthesis example 1

Will be bis- 10.6 parts of (3- amino-4-hydroxylphenyl) sulfone (Tokyo chemical conversion industry (strain) system), 4- (diethylamino) water 14.6 parts of poplar aldehyde (Tokyo chemical conversion industry (strain) system), 3.17 parts of benzoic acid (Tokyo chemical conversion industry (strain) system), 1- amylalcohol (Tokyo At industrial (strain) system) 183 parts and 8.61 parts of cyan-acetic ester (Tokyo chemical conversion industry (strain) system) mix, stirred at 120 DEG C It mixes 3 hours.14.6 parts of 4- (diethylamino) salicylide (Tokyo chemical conversion industry (strain) system), benzene first are added in the reaction solution 3.17 parts of sour (Tokyo chemical conversion industry (strain) system) and 8.61 parts of cyan-acetic ester (Tokyo chemical conversion industry (strain) system), in 120 It is stirred 12 hours at DEG C.After above-mentioned reaction solution is cooled to room temperature, the crystallization of precipitation is obtained as the residue filtered.In the residue 236 parts and 234 parts of isopropyl alcohol of middle addition acetonitrile, after stirring, insoluble matter is obtained as the residue filtered.It is added in the residue 236 parts and 234 parts of isopropyl alcohol of acetonitrile, after stirring, insoluble matter is obtained as the residue filtered.Chloroform is added in the residue It 2220 parts, is stirred, filters.530 parts of 5% sodium hydrate aqueous solution is added in the filtrate, is stirred, it is molten to take out chloroform Liquid layer.610 parts of 18% sodium-chloride water solution is added in the chloroformic solution, is stirred, takes out chloroformic solution layer.In the chloroform 10 parts of magnesium sulfate are added in solution, is filtered after being stirred.The solvent of filtrate is distilled off with rotary evaporator, then, in It is dried under reduced pressure at 60 DEG C, obtains 19.5 parts of compound of formula (1-148) expression.With¹H-NMR confirms structure.

¹H-NMR (500MHz, DMSO-d6): 1.14 (12H, t), 3.50 (8H, q), 6.61 (2H, d), 6.82 (2H, dd), 7.71 (2H, d), 7.95 (2H, d), 8.04 (2H, dd), 8.43 (2H, d), 8.83 (2H, s)

Synthesis example 2

Mix bis- (3- amino-4-hydroxylphenyl) dimethylmethanes (Changzhou Sunlight Medical Raw Material Co., Ltd.'s system) 10.1 Part, 15.2 parts of 4- (diethylamino) salicylide (Tokyo chemical conversion industry (strain) system), benzoic acid (Tokyo chemical conversion industry (strain) system) 3.26 parts, 191 parts of 1- amylalcohol (Tokyo chemical conversion industry (strain) system) and cyan-acetic ester (Tokyo chemical conversion industry (strain) system) It 8.89 parts, is stirred 3 hours at 120 DEG C.4- (diethylamino) salicylide (Tokyo chemical conversion industry is added in the reaction solution (strain) system) 8.39 parts, 1.80 parts of benzoic acid (Tokyo chemical conversion industry (strain) system), 1- amylalcohol (Tokyo chemical conversion industry (strain) system) 8.40 4.91 parts of part and cyan-acetic ester (Tokyo chemical conversion industry (strain) system), are stirred 12 hours at 120 DEG C.By above-mentioned reaction solution After being cooled to room temperature, the crystallization of precipitation is obtained as the residue filtered.332 parts of acetonitrile of addition, insoluble after stirring in the residue Object is obtained as the residue filtered.315 parts of acetonitrile, after stirring are added in the residue, insoluble matter is obtained as the residue filtered. The residue is dried under reduced pressure at 60 DEG C, obtains 23.6 parts of compound of formula (1-169) expression.With¹H-NMR confirms structure.

¹H-NMR (500MHz, DMSO-d6): 1.14 (12H, t), 1.80 (6H, s), 3.49 (8H, q), 6.60 (2H, d), 6.81 (2H, dd), 7.19 (2H, dd), 7.59 (2H, d), 7.67 (2H, d), 7.68 (2H, d), 8.75 (2H, s)

Synthesis example 3

Adjacent amino is mixed to benzylphenol (referring to Journal of the American Chemical Society (1935), 57,1697-8.) 10.3 parts, 10.0 parts of 4- (diethylamino) salicylide (Tokyo chemical conversion industry (strain) system), benzene first 2.16 parts of sour (Tokyo chemical conversion industry (strain) system), 125 parts of 1- amylalcohol (Tokyo chemical conversion industry (strain) system) and cyan-acetic ester 5.85 parts of (Tokyo chemical conversion industry (strain) system), is stirred 3 hours at 120 DEG C.4- (diethylamino) water is added in the solution 10.0 parts of poplar aldehyde (Tokyo chemical conversion industry (strain) system), 2.16 parts of benzoic acid (Tokyo chemical conversion industry (strain) system), 1- amylalcohol (Tokyo At industrial (strain) system) 12.5 parts and 5.85 parts of cyan-acetic ester (Tokyo chemical conversion industry (strain) system), stir 12 at 120 DEG C Hour.After above-mentioned reaction solution is cooled to room temperature, solvent is distilled off with rotary evaporator, obtains residue.With column chromatography pair The residue is purified, and the compound of formula (1-1) expression is obtained.

Synthesis example 4

Mix adjacent amino to 12.9 parts of phenyl sulfonyl phenol (referring to Japanese Patent Laid-Open No. Sho 49-126979 bulletin), 10.0 parts of 4- (diethylamino) salicylide (Tokyo chemical conversion industry (strain) system), benzoic acid (Tokyo chemical conversion industry (strain) system) 2.16 5.85 parts of part, 125 parts of 1- amylalcohol (Tokyo chemical conversion industry (strain) system) and cyan-acetic ester (Tokyo chemical conversion industry (strain) system), It is stirred 3 hours at 120 DEG C.4- (diethylamino) salicylide (Tokyo chemical conversion industry (strain) system) 10.0 is added in the solution Part, 2.16 parts of benzoic acid (Tokyo chemical conversion industry (strain) system), 12.5 parts of 1- amylalcohol (Tokyo chemical conversion industry (strain) system) and cyano 5.85 parts of ethyl acetate (Tokyo chemical conversion industry (strain) system), is stirred 12 hours at 120 DEG C.Above-mentioned reaction solution is cooled to room temperature Afterwards, solvent is distilled off with rotary evaporator, obtains residue.The residue is purified with column chromatography, obtains formula (1-60) The compound of expression.

