CN105732604A - Compound as dye - Google Patents
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- CN105732604A CN105732604A CN201510979743.2A CN201510979743A CN105732604A CN 105732604 A CN105732604 A CN 105732604A CN 201510979743 A CN201510979743 A CN 201510979743A CN 105732604 A CN105732604 A CN 105732604A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/74—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C215/76—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/74—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton
- C07C215/76—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring
- C07C215/82—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to carbon atoms of six-membered aromatic rings of the same carbon skeleton of the same non-condensed six-membered aromatic ring having the nitrogen atom of at least one of the amino groups further bound to a carbon atom of another six-membered aromatic ring
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C223/00—Compounds containing amino and —CHO groups bound to the same carbon skeleton
- C07C223/06—Compounds containing amino and —CHO groups bound to the same carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The subject of the invention is providing an excellent compound which serves as a dye for a colored filter used in display apparatuses such as a liquid crystal display apparatus. The solution is a compound expressed in the formula (I). (as shown in the description)
Description
Technical field
The present invention relates to (such as comprising its coloring agent, colored curable resin composition, color filter, liquid crystal indicator) such as the noval chemical compounds useful as dyestuff.
Background technology
Dyestuff is used in the utilization reflection light in the fields such as such as fibrous material, liquid crystal indicator, ink-jet or in transmission light display color.This dyestuff is known coumarin 6 (patent documentation 1).
Prior art
Patent documentation
Patent documentation 1 Japanese Patent Laid-Open 2006-154740 publication (embodiment 8)
Summary of the invention
The problem that invention to solve
The problem of the present invention is: provide a kind of excellent compound used as the dyestuff in the color filter of the display devices such as liquid crystal indicator.Additionally, the present invention also with the intermediate providing above-claimed cpd, comprise the coloring agent of above-claimed cpd, colored curable resin composition, color filter, liquid crystal indicator for problem.
Solve the means of problem
The present invention comprises invention below.
[1] compound that formula (I) represents.
[changing 1]
(in formula, L represents divalent alkyl or the sulfonyl of carbon number 1～20.
X represents oxygen atom or sulphur atom.
R1Expression can have the thiazolinyl of the carbon number 2～20 of substituent group or can have the cycloalkenyl group of carbon number 3～20 of substituent group, constitutes-the CH of this thiazolinyl or cycloalkenyl group2-can by oxygen atom ,-N (R10)-or carbonyl substituted.
R2Represent 1 valency alkyl of hydrogen atom or carbon number 1～20.
R3～R9Represent hydrogen atom, 1 valency alkyl of carbon number 1～20, halogen atom, cyano group, nitro, carbamoyl, sulfamoyl ,-SO independently of one another3M、-CO2M, hydroxyl, formoxyl or amino.
R2～R9In the aforesaid alkyl represented ,-CH2-can by oxygen atom, sulphur atom ,-N (R11)-, sulfonyl or carbonyl substituted, hydrogen atom can by halogen atom, cyano group, nitro, carbamoyl, sulfamoyl ,-SO3M、-CO2M, hydroxyl, formoxyl or amino replace.
R10And R11Represent 1 valency alkyl of hydrogen atom or carbon number 1～20 independently of one another, be respectively present multiple R10And R11Time, they each other can be identical or different.
M represents hydrogen atom or alkali metal atom.)
[2] compound as described in [1], R1For having the thiazolinyl of the carbon number 2～16 of substituent group or can have the cycloalkenyl group of carbon number 3～16 of substituent group.
[3] compound as described in [1] or [2], R1For having the thiazolinyl of the carbon number 2～10 of substituent group or can have the cycloalkenyl group of carbon number 3～10 of substituent group.
[4] compound as according to any one of [1]～[3], R2Aryl for the thiazolinyl of carbon number 2～10, the alkyl of carbon number 3～10, the cycloalkenyl group of carbon number 3～10 or carbon number 6～15.
[5] a kind of coloring agent, it is containing, for example the compound described in any one in [1]～[4].
[6] coloring agent as described in [5], it contains pigment further.
[7] a kind of colored curable resin composition, it contains the coloring agent described in [5] or [6], resin, polymerizable compound, polymerization initiator and solvent.
[8] a kind of color filter, its colored curable resin composition described in [7] is formed.
[9] a kind of liquid crystal indicator, it comprises the color filter described in [8].
[10] compound that a kind of formula (II) represents.
[changing 2]
(in formula, R1For having the thiazolinyl of the carbon number 2～20 of substituent group or can have the cycloalkenyl group of carbon number 3～20 of substituent group, constitute-the CH of this thiazolinyl or cycloalkenyl group2-can by oxygen atom ,-N (R10)-or carbonyl substituted.
R2Represent 1 valency alkyl of hydrogen atom or carbon number 1～20.
R3～R5Represent hydrogen atom, 1 valency alkyl of carbon number 1～20, halogen atom, cyano group, nitro, carbamoyl, sulfamoyl ,-SO independently of one another3M、-CO2M, hydroxyl, formoxyl or amino.
R2～R5In the aforementioned alkyl represented ,-CH2-can by oxygen atom, sulphur atom ,-N (R11)-, sulfonyl or carbonyl substituted, hydrogen atom can by halogen atom, cyano group, nitro, carbamoyl, sulfamoyl ,-SO3M、-CO2M, hydroxyl, formoxyl or amino replace.
R10And R11Represent 1 valency alkyl of hydrogen atom or carbon number 1～20 independently of one another, be respectively present multiple R10And R11Time, they each other can be identical or different.
M represents hydrogen atom or alkali metal atom.)
[11] compound that a kind of formula (III) represents.
[changing 3]
(in formula, R1For having the thiazolinyl of the carbon number 2～20 of substituent group or can have the cycloalkenyl group of carbon number 3～20 of substituent group, constitute-the CH of this thiazolinyl or cycloalkenyl group2-can by oxygen atom ,-N (R10)-or carbonyl substituted.
R2Represent 1 valency alkyl of hydrogen atom or carbon number 1～20.
R3～R5Represent hydrogen atom, 1 valency alkyl of carbon number 1～20, halogen atom, cyano group, nitro, carbamoyl, sulfamoyl ,-SO independently of one another3M、-CO2M, hydroxyl, formoxyl or amino.
R2～R5In the aforementioned alkyl represented ,-CH2-can by oxygen atom, sulphur atom ,-N (R11)-, sulfonyl or carbonyl substituted, hydrogen atom can by halogen atom, cyano group, nitro, carbamoyl, sulfamoyl ,-SO3M、-CO2M, hydroxyl, formoxyl or amino replace.
R10And R11Represent 1 valency alkyl of hydrogen atom or carbon number 1～20 independently of one another, be respectively present multiple R10And R11Time, they each other can be identical or different.
M represents hydrogen atom or alkali metal atom.)
Invention effect
Even if the painted coated film using above-claimed cpd manufacture be impregnated in NMP, the stripping quantity of the coloring agent dissolving in NMP from aforementioned painted coated film is also few, is therefore excellent in the compound of the present invention dyestuff as the color filter for display devices such as liquid crystal indicators.
Detailed description of the invention
The compound of the present invention is the compound (hereinafter sometimes referred to compound (I)) represented by formula (I).Compound (I) also includes its tautomer and salt thereof.
[changing 4]
(in formula, L represents divalent alkyl or the sulfonyl of carbon number 1～20.
X represents oxygen atom or sulphur atom.
R1Expression can have the thiazolinyl of the carbon number 2～20 of substituent group or can have the cycloalkenyl group of carbon number 3～20 of substituent group, constitutes-the CH of this thiazolinyl or cycloalkenyl group2-can by oxygen atom ,-N (R10)-or carbonyl substituted.
R2Represent 1 valency alkyl of hydrogen atom or carbon number 1～20.
R3～R9Represent hydrogen atom, 1 valency alkyl of carbon number 1～20, halogen atom, cyano group, nitro, carbamoyl, sulfamoyl ,-SO independently of one another3M、-CO2M, hydroxyl, formoxyl or amino.
R2～R9In the aforesaid alkyl represented ,-CH2-can by oxygen atom, sulphur atom ,-N (R11)-, sulfonyl or carbonyl substituted, hydrogen atom can by halogen atom, cyano group, nitro, carbamoyl, sulfamoyl ,-SO3M、-CO2M, hydroxyl, formoxyl or amino replace.
R10And R11Represent 1 valency alkyl of hydrogen atom or carbon number 1～20 independently of one another, be respectively present multiple R10And R11Time, they each other can be identical or different.
M represents hydrogen atom or alkali metal atom.)
In formula (I), L represents divalent alkyl or the sulfonyl of carbon number 1～20.
The divalent alkyl of carbon number 1～20 can enumerate the sturated aliphatic hydrocarbon bases such as methylene, dimethylene, trimethylene, tetramethylene, 1,1-ethylidene (that is, ethane-1,1-bis-base), 2,2-propylidene (that is, propane-2,2 two bases)；The ester ring type saturated hydrocarbyls such as ring propylidene, ring butylidene, ring pentylidene, cyclohexylene, ring Asia heptyl, cyclooctylene；Fluorenes-9, the aromatic hydrocarbyl such as 9-bis-base.
The divalent alkyl of the preferred carbon number 1～16 of L, more preferably the divalent alkyl of carbon number 1～14.This divalent alkyl can be above-mentioned aliphatic alkyl, ester ring type alkyl or aromatic hydrocarbyl, it is also possible to is their combination.
From the viewpoint of obtain raw material, the group of any one expression in L more preferably following formula (L1)～formula (L4), it is preferred that the group of any one expression in formula (L1)～formula (L3), the group that particularly preferably formula (L1) or formula (L2) represent, it is most preferred that the group that formula (L1) represents.It addition, in following formula ● represent bonding position.
[changing 5]
In formula (I), X represents oxygen atom or sulphur atom, it is preferable that oxygen atom.The color filter formed by the colored curable resin composition comprising coloring agent have the tendency that lightness is high, described coloring agent to comprise compound (I) that X is oxygen atom.
R in formula (I)1Expression can have the carbon number 2～20 of substituent group thiazolinyl or can have substituent group carbon number 3～20 cycloalkenyl group (following, sometimes these groups are referred to as " can have the thiazolinyl of the carbon number 2～20 of substituent group or the cycloalkenyl group of carbon number 3～20 ".), constitute-the CH of this thiazolinyl or cycloalkenyl group2-can by oxygen atom ,-N (R10)-or carbonyl substituted.
R1The thiazolinyl of carbon number 2～20 include, for example: the straight-chain alkenyls such as vinyl (ethenyl, vinyl), acrylic, cyclobutenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decene base, hendecene base, laurylene base, tridecylene base, tetradecene base, 15 thiazolinyls, hexadecylene base, 17 thiazolinyls, octadecylene base, 19 thiazolinyls, icosa alkene base；Isopropenyl, 1,1-dimethyl-2-acrylic, 1-ethyl-2-acrylic, 1,2-dimethyl-1-acrylic, 1-methyl isophthalic acid-cyclobutenyl etc. have the thiazolinyl etc. of side chain.Wherein R1Preferred carbon number 2～20 straight-chain alkenyl.
R1The cycloalkenyl group of carbon number 3～20 include, for example: cyclopropanyl, cyclobutane base, cyclopentenyl, cyclopentadienyl group, cyclohexenyl group, cyclohexadienyl etc..
R1Preferably can have the thiazolinyl of the carbon number 2～16 of substituent group or the cycloalkenyl group of carbon number 3～16, more preferably can have the thiazolinyl of the carbon number 2～10 of substituent group or the cycloalkenyl group of carbon number 3～10, it is preferred that the cycloalkenyl group of the thiazolinyl of carbon number 2～8 or carbon number 3～8.
The number of the ethylenic unsaturated bond comprised in foregoing alkenyl or cycloalkenyl group can be 1 (such as AE-1～99 described later, 101～105,107～114), can also be 2 (such as AE-100, AE-106 described later), it is also possible to be more than 3.The number of the ethylenic unsaturated bond comprised in foregoing alkenyl or cycloalkenyl group preferably 1.