Synthesis example 5

Mix 9.84 parts of bis- (3- amino-4-hydroxylphenyl) fluorenes of 9,9- (Tokyo chemical conversion industry (strain) system), 4- (diethyl amino Base) 10.0 parts of salicylide (Tokyo chemical conversion industry (strain) system), 2.16 parts of benzoic acid (Tokyo chemical conversion industry (strain) system), 1- amylalcohol 125 parts of (Tokyo chemical conversion industry (strain) system) and 5.86 parts of cyan-acetic ester (Tokyo chemical conversion industry (strain) system), is stirred in 120 DEG C It mixes 3 hours.By the reaction solution and 10.0 parts of 4- (diethylamino) salicylide (Tokyo chemical conversion industry (strain) system), benzoic acid 2.16 parts of (Tokyo chemical conversion industry (strain) system), 12.5 parts of 1- amylalcohol (Tokyo chemical conversion industry (strain) system) and cyan-acetic ester (Tokyo chemical conversion industry (strain) system) 5.86 parts of mixing, it is stirred 12 hours at 120 DEG C.Above-mentioned reaction solution is cooled to room temperature Afterwards, solvent is distilled off with rotary evaporator, obtains residue.The residue is purified with column chromatography, obtains formula (1-233) The compound of expression.

Synthesis example 6

Mix 10.0 parts of 4- amino-3-hydroxy formic acid (Tokyo chemical conversion industry (strain) system), 4- (diethylamino) bigcatkin willow 12.8 parts of aldehyde (Tokyo chemical conversion industry (strain) system), 2.73 parts of benzoic acid (Tokyo chemical conversion industry (strain) system), (the Tokyo chemical conversion of 1- amylalcohol Industrial (strain) system) 157 parts and 7.43 parts of cyan-acetic ester (Tokyo chemical conversion industry (strain) system), stirring 3 is small at 120 DEG C When.7.46 parts of cyan-acetic ester (Tokyo chemical conversion industry (strain) system), benzoic acid (Tokyo chemical conversion industry (strain) system) 2.79 is added Part, 49.8 parts of 1- amylalcohol (Tokyo chemical conversion industry (strain) system) and 4- (diethylamino) salicylide (Tokyo chemical conversion industry (strain) System) 12.7 parts, it is stirred 14 hours in 120 DEG C.3.76 parts of cyan-acetic ester (Tokyo chemical conversion industry (strain) system), benzoic acid is added 1.41 parts of (Tokyo chemical conversion industry (strain) system), 52.5 parts of 1- amylalcohol (Tokyo chemical conversion industry (strain) system) and 4- (diethylamino) 6.35 parts of salicylide (Tokyo chemical conversion industry (strain) system), is stirred 8 hours at 120 DEG C.After above-mentioned reaction solution is cooled to room temperature, The crystallization of precipitation is obtained as the residue filtered.140 parts of tetrahydrofuran, after stirring 1 hour at 70 DEG C are added in the residue, Insoluble matter is obtained as the residue filtered.120 parts of tetrahydrofuran of addition, insoluble after stirring 1 hour at 70 DEG C in the residue Object is obtained as the residue filtered.340 parts of n,N-Dimethylformamide are added in the residue, heating is allowed to dissolve at 90 DEG C Afterwards, it is stood at 0 DEG C~5 DEG C.The crystallization of precipitation is obtained as the residue filtered.The residue is dried under reduced pressure at 60 DEG C, is obtained 5.69 parts of compound indicated to formula (2-1).With¹H-NMR confirms structure.

¹H-NMR (500MHz, DMSO-d6): 1.14 (6H, t), 3.47 (4H, q), 6.57 (1H, d), 6.78 (1H, dd), 7.68 (1H, d), 7.79 (1H, d), 7.96 (1H, dd), 8.15 (1H, d), 8.80 (1H, s), 13.11 (1H, s)

Synthesis example 7: the synthesis for the compound (hereinafter, sometimes referred to as compound (3-1)) that formula (3-1) indicates

The third of 4- diethylamino salicylide 1.93g (10mmol), formula (pp " 5-1) expression that formula (pp " 1-1) is indicated Diethyl adipate 3.20g (20mmol) and piperidinyl-1 mL are dissolved in the dehydrated alcohol of 50mL.Then, side is stirred under reflux conditions 6 hours sides are mixed to be reacted.After reaction, ethyl alcohol is evaporated under reduced pressure and is removed, concentrated hydrochloric acid 10mL is added in the reactive mixture With glacial acetic acid 10mL, it is stirred for 6 hours.After reaction mixture is cooled to room temperature, it is put into the ice water of 200mL, it is further cold But then by the 30 mass % sodium hydrate aqueous solutions that drip in the reactive mixture, the pH of reaction mixture is about adjusted by Whole is 5.After reaction mixture is stirred 30 minutes, the sediment of generation is filtered, is washed with water, it is dry.By with toluene make as This obtained sediment recrystallization, obtains the 7- diethylamino cumarin of formula (pp " 2-1) expression.Yield is 1.74g (8.0mmol), yield 80%.

(mass spectral analysis) ionization mode=ESI+:m/z=[M+H]⁺218.1

Exact Mass:217.1

Under 0 DEG C, nitrogen atmosphere, dimethylformamide 2mL will be dehydrated and gently instill the reaction appearance equipped with phosphoryl chloride phosphorus oxychloride 2mL In device, then, it is warming up to room temperature, stirred 30 minutes.Then, 7- diethylamino cumarin formula (pp " 2-1) indicated 1.50g (6.91mmol) is dissolved in dehydration dimethylformamide 10mL, is put into reaction vessel, and it is small that 12 are stirred at 50 DEG C When.Reaction mixture is put into the ice water of 200mL, 20 mass % sodium hydrate aqueous solutions are added.The sediment generated is filtered, It washes with water, is dried.By recrystallizing the obtained sediment with ethyl alcohol, the 7- bis- of formula (pp " 3-1) expression is obtained Ethylamino cumarin -3- aldehyde.Yield is 1.20g (4.89mmol), yield 70%.

(mass spectral analysis) ionization mode=ESI+:m/z=[M+H]⁺246.1

Exact Mass:245.1

7- diethylamino cumarin -3- aldehyde 2.0g (8.15mmol), the formula (pp " 4- that formula (pp " 3-1) indicates 1) bis- (3- amino-4-hydroxylphenyl) the hexafluoropropane 1.49g (4.08mmol) and sodium acetate 12.6g of 2,2- indicated (163mmol) is dissolved in glacial acetic acid 40mL, is stirred 10 hours at 90 DEG C.Then, reaction mixture is put into the water of 200mL In.The sediment generated is filtered, is allowed to be dissolved in methylene chloride, it is put into togerther in separatory funnel with water, is cleaned.It is logical After crossing the dichloromethane layer sodium sulphate drying that will be recycled from separatory funnel, is purified with silica gel column chromatography, obtain chemical combination Object (3-1).Yield is 1.67g (2.04mmol), yield 50%.