Aforementioned ethylenic unsaturated bond may reside in thiazolinyl end (free end side), it is also possible to is present in the part beyond thiazolinyl end.When being present in the part beyond thiazolinyl end, it is possible to be cis, trans in any one isomers.Aforementioned ethylenic unsaturated bond can be such as-CH=CH-,-CH=CH2Etc. such ethylenic unsaturated bond without substituted type, it is also possible to be-CH=CRc-(such as RcAlkyl for carbon number 1～10) ,-CRc=CRd-(such as Rc、RdIdentical or different, alkyl for carbon number 1～10), it is also possible to it is-CRc=CH2(such as RcAlkyl for carbon number 1～10) etc. such there is alkyl substituent Rc、RdEthylenic unsaturated bond.
Aforementioned Rc、RdThe alkyl of the carbon numbers 1～10 such as preferred methyl, ethyl, propyl group, butyl (especially the tert-butyl group), amyl group, hexyl, heptyl, octyl group, nonyl, decyl.
The hydrogen atom comprised in foregoing alkenyl or cycloalkenyl group can be substituted with a substituent.
Substituent group can enumerate the aromatic radical such as phenyl, toluyl groups；The halogen atoms such as fluorine atom, chlorine atom, bromine atoms；The alkoxyl of the carbon numbers 1～10 such as methoxyl group, ethyoxyl, propoxyl group, butoxy；The alkoxy carbonyl group of the carbon number such as methoxycarbonyl group, carbethoxyl group 2～10；Hydroxyl；Carboxylic acid group；Itrile group etc..Can being bonded the substituent group of more than 2 in foregoing alkenyl or cycloalkenyl group, when more than 2 substituent groups of bonding, it can be bonded on same carbon atom.
Additionally, foregoing substituents can also be bonded on the carbon atom constituting aforementioned ethylenic unsaturated bond, it is also possible to be bonded on the carbon atom of the aforementioned ethylenic unsaturated bond of non-composition.Foregoing substituents is when carboxyl, alkoxyl or aromatic radical, and the situation being bonded on the carbon atom constituting aforementioned ethylenic unsaturated bond is many.
Further, as long as the aforementioned thiazolinyl can with substituent group or cycloalkenyl group have ethylenic unsaturated bond ,-the CH comprised in them2-just can by oxygen atom ,-N (R10)-or carbonyl substituted.
Aforementioned R10Represent 1 valency alkyl of hydrogen atom or carbon number 1～20.R10Alkyl such as comprise the alkyl of the carbon numbers 1～10 such as methyl, ethyl, propyl group, butyl, amyl group, hexyl；The thiazolinyl of the carbon numbers 2～10 such as vinyl, acrylic, cyclobutenyl, pentenyl, hexenyl, hexadienyl；The cycloalkenyl group etc. of the carbon numbers 3～10 such as cyclobutane base, cyclopentenyl, cyclohexenyl group, cyclohexadienyl.
-CH2-by carbonyl substituted when, the position of this carbonyl is not particularly limited, it is preferable that carbonyl has and formula (I)-NR1R2N bonding position.
Additionally ,-CH2-by carbonyl substituted when, be adjacent to-the CH of this carbonyl2-can by oxygen atom and-N (R10)-in more than 1 replacement.That is ,-CH2-CH2-can by carboxyl or-C (=O)-N (R10)-replace.
This thiazolinyl can with substituent group or cycloalkenyl group can enumerate the group that following formula (AE-1)～formula (AE-114) represents.In following formula, ● represent and-NR1R2N bonding position.
[changing 6]
[changing 7]
[changing 8]
[changing 9]
[changing 10]
[changing 11]
[changing 12]
[changing 13]
[changing 14]
[changing 15]
Deliquescent viewpoint from the solvent at compound (I) considers, R1The group of any one expression in preferred formula (AE-1)～formula (AE-25), formula (AE-38)～formula (AE-44), formula (AE-61)～formula (AE-64) or formula (AE-80)～formula (AE-81), more preferably the group of any one expression in formula (AE-1)～formula (AE-25), formula (AE-61)～formula (AE-64) or formula (AE-80)～formula (AE-81), it is particularly preferred to the group of formula (AE-1)～formula (AE-19) or any one expression in formula (AE-80)～formula (AE-81).
R2Represent 1 valency alkyl of hydrogen atom or carbon number 1～20.
R3～R9Represent hydrogen atom, 1 valency alkyl of carbon number 1～20, halogen atom, cyano group, nitro, carbamoyl, sulfamoyl ,-SO independently of one another3M、-CO2M, hydroxyl, formoxyl or amino.
R2～R9In alkyl can enumerate: the thiazolinyl that above-mentioned formula (AE-1)～formula (AE-25), formula (AE-38)～formula (AE-44) or formula (AE-61)～formula (AE-63) represent；The aliphatic alkyls such as alkyl such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, (2-ethyl) butyl, 1,3-butadiene base, amyl group, isopentyl, 3-amyl group, neopentyl, tertiary pentyl, 1-methyl amyl, 2-methyl amyl, pentenyl, (3-ethyl) amyl group, hexyl, isohesyl, 5-methylhexyl, (2-ethyl) hexyl, heptyl, (3-ethyl) heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, octadecyl；
The cycloalkenyl groups such as cyclopentenyl, cyclohexenyl group (compound that such as formula (AE-64) represents), cycloheptenyl, cyclo-octene base；Cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1, 2-Dimethylcyclohexyl, 1, 3-Dimethylcyclohexyl, 1, 4-Dimethylcyclohexyl, 2, 3-Dimethylcyclohexyl, 2, 4-Dimethylcyclohexyl, 2, 5-Dimethylcyclohexyl, 2, 6-Dimethylcyclohexyl, 3, 4-Dimethylcyclohexyl, 3, 5-Dimethylcyclohexyl, 2, 2-Dimethylcyclohexyl, 3, 3-Dimethylcyclohexyl, 4, 4-Dimethylcyclohexyl, 2, 4, 6-trimethylcyclohexyl, 2, 2, 6, 6-tetramethyl-ring hexyl, 3, 3, 5, the cycloalkyl such as 5-tetramethyl-ring hexyl；In ester ring type alkyl；
Phenyl, o-tolyl, a tolyl, p-methylphenyl, 2,3-3,5-dimethylphenyl, 2,4-3,5-dimethylphenyl, 2,5-3,5-dimethylphenyl, 2,6-3,5-dimethylphenyl, 3,4-3,5-dimethylphenyl, 3,5-3,5-dimethylphenyls, sym-trimethylbenzene. base (メ シ チ Le base), adjacent cumenyl, a cumenyl, to monocyclic aromatic alkyl such as cumenyl, 2,6-double; two (2-propyl group) phenyl；The Ppolynuclear aromatic alkyl such as 1-naphthyl, 2-naphthyl, xenyl；Deng aromatic hydrocarbyl.The group that cyclohexyl methyl, benzyl, phenethyl etc. additionally also can be enumerated to combine aforementioned group and formed.