(mass spectral analysis) ionization mode=ESI+:m/z=[M+H]⁺817.3

Exact Mass:816.2

Synthesis example 8

By 14.9 parts of 1-amino-2-naphthol-4-sulfonic acid (Tokyo chemical conversion industry (strain) system), 4- (diethylamino) salicylide (Tokyo is melted into work for 12.0 parts of (Tokyo chemical conversion industry (strain) system), 2.61 parts of benzoic acid (Tokyo chemical conversion industry (strain) system), 1- amylalcohol Industry (strain) system) 151 parts and 7.12 parts of cyan-acetic ester (Tokyo chemical conversion industry (strain) system) mix, stir 12 at 120 DEG C Hour.After above-mentioned reaction solution is cooled to room temperature, the crystallization of precipitation is obtained as the residue filtered.Acetonitrile is added in the residue 320 parts, after stirring, insoluble matter is obtained as the residue filtered.236 parts of acetonitrile, after stirring are added in the residue, insoluble matter is made It is obtained for the residue of suction filtration.The residue is dried under reduced pressure at 60 DEG C, to obtain 25.7 parts of compound of formula (4-5) expression. With¹H-NMR confirms structure.

¹H-NMR (500MHz, DMSO-d6): 1.13 (6H, t), 3.46 (4H, q), 6.59 (1H, d), 6.78 (1H, dd), 7.10 (1H, s), 7.60 (1H, ddd), 7.70 (1H, ddd), 7.71 (1H, d), 8.27 (1H, s), 8.42 (1H, dd), 8.83 (1H, s), 9.01 (1H, dd)

Synthesis example 9

By 14.9 parts of 1-amino-2-naphthol-4-sulfonic acid (Tokyo chemical conversion industry (strain) system), 4- (dibutylamino) salicylide (Tokyo is melted into work for 15.5 parts of (Tokyo chemical conversion industry (strain) system), 2.59 parts of benzoic acid (Tokyo chemical conversion industry (strain) system), 1- amylalcohol Industry (strain) system) 150 parts and 7.02 parts of cyan-acetic ester (Tokyo chemical conversion industry (strain) system) mix, stir 12 at 120 DEG C Hour.After above-mentioned reaction solution is cooled to room temperature, solvent is distilled off with rotary evaporator, obtains residue.With column chromatography pair The residue is purified, and the compound of formula (4-12) expression is obtained.

Synthesis example 10

By 14.9 parts of 1-amino-2-naphthol-4-sulfonic acid (Tokyo chemical conversion industry (strain) system), 8- hydroxyl julolidine -9- carboxylic 13.5 parts of base aldehyde (Tokyo chemical conversion industry (strain) system), 2.59 parts of benzoic acid (Tokyo chemical conversion industry (strain) system), 1- amylalcohol (Tokyo At industrial (strain) system) 150 parts and 7.02 parts of cyan-acetic ester (Tokyo chemical conversion industry (strain) system) mix, stirred at 120 DEG C It mixes 12 hours.After above-mentioned reaction solution is cooled to room temperature, solvent is distilled off with rotary evaporator, obtains residue.Use column chromatography Method purifies the residue, obtains the compound of formula (4-285) expression.

Synthesis example 11

By 14.9 parts of 1-amino-2-naphthol-4-sulfonic acid (Tokyo chemical conversion industry (strain) system), 8- hydroxyl -1,1,7,7- tetramethyls 17.0 parts of base julolidine -9- carboxyl aldehyde (Tokyo chemical conversion industry (strain) system), benzoic acid (Tokyo chemical conversion industry (strain) system) 2.59 7.02 parts of part, 150 parts of 1- amylalcohol (Tokyo chemical conversion industry (strain) system) and cyan-acetic ester (Tokyo chemical conversion industry (strain) system) Mixing, is stirred 12 hours at 120 DEG C.After above-mentioned reaction solution is cooled to room temperature, solvent is distilled off with rotary evaporator, obtains To residue.The residue is purified with column chromatography, obtains the compound of formula (4-397) expression.

Synthesis example 12

It is passed through suitable nitrogen in the flask for having reflux cooler, dropping funel and blender, is made nitrogen gas Atmosphere is put into 100 parts of propylene glycol monomethyl ether, is heated to 85 DEG C while stirring.Then, by 19 parts of methacrylic acid, third Olefin(e) acid ester 3,4- epoxy tricyclic [5.2.1.0^2,6] decane -8- base and acrylic acid 3,4- epoxy tricyclic [5.2.1.0^2,6] decane- 9- base ester mixture (containing than with molar ratio computing for 50: 50) 171 parts be dissolved in 40 parts of propylene glycol monomethyl ether, will Thus obtained solution dropping liquid pump lasts about 5 hours and instills in the flask.On the other hand, by 2,2 '-azo of polymerization initiator 26 parts of bis- (2,4- methyl pentane nitriles), which are dissolved in 120 parts of obtained solution of propylene glycol monomethyl ether and are pumped with another dropping liquid, to be gone through When about 5 hours instillation flasks in.After the instillation of polymerization initiator, is kept for synthermal about 3 hours, then, is cooled to room temperature, Obtain copolymer (resin B 1) solution of solid component 43.5%.The weight average molecular weight of obtained resin B 1 is 8000, molecule The acid value that amount is distributed as the conversion of 1.98, solid component is 53mgKOH/g.

Synthesis example 13

By propylene glycol monomethyl ether 333g importing have blender, thermometer, reflux cooling tube, dropping funel with And in the flask of the 1000ml of gas-guide tube.Then, nitrogen is imported in flask using gas-guide tube, the atmosphere in flask is replaced as Nitrogen.Then, after the solution in flask being warming up to 100 DEG C, lasting 2 hours with dropping funel will be by two ring penta of methacrylic acid Base ester (FA-513M；Hitachi Chemical Industries (Ltd.) system) 22.0g (0.10 mole), (0.40 rubs benzyl methacrylate 70.5g You), methacrylic acid 43.0g (0.5 mole), azodiisobutyronitrile 3.6g and propylene glycol monomethyl ether 164g composition Mixture instill in flask, after instillation, then continue at 100 DEG C stirring 5 hours.

It after stirring, using gas-guide tube, directs the air into flask, makes in flask after atmosphere air, by methyl-prop [0.25 mole (methacrylic acid used relative to this reaction, mole fraction rub olefin(e) acid glycidyl esters 35.5g for 50 Your %)], three (dimethylaminomethyl) phenol 0.9g and quinhydrones 0.145g put into flask, the reaction was continued at 110 DEG C 6 hours, obtain 2 solution of resin B of 38.7 mass % of solid component.The weight average molecular weight of resin B 2 is 9,800, and solid component changes The acid value of calculation is 82mgKOH/g.

(preparation of colored curable resin composition)

Embodiment 1

By colorant (A): 48 parts of C.I. pigment Green 7 (pigment),

22 parts of acrylic acid series pigment dispersing agent,

Resin (B): 17 parts of resin B 1 (solid component conversion) and

Solvent (E): 310 parts of propylene glycol monomethyl ether

Mixing, disperses pigment fully using ball mill, obtains dispersible pigment dispersion；

By colorant (A): 7.5 parts of C.I. pigment Yellow 12 9 (pigment),

6.0 parts of acrylic acid series pigment dispersing agent and

Solvent (E): 44 parts of propylene glycol monomethyl ether

By above-mentioned two dispersible pigment dispersion with

Colorant (A): 7.5 parts of compound of formula (1-148) expression；

Resin (B): 10 parts of resin B 1 (solid component conversion)；

Polymerizable compound (C): six acrylic acid of dipentaerythritol (KAYARAD (registered trademark) DPHA；Japanese chemical drug (strain) System) 27 parts；

Polymerization initiator (D): N- benzoyloxy -1- (4- Phenylsulfanylphenyl) -1- octanone -2- imines (gorgeous good solid (registration Trade mark) OXE-01；BASF society system；O- acyl group oxime compound)

5.4 part；

Solvent (E): 13 parts of propylene glycol monomethyl ether；

Solvent (E): 480 parts of N-Methyl pyrrolidone and

Levelling agent (F): polyether modified silicone oil

(TORAY silicone SH8400；East beautiful DOW CORNING (strain) system) 0.50 part

Mixing, obtains colored curable resin composition.

Embodiment 2

By colorant (A): 37 parts of C.I. pigment Green 7 (pigment),

17 parts of acrylic acid series pigment dispersing agent,

Resin (B): 13 parts of resin B 1 (solid component conversion) and

Solvent (E): 240 parts of propylene glycol monomethyl ether

By colorant (A): 13 parts of C.I. pigment Yellow 12 9 (pigment),

10 parts of acrylic acid series pigment dispersing agent and

Solvent (E): 77 parts of propylene glycol monomethyl ether

By above-mentioned two dispersible pigment dispersion with

Colorant (A): 13 parts of compound of formula (1-169) expression；

Resin (B): 14 parts of resin B 1 (solid component conversion)；

5.4 part；

Solvent (E): 18 parts of propylene glycol monomethyl ether；

Solvent (E): 510 parts of N-Methyl pyrrolidone and

Levelling agent (F): polyether modified silicone oil

(TORAY silicone SH8400；East beautiful DOW CORNING (strain) system) 0.50 part

Mixing, obtains colored curable resin composition.

Embodiment 3

By colorant (A): 46 parts of C.I. pigment Green 7 (pigment),

21 parts of acrylic acid series pigment dispersing agent,

Resin (B): 16 parts of resin B 1 (solid component conversion) and

Solvent (E): 300 parts of propylene glycol monomethyl ether

By colorant (A): 8.6 parts of C.I. pigment Yellow 12 9 (pigment),

6.9 parts of acrylic acid series pigment dispersing agent and

Solvent (E): 51 parts of propylene glycol monomethyl ether

By above-mentioned two dispersible pigment dispersion with

Colorant (A): 8.6 parts of compound of formula (2-1) expression；

Resin (B): 11 parts of resin B 1 (solid component conversion)；

5.4 part；

Solvent (E): 14 parts of propylene glycol monomethyl ether；

Solvent (E): 490 parts of N-Methyl pyrrolidone and

Levelling agent (F): polyether modified silicone oil

(TORAY silicone SH8400；East beautiful DOW CORNING (strain) system) 0.50 part

Mixing, obtains colored curable resin composition.

Embodiment 4

By colorant (A): 40 parts of C.I. pigment Green 7 (pigment),

18 parts of acrylic acid series pigment dispersing agent,

Resin (B): 14 parts of resin B 1 (solid component conversion) and

Solvent (E): 260 parts of propylene glycol monomethyl ether

Colorant (A): 12 parts of C.I. pigment Yellow 12 9 (pigment),

9.2 parts of acrylic acid series pigment dispersing agent and

Solvent (E): 68 parts of propylene glycol monomethyl ether

By above-mentioned two dispersible pigment dispersion with

Colorant (A): 12 parts of compound of formula (3-1) expression；

Resin (B): 13 parts of resin B 1 (solid component conversion)；

5.4 part；

Solvent (E): 17 parts of propylene glycol monomethyl ether；

Solvent (E): 500 parts of N-Methyl pyrrolidone and

Levelling agent (F): polyether modified silicone oil

(TORAY silicone SH8400；East beautiful DOW CORNING (strain) system) 0.50 part

Mixing, obtains colored curable resin composition.

Embodiment 5

By colorant (A): 49 parts of C.I. pigment Green 7 (pigment),

22 parts of acrylic acid series pigment dispersing agent,

Resin (B): 17 parts of resin B 1 (solid component conversion) and

Solvent (E): 320 parts of propylene glycol monomethyl ether

By colorant (A): 6.8 parts of C.I. pigment Yellow 12 9 (pigment),

5.5 parts of acrylic acid series pigment dispersing agent and

Solvent (E): 40 parts of propylene glycol monomethyl ether

By above-mentioned two dispersible pigment dispersion with

Colorant (A): 6.8 parts of compound of formula (4-5) expression；

Resin (B): 9.5 parts of resin B 1 (solid component conversion)；

5.3 part；

Solvent (E): 12 parts of propylene glycol monomethyl ether；

Solvent (E): 480 parts of N-Methyl pyrrolidone and

Levelling agent (F): polyether modified silicone oil

(TORAY silicone SH8400；East beautiful DOW CORNING (strain) system) 0.50 part

Mixing, obtains colored curable resin composition.

Embodiment 6

By colorant (A): 58 parts of C.I. pigment green 36 (pigment),

26 parts of acrylic acid series pigment dispersing agent,

Resin (B): 20 parts of resin B 1 (solid component conversion) and

Solvent (E): 380 parts of propylene glycol monomethyl ether

By colorant (A): 2.3 parts of C.I. pigment Yellow 12 9 (pigment),

1.8 parts of acrylic acid series pigment dispersing agent and

Solvent (E): 13 parts of propylene glycol monomethyl ether

By above-mentioned two dispersible pigment dispersion with

Colorant (A): 2.3 parts of compound of formula (1-148) expression；

Resin (B): 6.1 parts of resin B 1 (solid component conversion)；

5.3 part；

Solvent (E): 7.9 parts of propylene glycol monomethyl ether；

Solvent (E): 450 parts of N-Methyl pyrrolidone and

Levelling agent (F): polyether modified silicone oil

(TORAY silicone SH8400；East beautiful DOW CORNING (strain) system) 0.50 part

Mixing, obtains colored curable resin composition.