R2～R9In the 1 aforementioned aliphatic alkyl of valency of the 1 preferred carbon number of valency alkyl 1～10 of carbon number 1～20, aforementioned ester ring type alkyl or aforementioned fragrance race alkyl.
Aforementioned aliphatic alkyl is preferably saturated or unsaturated fatty hydrocarbons base, more preferably thiazolinyl, alkyl etc..
The aforementioned preferred monocycle of ester ring type alkyl or multi-ring ester ring type alkyl, more preferably cycloalkenyl group, cycloalkyl.
The preferred monocycle of aforementioned fragrance race alkyl or Ppolynuclear aromatic alkyl.
R11Represent 1 valency alkyl of hydrogen atom or carbon number 1～20.There is multiple R11Time, they each other can be identical or different.R11With aforementioned R10Represent the identical meaning.
Constitute R2～R9In-the CH of 1 valency alkyl2-by oxygen atom, sulphur atom ,-N (R11)-, sulfonyl or carbonyl substituted after group and/or, the hydrogen atom that comprises of this 1 valency alkyl is by halogen atom, cyano group, nitro, carbamoyl, sulfamoyl ,-SO3M、-CO2Group after M, hydroxyl, formoxyl or amino replacement can be enumerated:
The alkoxyls such as methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, amoxy, (2-ethyl) hexyloxy；
The aryloxy group such as phenoxy group；
The aralkoxies such as benzyloxy；
The straight chained alkyl carbonyls such as acetyl group, ethylcarbonyl group, propyl group carbonyl, butyl carbonyl, pentylcarbonyl, hexyl carbonyl, heptyl carbonyl, octyl group carbonyl, nonyl carbonyl, decyl carbonyl, dodecylcarbonyl, dodecyl carbonyl, butyl carbonyl；Isopropylcarbonyl, butylcarbonyl, sec-butylcarbonyl group, tert-butyl carbonyl, (1-ethyl) butyl carbonyl, (2-ethyl) butyl carbonyl, i, neopentyl carbonyl, tertiary pentyl carbonyl, 1-methyl amyl carbonyl, 2-methyl amyl carbonyl, (1-ethyl) pentylcarbonyl, (3-ethyl) pentylcarbonyl, isohexylcarbonyl, 5-methylhexyl carbonyl, (2-ethyl) hexyl carbonyl, (3-ethyl) heptyl carbonyl etc. have the alkyl-carbonyl of side chain；The alkenyl carbonyls such as isopropenyl carbonyl, 1-acrylic carbonyl, 2-acrylic carbonyl, crotyl carbonyl, 1,3-butadiene base carbonyl, pentenyl carbonyl；The acyl groups such as naphthene base carbonyl such as cyclohexylmethylcarbonyl, cyclopropyl carbonyl, cyclobutyl carbonyl, cyclopentylcarbonyl, cyclohexyl-carbonyl；
The acyloxy such as acetoxyl group, benzoyloxy；
The alkoxy carbonyls such as methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl；
The thiazolinyl that above-mentioned formula (AE-26)～formula (AE-37), formula (AE-45)～formula (AE-60) or formula (AE-65)～formula (AE-102) represent；
The N-straight chained alkyl carbamoyls such as N-methylcarbamoyl, N-ethylaminocarbonyl, N-propvlcarbamovl, N-Butylcarbamoyl, N-pentylcarbamoy, N-hexylamino formoxyl, N-heptyl carbamoyl, N-octyl amino formoxyl；nullN-isopropylcarbamoyl、N-butylcarbamoyl、N-s-butylamino formoxyl、N-t-Butylcarbamoyl、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) carbamoyl、N-(2-methyl butyl) carbamoyl、N-(3-methyl butyl) carbamoyl、N-(1，3-dimethylbutyl) carbamoyl、N-(3，3-dimethylbutyl) carbamoyl、N-(1-methylhexyl) carbamoyl、N-(1，4-dimethyl amyl group) carbamoyl、N-(2-ethylhexyl) carbamoyl、N-(1，5-dimethyl) hexylamino formoxyl、N-(1，1，2，2-tetramethyl butyl) the N-containg branched alkyl radical carbamoyl such as carbamoyl；The one substituted-amino formoxyls such as N-cycloalkylcarbamoyl such as N-cyclopentylcarbamoyl；
N, N-formyl-dimethylamino, N, N-ethylmethylamino formoxyl, N; N-diethylamino formoxyl, N, N-propyl-methylamino formoxyl, N, N-butyl ethyl carbamoyl, N; N, the N-straight chained alkyl straight chained alkyl carbamoyls such as N-hept-ylmethyl carbamoyl；N, the N-containg branched alkyl radical straight chained alkyl carbamoyls such as N, N-isopropylmethylamino formoxyl, N, N-tertbutyl methyl carbamoyl；The disubstituted amido formoxyls such as N, N-containg branched alkyl radical containg branched alkyl radical carbamoyl such as double; two (1-methyl-propyl) carbamoyl of N, N-, double; two (2-ethylhexyl) carbamoyls of N, N-；
The N-straight chained alkyl sulfamoyls such as N-Methylsulfamoyl, N-ethylsulfamovl, N-propylsulfamov, N-Butylsulfamoyl base, N-amyl group sulfamoyl, N-hexyl sulfamoyl, N-heptyl sulfamoyl, N-octyl group sulfamoyl；nullN-isopropylsulfamoyl base、N-isobutyl group sulfamoyl、N-sec-butyl sulfamoyl、N-tert-butyl group 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-(1，3-dimethylbutyl) sulfamoyl、N-(3，3-dimethylbutyl) sulfamoyl、N-(1-methylhexyl) sulfamoyl、N-(1，4-dimethyl amyl group) sulfamoyl、N-(2-ethylhexyl) sulfamoyl、N-(1，5-dimethyl) hexyl sulfamoyl、N-(1，1，2，2-tetramethyl butyl) the N-containg branched alkyl radical sulfamoyl such as sulfamoyl、The N-cycloalkyl sulfamoyls such as N-Cyclopentylsulfamoyl base etc. one replace sulfamoyl；