Embodiment 7

By colorant (A): 53 parts of C.I. pigment green 36 (pigment),

24 parts of acrylic acid series pigment dispersing agent,

Resin (B): 19 parts of resin B 1 (solid component conversion) and

Solvent (E): 350 parts of propylene glycol monomethyl ether

By colorant (A): 4.8 parts of C.I. pigment Yellow 12 9 (pigment),

3.8 parts of acrylic acid series pigment dispersing agent and

Solvent (E): 28 parts of propylene glycol monomethyl ether

By above-mentioned two dispersible pigment dispersion with

Colorant (A): 4.8 parts of compound of formula (1-169) expression；

Resin (B): 7.9 parts of resin B 1 (solid component conversion)；

5.3 part；

Solvent (E): 10 parts of propylene glycol monomethyl ether；

Solvent (E): 460 parts of N-Methyl pyrrolidone and

Levelling agent (F): polyether modified silicone oil

(TORAY silicone SH8400；East beautiful DOW CORNING (strain) system) 0.50 part

Mixing, obtains colored curable resin composition.

Embodiment 8

By colorant (A): 58 parts of C.I. pigment green 36 (pigment),

26 parts of acrylic acid series pigment dispersing agent,

Resin (B): 20 parts of resin B 1 (solid component conversion) and

Solvent (E): 380 parts of propylene glycol monomethyl ether

By colorant (A): 2.7 parts of C.I. pigment Yellow 12 9 (pigment),

2.2 parts of acrylic acid series pigment dispersing agent and

Solvent (E): 16 parts of propylene glycol monomethyl ether

By above-mentioned two dispersible pigment dispersion with

Colorant (A): 2.7 parts of compound of formula (2-1) expression；

Resin (B): 6.4 parts of resin B 1 (solid component conversion)；

5.3 part；

Solvent (E): 8.3 parts of propylene glycol monomethyl ether；

Solvent (E): 450 parts of N-Methyl pyrrolidone and

Levelling agent (F): polyether modified silicone oil

(TORAY silicone SH8400；East beautiful DOW CORNING (strain) system) 0.50 part

Mixing, obtains colored curable resin composition.

Embodiment 9

By colorant (A): 55 parts of C.I. pigment green 36 (pigment),

25 parts of acrylic acid series pigment dispersing agent,

Resin (B): 19 parts of resin B 1 (solid component conversion) and

Solvent (E): 360 parts of propylene glycol monomethyl ether

By colorant (A): 4.0 parts of C.I. pigment Yellow 12 9 (pigment),

3.2 parts of acrylic acid series pigment dispersing agent and

Solvent (E): 24 parts of propylene glycol monomethyl ether

By above-mentioned two dispersible pigment dispersion with

Colorant (A): 4.0 parts of compound of formula (3-1) expression；

Resin (B): 7.4 parts of resin B 1 (solid component conversion)；

5.3 part；

Solvent (E): 10 parts of propylene glycol monomethyl ether；

Solvent (E): 460 parts of N-Methyl pyrrolidone and

Levelling agent (F): polyether modified silicone oil

(TORAY silicone SH8400；East beautiful DOW CORNING (strain) system) 0.50 part

Mixing, obtains colored curable resin composition.

Embodiment 10

By colorant (A): 59 parts of C.I. pigment green 36 (pigment),

27 parts of acrylic acid series pigment dispersing agent,

Resin (B): 21 parts of resin B 1 (solid component conversion) and

Solvent (E): 390 parts of propylene glycol monomethyl ether

By colorant (A): 2.0 parts of C.I. pigment Yellow 12 9 (pigment),

1.6 parts of acrylic acid series pigment dispersing agent and

Solvent (E): 12 parts of propylene glycol monomethyl ether

By above-mentioned two dispersible pigment dispersion with

Colorant (A): 2.0 parts of compound of formula (4-5) expression；

Resin (B): 5.9 parts of resin B 1 (solid component conversion)；

5.3 part；

Solvent (E): 7.6 parts of propylene glycol monomethyl ether；

Solvent (E): 450 parts of N-Methyl pyrrolidone and

Levelling agent (F): polyether modified silicone oil

(TORAY silicone SH8400；East beautiful DOW CORNING (strain) system) 0.50 part

Mixing, obtains colored curable resin composition.

Embodiment 11

By colorant (A): 60 parts of C.I. naphthol green 58 (pigment),

27 parts of acrylic acid series pigment dispersing agent,

Resin (B): 21 parts of resin B 1 (solid component conversion) and

Solvent (E): 390 parts of propylene glycol monomethyl ether

By colorant (A): 1.4 parts of C.I. pigment Yellow 12 9 (pigment),

1.1 parts of acrylic acid series pigment dispersing agent and

Solvent (E): 8.1 parts of propylene glycol monomethyl ether

By above-mentioned two dispersible pigment dispersion with

Colorant (A): 1.4 parts of compound of formula (1-148) expression；

Resin (B): 5.4 parts of resin B 1 (solid component conversion)；

Polymerizable compound (C): six acrylic acid of dipentaerythritol (KAYARAD (registered trademark) DPHA；Japanese chemical drug (strain) System) 26 parts；

5.3 part；

Solvent (E): 7.0 parts of propylene glycol monomethyl ether；

Solvent (E): 440 parts of N-Methyl pyrrolidone and

Levelling agent (F): polyether modified silicone oil

(TORAY silicone SH8400；East beautiful DOW CORNING (strain) system) 0.50 part

Mixing, obtains colored curable resin composition.

Embodiment 12

By colorant (A): 57 parts of C.I. naphthol green 58 (pigment),

26 parts of acrylic acid series pigment dispersing agent,

Resin (B): 20 parts of resin B 1 (solid component conversion) and

Solvent (E): 370 parts of propylene glycol monomethyl ether

By colorant (A): 2.9 parts of C.I. pigment Yellow 12 9 (pigment),

2.3 parts of acrylic acid series pigment dispersing agent and

Solvent (E): 17 parts of propylene glycol monomethyl ether

By above-mentioned two dispersible pigment dispersion with

Colorant (A): 2.9 parts of compound of formula (1-169) expression；

Resin (B): 6.5 parts of resin B 1 (solid component conversion)；

5.3 part；

Solvent (E): 8.5 parts of propylene glycol monomethyl ether；

Solvent (E): 450 parts of N-Methyl pyrrolidone and

Levelling agent (F): polyether modified silicone oil

(TORAY silicone SH8400；East beautiful DOW CORNING (strain) system) 0.50 part

Mixing, obtains colored curable resin composition.