N, the N-straight chained alkyl straight chained alkyl sulfamoyls such as N, N-DimethylsuIfamoyl, N, N-ethyl-methyl sulfamoyl, N, N-diethyl amino sulfonyl, N, N-hydroxypropyl methyl sulfamoyl, N, N-butyl ethyl sulfamoyl, N, N-hept-ylmethyl sulfamoyl；N, the N-containg branched alkyl radical straight chained alkyl sulfamoyls such as N, N-isopropyl methyl sulfamoyl, N, N-tertbutyl methyl sulfamoyl；N, the N-containg branched alkyl radical containg branched alkyl radical sulfamoyls such as double; two (1-methyl-propyl) sulfamoyl of N, N-, double; two (2-ethylhexyl) sulfamoyls of N, N-etc. two replace sulfamoyl；
N-methylamino, N-ethylamino, N-propylcarbamic, N-butylamino, N-hexylamino, N-heptyl amino, N-octyl amino, etc. N-straight chained alkyl amino；nullN-isopropylamino、N-isobutylamino、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-methyl butyl) amino、N-(3-methyl butyl) amino、N-(1，3-dimethylbutyl) amino、N-(3，3-dimethylbutyl) amino、N-(1-methylhexyl) amino、N-(1，4-dimethyl amyl group) amino、N-(2-ethylhexyl) amino、N-(1，5-dimethyl) hexylamino、N-(1，1，2，2-tetramethyl butyl) the N-containg branched alkyl radical amino such as amino；The N-alkyl aminos such as N-cycloalkyl amino such as N-clopentylamino；
N, the N-straight chained alkyl straight chained alkyl amino such as N, N-dimethylamino, N, N-ethylmethylamino, N, N-diethylamino, N, N-propyl-methylamino, N, N-butyl ethyl amino, N, N-hept-ylmethyl amino；N, the N-containg branched alkyl radical straight chained alkyl amino such as N, N-isopropylmethylamino, N, N-tertbutyl methyl amino；N, the N-dialkyl amidos such as N, N-containg branched alkyl radical containg branched alkyl radical amino such as double; two (1-methyl-propyl) amino of N, N-, double; two (2-ethylhexyl) amino of N, N-；
The N-straight chained alkyl amino methyls such as N-Methylaminomethyl, N-ethylaminomethyl, N-propylcarbamic methyl, N-pentyl amino methyl, N-hexylamino methyl, N-heptyl amino methyl, N-octilaminomethyl；nullN-isopropylaminomethyl、N-isobutylamino methyl、N-s-butylamino methyl、N-tert-butylamino 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-(1，3-dimethylbutyl) amino methyl、N-(3，3-dimethylbutyl) amino methyl、N-(1-methylhexyl) amino methyl、N-(1，4-dimethyl amyl group) amino methyl、N-(2-ethylhexyl) amino methyl、N-(1，5-dimethyl) hexylamino methyl、N-(1，1，2，2-tetramethyl butyl) the N-containg branched alkyl radical amino methyl such as amino methyl；The N-alkylamidomethyl such as N-cycloalkylaminomethyl such as N-clopentylamino methyl；
N, the N-straight chained alkyl straight chained alkyl amino methyls such as N, N-dimethylaminomethyl, N, N-ethylmethylaminomethyl, N, N-diethylamino methyl, N, N-propyl-methylamino methyl, N, N-butyl ethyl amino methyl, N, N-hept-ylmethyl amino methyl；N, the N-containg branched alkyl radical straight chained alkyl amino methyls such as N, N-isopropylmethylamino methyl, N, N-tertbutyl methyl amino methyl；N, the N-dialkylaminomethyl group such as N, N-containg branched alkyl radical containg branched alkyl radical amino methyl such as double; two (1-methyl-propyl) amino methyl of N, N-, double; two (2-Octyl Nitrite) amino methyls of N, N-；
The perfluor straight chained alkyls such as trifluoromethyl, perfluoro-ethyl, perfluoro propyl, perfluoro butyl, perfluoropentyl, perfluoro hexyl, perfluor heptyl, perfluoro capryl, perfluor nonyl, perfluoro decyl, perfluor undecyl, perfluorododecyl, perfluor octadecyl；The perfluor containg branched alkyl radicals such as perfluoroisopropyl, perfluor isobutyl group, perfluor sec-butyl, perfluoro-t-butyl, perfluor isopentyl, perfluor (3-amyl group) base, perfluor neopentyl, perfluor tertiary pentyl, perfluor (1-methyl amyl) base, perfluor (2-methyl amyl) base, perfluor isohesyl, perfluor (5-methylhexyl) base, perfluor (2-ethylhexyl) base；The perfluors etc. such as perfluor isopropenyl, perfluor (1-acrylic) base, perfluor (2-acrylic) base, perfluor (crotyl) base, perfluor (1,3-butadiene base) base, perfluor (pentenyl) base have the aliphatic alkyl of fluorine atom；