Embodiment 13

By colorant (A): 60 parts of C.I. naphthol green 58 (pigment),

27 parts of acrylic acid series pigment dispersing agent,

Resin (B): 21 parts of resin B 1 (solid component conversion) and

Solvent (E): 390 parts of propylene glycol monomethyl ether

By colorant (A): 1.6 parts of C.I. pigment Yellow 12 9 (pigment),

1.3 parts of acrylic acid series pigment dispersing agent and

Solvent (E): 9.6 parts of propylene glycol monomethyl ether

By above-mentioned two dispersible pigment dispersion with

Colorant (A): 1.6 parts of compound of formula (2-1) expression；

Resin (B): 5.6 parts of resin B 1 (solid component conversion)；

5.3 part；

Solvent (E): 7.3 parts of propylene glycol monomethyl ether；

Solvent (E): 440 parts of N-Methyl pyrrolidone and

Levelling agent (F): polyether modified silicone oil

(TORAY silicone SH8400；East beautiful DOW CORNING (strain) system) 0.50 part

Mixing, obtains colored curable resin composition.

Embodiment 14

By colorant (A): 58 parts of C.I. naphthol green 58 (pigment),

26 parts of acrylic acid series pigment dispersing agent,

Resin (B): 20 parts of resin B 1 (solid component conversion) and

Solvent (E): 380 parts of propylene glycol monomethyl ether

By colorant (A): 2.4 parts of C.I. pigment Yellow 12 9 (pigment),

1.9 parts of acrylic acid series pigment dispersing agent and

Solvent (E): 14 parts of propylene glycol monomethyl ether

By above-mentioned two dispersible pigment dispersion with

Colorant (A): 2.4 parts of compound of formula (3-1) expression；

Resin (B): 6.2 parts of resin B 1 (solid component conversion)；

5.3 part；

Solvent (E): 8.0 parts of propylene glycol monomethyl ether；

Solvent (E): 450 parts of N-Methyl pyrrolidone and

Levelling agent (F): polyether modified silicone oil

(TORAY silicone SH8400；East beautiful DOW CORNING (strain) system) 0.50 part

Mixing, obtains colored curable resin composition.

Embodiment 15

By colorant (A): 61 parts of C.I. naphthol green 58 (pigment),

27 parts of acrylic acid series pigment dispersing agent,

Resin (B): 21 parts of resin B 1 (solid component conversion) and

Solvent (E): 400 parts of propylene glycol monomethyl ether

By colorant (A): 1.2 parts of C.I. pigment Yellow 12 9 (pigment),

0.96 part of acrylic acid series pigment dispersing agent and

Solvent (E): 7.0 parts of propylene glycol monomethyl ether

By above-mentioned two dispersible pigment dispersion with

Colorant (A): 1.2 parts of compound of formula (4-5) expression；

Resin (B): 5.3 parts of resin B 1 (solid component conversion)；

5.3 part；

Solvent (E): 6.8 parts of propylene glycol monomethyl ether；

Solvent (E): 440 parts of N-Methyl pyrrolidone and

Levelling agent (F): polyether modified silicone oil

(TORAY silicone SH8400；East beautiful DOW CORNING (strain) system) 0.50 part

Mixing, obtains colored curable resin composition.

Comparative example 1

By colorant (A): 58 66 parts of C.I. naphthol green,

30 parts of pigment dispersing agent,

Resin (B): 23 parts of resin B 2 (solid component conversion) and

Solvent (E): 429 parts of propylene glycol monomethyl ether

Mixing, is allowed to disperse, obtains dispersible pigment dispersion；

By the dispersible pigment dispersion with

Colorant: 48 parts of compound of formula (z) expression；

Resin (B): 32 parts of resin B 2 (solid component conversion)；

Polymerizable compound (C): 45 parts of six acrylic acid of dipentaerythritol；

Polymerization initiator (D): gorgeous good solid 20 parts of (registered trademark) 369 (BASF society system)；

Polymerization trigger auxiliary agent (D1): 4,4 '-bis- 7.0 parts of (diethylamino) benzophenone；

Surfactant: 0.91 part of メガ Off ア Star Network (registered trademark) F475 (DIC (strain) system)；

Solvent (E): 878 parts of propylene glycol monomethyl ether and

Solvent (E): 231 parts of propylene glycol monomethyl ether

Mixing, obtains colored curable resin composition.

(production of colored pattern)

In glass substrate (the mono- グ Le XG of イ of 2 inch squares；One ニ Application グ society system of U) on, it is coated with and is coloured by spin-coating method After solidification compound, preliminary drying 3 minutes at 100 DEG C obtain coloring compositions nitride layer.After cooling, make to be formed with coloured composition 200 μm are divided between the glass substrate and quartz glass photomask of layer, uses exposure machine (TME-150RSK；トプコン (strain) system), under air atmosphere, with 80mJ/cm²Light exposure (365nm benchmark) be exposed.In addition, making as photomask With the photomask of the line width and line intermittent pattern (Line and Space Pattern) that form 100 μm.By after exposure Color composition layer is immersed in the aqueous solution containing nonionic surfactants 0.12% and potassium hydroxide 0.04% at 25 DEG C In develop within 70 seconds, after washing, carry out rear baking in 20 minutes in baking oven, at 230 DEG C, obtain colored pattern.

(film thickness measuring)

For the colored pattern of acquisition, film thickness measuring device (DEKTAK3 is used；Japanese vacuum technique (strain) system)) measurement Its film thickness.As a result it indicates in table 166.

(chromaticity evaluation)

For the colored pattern of acquisition, color measurement instrument (OSP-SP-200 is used；Olympus (strain) system) measurement light splitting (light Spectrum), the xy chromaticity coordinate (x, y) and tristimulus values Y in the XYZ colour system of CIE are measured by the characteristic function of illuminant-C.Y's It is higher to be worth bigger expression brightness.As a result in shown in table 1 66.

[table 1]

Embodiment 16

Other than the compound that the compound for using synthesis example 3 to synthesize replaces synthesis example 1 to synthesize, other and embodiment 1 Equally obtain colored curable resin composition and colour filter.

Embodiment 17

Other than the compound that the compound for using synthesis example 4 to synthesize replaces synthesis example 1 to synthesize, other and embodiment 1 Equally obtain colored curable resin composition and colour filter.

Embodiment 18

Other than the compound that the compound for using synthesis example 5 to synthesize replaces synthesis example 1 to synthesize, other and embodiment 1 Equally obtain colored curable resin composition and colour filter.

Embodiment 19

Other than the compound that the compound for using synthesis example 9 to synthesize replaces synthesis example 8 to synthesize, other and embodiment 5 Equally obtain colored curable resin composition and colour filter.

Embodiment 20

Other than the compound that the compound for using synthesis example 10 to synthesize replaces synthesis example 8 to synthesize, other and embodiment 5 Equally obtain colored curable resin composition and colour filter.

Embodiment 21

Other than the compound that the compound for using synthesis example 11 to synthesize replaces synthesis example 8 to synthesize, other and embodiment 5 Equally obtain colored curable resin composition and colour filter.