The perfluorocycloalkyl groups such as perfluor cyclopropyl, perfluorocyclobutanearyl, perfluor cyclopenta, perfluorocyclohexyl, perfluor suberyl；nullPerfluor (1-methylcyclohexyl) base、Perfluor (2-methylcyclohexyl) base、Perfluor (3-methylcyclohexyl) base、Perfluor (4-methylcyclohexyl) base、Perfluor (1，2-Dimethylcyclohexyl) base、Perfluor (1，3-Dimethylcyclohexyl) base、Perfluor (1，4-Dimethylcyclohexyl) base、Perfluor (2，3-Dimethylcyclohexyl) base、Perfluor (2，4-Dimethylcyclohexyl)、Perfluor (2，5-Dimethylcyclohexyl) base、Perfluor (2，6-methylcyclohexyl) base、Perfluor (3，4-Dimethylcyclohexyl) base、Perfluor (3，5-Dimethylcyclohexyl) base、Perfluor (2，2-Dimethylcyclohexyl) base、Perfluor (3，3-Dimethylcyclohexyl) base、Perfluor (4，4-Dimethylcyclohexyl) base、Perfluor (2，4，6-trimethylcyclohexyl) base、Perfluor (2，2，6，6-tetramethyl-ring hexyl) base、Perfluor (3，3，5，5-tetramethyl-ring hexyl) the perfluor substituted cycloalkyl such as base；The perfluor cycloalkenyl groups etc. such as perfluor cyclohexenyl group have fluorine atom ester ring type alkyl；
Perfluorophenyl, perfluor o-tolyl, tolyl between perfluor, perfluor p-methylphenyl, perfluoroxylene base, perfluor sym-trimethylbenzene. base, perfluor neighbour's cumenyl, cumenyl between perfluor, perfluor is to cumenyl, perfluor benzyl, perfluor phenethyl, perfluorinated biphenyl, perfluor (1-naphthyl) base, perfluor (2-naphthyl) base, 1-trifluoromethyl, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 2, double, two (trifluoromethyl) phenyl methyl of 3-, 2, double, two (trifluoromethyl) phenyl methyl of 4-, 2, double, two (trifluoromethyl) phenyl methyl of 5-, 2, double, two (trifluoromethyl) phenyl methyl of 6-, 3, double, two (trifluoromethyl) phenyl methyl of 4-, 3, double, two (trifluoromethyl) phenyl methyl etc. of 5-has the aromatic hydrocarbyl of fluorine atom；
The perfluoro alkoxies such as perfluoromethoxy, pentafluoroethoxy, perfluor propoxyl group, perfluor butoxy, perfluor amoxy；Perfluoroisopropoxy groups, perfluoroisobutoxy, perfluor sec-butoxy, perfluor tert .-butoxy, (perfluoro-ethyl) methoxyl group, (perfluoro propyl) methoxyl group, (perfluoro butyl) methoxyl group, (perfluoropentyl) methoxyl group, (perfluoro 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, the perfluor straight chained alkyl alkoxyls such as (perfluor octadecyl) methoxyl group；(perfluoroisopropyl) methoxyl group, (perfluor isobutyl group) methoxyl group, (perfluor sec-butyl) methoxyl group, (perfluoro-t-butyl) methoxyl group, (perfluor isopentyl) methoxyl group, (perfluor (3-amyl group)) methoxyl group, (perfluor neopentyl) methoxyl group, (perfluor tertiary pentyl) methoxyl group, (perfluor (1-methyl amyl) methoxyl group, (perfluor (2-methyl amyl)) methoxyl group, (perfluor isohesyl) methoxyl group, (perfluor (5-methylhexyl) methoxyl group, the perfluor containg branched alkyl radical alkoxyls such as (perfluor ((2-ethyl) hexyl)) methoxyl group；The perfluor aryloxy group such as perfluor phenoxy group；The perfluor aralkyl oxies such as perfluor benzyloxy；(perfluor isopropenyl) methoxyl group, (perfluor (1-acrylic)) methoxyl group, (perfluor (2-acrylic)) methoxyl group, (perfluor (crotyl)) methoxyl group, (the perfluor alkoxyl such as perfluor (1,3-butadiene base) methoxyl group, (perfluor (pentenyl)) methoxyl group；2,2,2-trifluoro ethoxies etc. have the substituted oxy of fluorine atom；Deng.
M represents hydrogen atom or alkali metal atom.Alkali metal atom can enumerate sodium atom and potassium atom.The preferred hydrogen atom of M.
Halogen atom can enumerate fluorine atom, chlorine atom, bromine atoms and atomic iodine.
R3～R9Especially preferred hydrogen atom.
Aforementioned R2Alkyl can enumerate: the thiazolinyl that above-mentioned formula (AE-1)～formula (AE-14), formula (AE-20)～formula (AE-25), formula (AE-38)～formula (AE-44) or formula (AE-61)～formula (AE-63), 1,3-butadiene base, pentenyl represent；The alkyl etc. such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, (2-ethyl) butyl, amyl group, isopentyl, 3-amyl group, neopentyl, tertiary pentyl, 1-methyl amyl, 2-methyl amyl, (3-ethyl) amyl group, hexyl, isohesyl, 5-methylhexyl, (2-ethyl) hexyl, heptyl, (3-ethyl) heptyl, octyl group, nonyl, decyl, undecyl, dodecyl；Deng aliphatic alkyl；
Phenyl, o-tolyl, a tolyl, p-methylphenyl, 2,3-3,5-dimethylphenyl, 2,4-3,5-dimethylphenyl, 2,5-3,5-dimethylphenyl, 2,6-3,5-dimethylphenyl, 3,4-3,5-dimethylphenyl, 3,5-3,5-dimethylphenyls, sym-trimethylbenzene. base, adjacent cumenyl, a cumenyl, to aromatic hydrocarbyls such as aryl such as cumenyl, 2,6-double; two (2-propyl group) phenyl.
The alkyl of the carbon numbers 1～10 such as group that wherein particularly preferably above-mentioned formula (AE-1)～formula (AE-10) represents, methyl, ethyl, propyl group, isopropyl, 2-acrylic, butyl, amyl group, hexyl, (2-ethyl) hexyl, heptyl, octyl group, nonyl, decyl；The aromatic radical of the carbon numbers 1～10 such as phenyl, o-tolyl, p-methylphenyl, 2,3-3,5-dimethylphenyls, 2,4-3,5-dimethylphenyls, 2,5-3,5-dimethylphenyls, 2,6-3,5-dimethylphenyls, sym-trimethylbenzene. base, adjacent cumenyl.
R2Compound for the present invention of these groups is excellent in the dissolubility of solvent.
Consider from compound (I) deliquescent viewpoint in a solvent, R21 valency alkyl of preferred carbon number 1～15, more preferably 1 valency aliphatic alkyl of carbon number 1～15, ester ring type alkyl or aromatic hydrocarbyl, it is preferred that the aromatic radical of the cycloalkenyl group of the thiazolinyl of carbon number 2～10, the alkyl of carbon number 3～10, carbon number 3～10 or carbon number 6～15, the aromatic radical of the more preferably thiazolinyl of carbon number 2～8, the alkyl of carbon number 3～8 or carbon number 6～10 further.
R3It can be the combination of more than 1 of aforementioned aliphatic alkyl, ester ring type alkyl and aromatic hydrocarbon.
In formula (I), R1～R9Each exist 2, and can be mutually identical between each 2 can also be mutually different.
Concrete compound (I) can enumerate the compound that the compound represented with the formula (IA) shown in table 1 below～table 16 is basic structure.
[changing 16]
It addition, in table 1 below～table 16,
The group that " L1 " expression (L1) represents, the group that " L2 " expression (L2) represents, the group that " L3 " expression (L3) represents, the group that " L4 " expression (L4) represents, " O " represents oxygen atom, and " S " represents sulphur atom
The group that " AE2 " expression (AE-2) represents,
The group that " AE3 " expression (AE-3) represents,
The group that " AE4 " expression (AE-4) represents,
The group that " AE5 " expression (AE-5) represents,
The group that " AE7 " expression (AE-7) represents,
The group that " AE9 " expression (AE-9) represents,
The group that " AE10 " expression (AE-10) represents,
The group that " AE17 " expression (AE-17) represents,
" EHx " represents 2-ethyl-1-hexyl,
" Oct " shows octyl group,
" Ph " shows phenyl,
" Tol " represents o-tolyl,
" DMP " represents 2,4-3,5-dimethylphenyls,
" MES " represents sym-trimethylbenzene. base.
[table 1]
| XA | LA | R1A | R2A | |
| I-1 | O | L1 | AE2 | AE2 |
| I-2 | O | L1 | AE2 | EHx |
| I-3 | O | L1 | AE2 | Oct |
| I-4 | O | L1 | AE2 | Ph |
| I-5 | O | L1 | AE2 | Tol |
| I-6 | O | L1 | AE2 | DMP |
| I-7 | O | L1 | AE2 | MES |
| I-8 | O | L1 | AE3 | AE3 |
| I-9 | O | L1 | AE3 | EHx |
| I-10 | O | L1 | AE3 | Oct |
| I-11 | O | L1 | AE3 | Ph |
| I-12 | O | L1 | AE3 | Tol |
| I-13 | O | L1 | AE3 | DMP |
| I-14 | O | L1 | AE3 | MES |
| I-15 | O | L1 | AE4 | AE4 |
| I-16 | O | L1 | AE4 | EHx |
| I-17 | O | L1 | AE4 | Oct |
| I-18 | O | L1 | AE4 | Ph |
| I-19 | O | L1 | AE4 | Tol |
| I-20 | O | L1 | AE4 | DMP |
| I-21 | O | L1 | AE4 | MES |
| I-22 | O | L1 | AE5 | AE5 |
| I-23 | O | L1 | AE5 | EHx |
| I-24 | O | L1 | AE5 | Oct |
| I-25 | O | L1 | AE5 | Ph |
| I-26 | O | L1 | AE5 | Tol |
| I-27 | O | L1 | AE5 | DMP |
| I-28 | O | L1 | AE5 | MES |
[table 2]
| XA | LA | R1A | R2A | |
| I-29 | O | L1 | AE7 | AE7 15 --> |
| I-30 | O | L1 | AE7 | EHx |
| I-31 | O | L1 | AE7 | Oct |
| I-32 | O | L1 | AE7 | Ph |
| I-33 | O | L1 | AE7 | Tol |
| I-34 | O | L1 | AE7 | DMP |
| I-35 | O | L1 | AE7 | MES |
| I-36 | O | L1 | AE9 | AE9 |
| I-37 | O | L1 | AE9 | EHx |
| I-38 | O | L1 | AE9 | Oct |
| I-39 | O | L1 | AE9 | Ph |
| I-40 | O | L1 | AE9 | Tol |
| I-41 | O | L1 | AE9 | DMP |
| I-42 | O | L1 | AE9 | MES |
| I-43 | O | L1 | AE10 | AE10 |
| I-44 | O | L1 | AE10 | EHx |
| I-45 | O | L1 | AE10 | Oct |
| I-46 | O | L1 | AE10 | Ph |
| I-47 | O | L1 | AE10 | Tol |
| I-48 | O | L1 | AE10 | DMP |
| I-49 | O | L1 | AE10 | MES |
| I-50 | O | L1 | AE17 | AE17 |
| I-51 | O | L1 | AE17 | EHx |
| I-52 | O | L1 | AE17 | Oct |
| I-53 | O | L1 | AE17 | Ph |
| I-54 | O | L1 | AE17 | Tol |
| I-55 | O | L1 | AE17 | DMP |
| I-56 | O | L1 | AE17 | MES |
[table 3]
| XA | LA | R1A | R2A | |
| I-57 | O | L2 | AE2 | AE2 |
| I-58 | O | L2 | AE2 | EHx |