Embodiment 22

Other than the compound that the compound for using synthesis example 3 to synthesize replaces synthesis example 1 to synthesize, other and embodiment 6 Equally obtain colored curable resin composition and colour filter.

Embodiment 23

Other than the compound that the compound for using synthesis example 4 to synthesize replaces synthesis example 1 to synthesize, other and embodiment 6 Equally obtain colored curable resin composition and colour filter.

Embodiment 24

Other than the compound that the compound for using synthesis example 5 to synthesize replaces synthesis example 1 to synthesize, other and embodiment 6 Equally obtain colored curable resin composition and colour filter.

Embodiment 25

Other than the compound that the compound for using synthesis example 9 to synthesize replaces synthesis example 8 to synthesize, other and embodiment 10 Equally obtain colored curable resin composition and colour filter.

Embodiment 26

Other than the compound that the compound for using synthesis example 10 to synthesize replaces synthesis example 8 to synthesize, other and embodiment 10 equally obtain colored curable resin composition and colour filter.

Embodiment 27

Other than the compound that the compound for using synthesis example 11 to synthesize replaces synthesis example 8 to synthesize, other and embodiment 10 equally obtain colored curable resin composition and colour filter.

Embodiment 28

Other than the compound that the compound for using synthesis example 3 to synthesize replaces synthesis example 1 to synthesize, other and embodiment 11 Equally obtain colored curable resin composition and colour filter.

Embodiment 29

Other than the compound that the compound for using synthesis example 4 to synthesize replaces synthesis example 1 to synthesize, other and embodiment 11 Equally obtain colored curable resin composition and colour filter.

Embodiment 30

Other than the compound that the compound for using synthesis example 5 to synthesize replaces synthesis example 1 to synthesize, other and embodiment 11 Equally obtain colored curable resin composition and colour filter.

Embodiment 31

Other than the compound that the compound for using synthesis example 9 to synthesize replaces synthesis example 8 to synthesize, other and embodiment 15 Equally obtain colored curable resin composition and colour filter.

Embodiment 32

Other than the compound that the compound for using synthesis example 10 to synthesize replaces synthesis example 8 to synthesize, other and embodiment 15 equally obtain colored curable resin composition and colour filter.

Embodiment 33

Other than the compound that the compound for using synthesis example 11 to synthesize replaces synthesis example 8 to synthesize, other and embodiment 15 equally obtain colored curable resin composition and colour filter.

According to the present invention, it is possible to provide the colored curable resin composition of the colour filter of high brightness can be manufactured.By this Color hardening resin composition manufacture high brightness colour filter can be suitably used for liquid crystal display device, organic el device, In the display devices such as Electronic Paper or solid-state imager.

Claims

1. a kind of colored curable resin composition, containing colorant, resin, polymerizable compound and polymerization initiator, The colorant contains compound and C.I. pigment Yellow 12 9 with cumarin skeleton,

Compound with the cumarin skeleton is that formula (1), formula (1 '), formula (2), formula (3), formula (4) or formula (5) indicate Compound,

In formula (1),

L indicates the divalent alkyl of carbon atom number 1~20, and the methylene for constituting the divalent alkyl can be by oxygen atom, sulphur atom ,-N (R¹⁰)-, sulfonyl or carbonyl replace, hydrogen atom contained by the divalent alkyl can be by cyano, nitro, carbamoyl, ammonia sulphur Acyl group, sulfo group, carboxyl, hydroxyl, chlorine atom, bromine atom, imidazoles -1- base or amino replace,

X indicates oxygen atom, sulphur atom or-N (R¹⁰)-,

AA indicates the aryl of carbon atom number 6~20, and hydrogen atom contained by the aryl can be by halogen atom, cyano, nitro, amino first Acyl group, sulfamoyl, sulfo group, carboxyl, hydroxyl, imidazoles -1- base, amino or carbon atom number 1~20 1 valency alkyl replace, structure It can be by oxygen atom, sulphur atom ,-N (R at the methylene of 1 valency alkyl¹⁰)-, sulfonyl or carbonyl replace, the 1 valency alkyl institute The hydrogen atom contained can be by halogen atom, cyano, nitro, carbamoyl, sulfamoyl, sulfo group, carboxyl, hydroxyl, imidazoles -1- Base or amino replace,

R¹~R⁴Separately indicate 1 valency alkyl or R of hydrogen atom or carbon atom number 1~20¹With R³Bonding and with it is adjacent Ring or R is collectively formed in the nitrogen-atoms of carbon atom and adjoining on phenyl ring²With R⁴Bonding and it is former with the carbon on adjacent phenyl ring Ring is collectively formed in son and adjacent nitrogen-atoms, and the methylene for constituting 1 valency alkyl can be by oxygen atom, sulphur atom ,-N (R¹⁰)-, sulfonyl or carbonyl replace, hydrogen atom contained by 1 valency alkyl can be by halogen atom, cyano, nitro, carbamyl Base, sulfamoyl, sulfo group, carboxyl, hydroxyl, imidazoles -1- base or amino replace,

R⁵~R⁹Separately indicate hydrogen atom, halogen atom, cyano, nitro, carbamoyl, sulfamoyl, sulfo group, carboxyl, 1 valency alkyl or R of hydroxyl, amino or carbon atom number 1~20⁵With R⁶It is bonded and ring is collectively formed with adjacent carbon atom, or Person R⁷With R⁸It is bonded and ring is collectively formed with adjacent carbon atom, the methylene for constituting 1 valency alkyl can be former by oxygen atom, sulphur Son ,-N (R¹⁰)-, sulfonyl or carbonyl replace, hydrogen atom contained by 1 valency alkyl can be by halogen atom, cyano, nitro, ammonia Base formoxyl, sulfamoyl, sulfo group, carboxyl, hydroxyl, imidazoles -1- base or amino replace,

R¹⁰Indicate 1 valency alkyl of hydrogen atom or carbon atom number 1~20, there are multiple R¹⁰When, they are mutually identical or difference,

In formula (1 '), R¹~R⁹, X and L respectively indicate meaning same as described above,

In formula (2), Q¹And Q²Separately indicate hydrogen atom or-CO₂M, Q¹And Q²In any one expression-CO₂M,

R¹¹~R¹⁴Separately indicate 1 valency alkyl or R of hydrogen atom or carbon atom number 1~20¹¹And R¹³Bonding and with Ring or R is collectively formed in the nitrogen-atoms of carbon atom and adjoining on adjacent phenyl ring¹²And R¹⁴Bonding and with adjacent benzene Ring is collectively formed in the nitrogen-atoms of carbon atom and adjoining on ring, and the methylene for constituting 1 valency alkyl can be former by oxygen atom, sulphur Son ,-N (R¹⁵)-, sulfonyl or carbonyl replace, hydrogen atom contained by 1 valency alkyl can be by halogen atom, cyano, nitro, ammonia Base formoxyl, sulfamoyl ,-SO₃M ,-CO₂M, hydroxyl or amino replace,

R¹⁵Indicate 1 valency alkyl of hydrogen atom or carbon atom number 1~20, there are multiple R¹⁵When, they are same to each other or different,

M indicates hydrogen atom or alkali metal atom,

In formula (3),

L ' indicates the divalent alkyl of carbon atom number 1~20, and the methylene for constituting the divalent alkyl can be by oxygen atom, sulphur atom ,-N (R²⁵)-, sulfonyl or carbonyl replace, hydrogen atom contained by the divalent alkyl can be by halogen atom, cyano, nitro, carbamyl Base, sulfamoyl ,-SO₃M ' ,-CO₂M ', hydroxyl or amino replace, wherein in hydrogen atom contained by the divalent alkyl at least One is replaced by fluorine atoms,

X ' indicates the 16th race's atom ,-N (R in the periodic table of elements²⁵)-or-C (R²⁵)(R²⁶)-,

R¹⁶~R²⁴Separately indicate hydrogen atom, halogen atom, cyano, nitro, carbamoyl, sulfamoyl ,- SO₃M ' ,-CO₂M ', hydroxyl, amino or carbon atom number 1~20 1 valency alkyl or R¹⁶And R¹⁸Bonding and with adjacent benzene Ring or R is collectively formed in the nitrogen-atoms of carbon atom and adjoining on ring¹⁷And R¹⁹Bonding and with the carbon on adjacent phenyl ring Ring is collectively formed in atom and the nitrogen-atoms of adjoining, and the methylene for constituting 1 valency alkyl can be by oxygen atom, sulphur atom ,-N (R²⁷)-, sulfonyl or carbonyl replace, hydrogen atom contained by 1 valency alkyl can be by halogen atom, cyano, nitro, carbamyl Base, sulfamoyl ,-SO₃M ' ,-CO₂M ', hydroxyl or amino replace,

R²⁵And R²⁶1 valency alkyl for separately indicating hydrogen atom or carbon atom number 1~20, constitutes the methylene of 1 valency alkyl Base can be by oxygen atom, sulphur atom ,-N (R²⁷)-, sulfonyl or carbonyl replace, hydrogen atom contained by 1 valency alkyl can be by Halogen atom, cyano, nitro, carbamoyl, sulfamoyl ,-SO₃M ' ,-CO₂M ', hydroxyl or amino replace,

R²⁷Indicate 1 valency alkyl of hydrogen atom or carbon atom number 1~20, there are multiple R²⁷When, they are same to each other or different,

M ' indicates hydrogen atom or alkali metal atom,

In formula (4) and formula (5),

X " indicates the 16th race's atom ,-N (R in the periodic table of elements³⁴)-or-C (R³⁴)(R³⁵)-,

R²⁸~R⁴¹Separately indicate hydrogen atom, halogen atom, cyano, nitro, carbamoyl, sulfamoyl ,- SO₃M " ,-CO₂M ", hydroxyl, amino or carbon atom number 1~20 1 valency alkyl or R²⁸And R³⁰Bonding and with adjacent benzene Ring or R is collectively formed in the nitrogen-atoms of carbon atom and adjoining on ring²⁹And R³¹Bonding and with the carbon on adjacent phenyl ring Ring is collectively formed in atom and the nitrogen-atoms of adjoining, and the methylene for constituting 1 valency alkyl can be by oxygen atom, sulphur atom ,-N (R⁴²)-, sulfonyl or carbonyl replace, hydrogen atom contained by 1 valency alkyl can be by halogen atom, cyano, nitro, carbamyl Base, sulfamoyl ,-SO₃M " ,-CO₂M ", hydroxyl, imidazoles -1- base or amino replace, wherein R³⁶~R⁴¹In at least one A is-SO₃M ",

R⁴²Indicate 1 valency alkyl of hydrogen atom or carbon atom number 1~20, there are multiple R⁴²When, they are same to each other or different,

M " indicates hydrogen atom or alkali metal atom.

2. colored curable resin composition according to claim 1, wherein colorant also contains pigment.

3. colored curable resin composition according to claim 2, wherein pigment is selected from by halogenated copper phthalocyanine pigment And at least one of the group of halogenated ZnPc pigment composition.

4. colored curable resin composition according to claim 2 or 3, wherein pigment is selected from by chloro copper phthalocyanine At least one of pigment, bromo copper phthalocyanine and group of bromo ZnPc pigment composition.

5. colored curable resin composition according to claim 2, wherein pigment is viridine green.

6. colored curable resin composition according to claim 2, wherein pigment be selected from by C.I. pigment Green 7, C.I. at least one of the group that pigment green 36 and C.I. naphthol green 58 form.

7. colored curable resin composition according to claim 2, wherein pigment is C.I. pigment Green 7.

8. colored curable resin composition according to claim 1, wherein X is oxygen atom or sulphur atom.

9. colored curable resin composition according to claim 1 or 8, wherein X is oxygen atom.

10. colored curable resin composition according to claim 1, wherein L is the methylene that can have substituent group Or sulfonyl.

11. colored curable resin composition according to claim 1, wherein L is dimethylmethylene or sulfonyl.

12. colored curable resin composition according to claim 1, wherein R⁵~R⁹It is hydrogen atom.

13. colored curable resin composition according to claim 1, wherein X ' is oxygen atom, sulphur atom ,-N (R²⁵)-or-C (R²⁵)(R²⁶)-.

14. colored curable resin composition according to claim 1, wherein X ' is oxygen atom, sulphur atom or-N (R²⁵)-.

15. colored curable resin composition according to claim 1, wherein X ' is oxygen atom or sulphur atom.

16. colored curable resin composition according to claim 1, wherein X ' is oxygen atom.

17. colored curable resin composition according to claim 1, wherein L ' is bis- (trifluoromethyl) methylene.

18. colored curable resin composition according to claim 1, wherein R¹⁸~R²⁴It is hydrogen atom.

19. colored curable resin composition according to claim 1, wherein the chemical combination with cumarin skeleton The compound that object is formula (4) or formula (5) indicates.

20. colored curable resin composition according to claim 1, wherein X " is oxygen atom, sulphur atom ,-N (R³⁴)-or-C (R³⁴)(R³⁵)-.

21. colored curable resin composition according to claim 1, wherein X " is oxygen atom.

22. colored curable resin composition according to claim 1, wherein R⁴⁰For-SO₃M”。

23. colored curable resin composition according to claim 1, wherein relative to the total amount of dyestuff and pigment, formula (1) content for the compound that any of~(5) indicate is 1 mass % or more, 65 mass % or less.

24. a kind of colour filter uses colored curable resin composition described in any one of claim 1~23 and shape At.

25. a kind of liquid crystal display device, it includes the colour filters described in claim 24.