| I-59 | O | L2 | AE2 | Oct |
| I-60 | O | L2 | AE2 | Ph |
| I-61 | O | L2 | AE2 | Tol |
| I-62 | O | L2 | AE2 | DMP |
| I-63 | O | L2 | AE2 | MES |
| I-64 | O | L2 | AE3 | AE3 |
| I-65 | O | L2 | AE3 | EHx 16 --> |
| I-66 | O | L2 | AE3 | Oct |
| I-67 | O | L2 | AE3 | Ph |
| I-68 | O | L2 | AE3 | Tol |
| I-69 | O | L2 | AE3 | DMP |
| I-70 | O | L2 | AE3 | MES |
| I-71 | O | L2 | AE4 | AE4 |
| I-72 | O | L2 | AE4 | EHx |
| I-73 | O | L2 | AE4 | Oct |
| I-74 | O | L2 | AE4 | Ph |
| I-75 | O | L2 | AE4 | Tol |
| I-76 | O | L2 | AE4 | DMP |
| I-77 | O | L2 | AE4 | MES |
| I-78 | O | L2 | AE5 | AE5 |
| I-79 | O | L2 | AE5 | EHx |
| I-80 | O | L2 | AE5 | Oct |
| I-81 | O | L2 | AE5 | Ph |
| I-82 | O | L2 | AE5 | Tol |
| I-83 | O | L2 | AE5 | DMP |
| I-84 | O | L2 | AE5 | MES |
[table 4]
| XA | LA | R1A | R2A | |
| I-85 | O | L2 | AE7 | AE7 |
| I-86 | O | L2 | AE7 | EHx |
| I-87 | O | L2 | AE7 | Oct |
| I-88 | O | L2 | AE7 | Ph |
| I-89 | O | L2 | AE7 | Tol |
| I-90 | O | L2 | AE7 | DMP |
| I-91 | O | L2 | AE7 | MES |
| I-92 | O | L2 | AE9 | AE9 |
| I-93 | O | L2 | AE9 | EHx |
| I-94 | O | L2 | AE9 | Oct |
| I-95 | O | L2 | AE9 | Ph |
| I-96 | O | L2 | AE9 | Tol |
| I-97 | O | L2 | AE9 | DMP |
| I-98 | O | L2 | AE9 | MES |
| I-99 | O | L2 | AE10 | AE10 |
| I-100 | O | L2 | AE10 | EHx |
| I-101 | O | L2 | AE10 | Oct 17 --> |
| I-102 | O | L2 | AE10 | Ph |
| I-103 | O | L2 | AE10 | Tol |
| I-104 | O | L2 | AE10 | DMP |
| I-105 | O | L2 | AE10 | MES |
| I-106 | O | L2 | AE17 | AE17 |
| I-107 | O | L2 | AE17 | EHx |
| I-108 | O | L2 | AE17 | Oct |
| I-109 | O | L2 | AE17 | Ph |
| I-110 | O | L2 | AE17 | Tol |
| I-111 | O | L2 | AE17 | DMP |
| I-112 | O | L2 | AE17 | MES |
[table 5]
| XA | LA | R1A | R2A | |
| I-113 | O | L3 | AE2 | AE2 |
| I-114 | O | L3 | AE2 | EHx |
| I-115 | O | L3 | AE2 | Oct |
| I-116 | O | L3 | AE2 | Ph |
| I-117 | O | L3 | AE2 | Tol |
| I-118 | O | L3 | AE2 | DMP |
| I-119 | O | L3 | AE2 | MES |
| I-120 | O | L3 | AE3 | AE3 |
| I-121 | O | L3 | AE3 | EHx |
| I-122 | O | L3 | AE3 | Oct |
| I-123 | O | L3 | AE3 | Ph |
| I-124 | O | L3 | AE3 | Tol |
| I-125 | O | L3 | AE3 | DMP |
| I-126 | O | L3 | AE3 | MES |
| I-127 | O | L3 | AE4 | AE4 |
| I-128 | O | L3 | AE4 | EHx |
| I-129 | O | L3 | AE4 | Oct |
| I-130 | O | L3 | AE4 | Ph |
| I-131 | O | L3 | AE4 | Tol |
| I-132 | O | L3 | AE4 | DMP |
| I-133 | O | L3 | AE4 | MES |
| I-134 | O | L3 | AE5 | AE5 |
| I-135 | O | L3 | AE5 | EHx |
| I-136 | O | L3 | AE5 | Oct |
| I-137 | O | L3 | AE5 | Ph 18 --> |
| I-138 | O | L3 | AE5 | Tol |
| I-139 | O | L3 | AE5 | DMP |
| I-140 | O | L3 | AE5 | MES |
[table 6]
| XA | LA | R1A | R2A | |
| I-141 | O | L3 | AE7 | AE7 |
| I-142 | O | L3 | AE7 | EHx |
| I-143 | O | L3 | AE7 | Oct |
| I-144 | O | L3 | AE7 | Ph |
| I-145 | O | L3 | AE7 | Tol |
| I-146 | O | L3 | AE7 | DMP |
| I-147 | O | L3 | AE7 | MES |
| I-148 | O | L3 | AE9 | AE9 |
| I-149 | O | L3 | AE9 | EHx |
| I-150 | O | L3 | AE9 | Oct |
| I-151 | O | L3 | AE9 | Ph |
| I-152 | O | L3 | AE9 | Tol |
| I-153 | O | L3 | AE9 | DMP |
| I-154 | O | L3 | AE9 | MES |
| I-155 | O | L3 | AE10 | AE10 |
| I-156 | O | L3 | AE10 | EHx |
| I-157 | O | L3 | AE10 | Oct |
| I-158 | O | L3 | AE10 | Ph |
| I-159 | O | L3 | AE10 | Tol |
| I-160 | O | L3 | AE10 | DMP |
| I-161 | O | L3 | AE10 | MES |
| I-162 | O | L3 | AE17 | AE17 |
| I-163 | O | L3 | AE17 | EHx |
| I-164 | O | L3 | AE17 | Oct |
| I-165 | O | L3 | AE17 | Ph |
| I-166 | O | L3 | AE17 | Tol |
| I-167 | O | L3 | AE17 | DMP |
| I-168 | O | L3 | AE17 | MES |
[table 7]
| XA | LA | R1A | R2A | |
| I-169 | O | L4 | AE2 | AE2 |
| I-170 | O | L4 | AE2 | EHx 19 --> |
| I-171 | O | L4 | AE2 | Oct |
| I-172 | O | L4 | AE2 | Ph |
| I-173 | O | L4 | AE2 | Tol |
| I-174 | O | L4 | AE2 | DMP |
| I-175 | O | L4 | AE2 | MES |
| I-176 | O | L4 | AE3 | AE3 |
| I-177 | O | L4 | AE3 | EHx |
| I-178 | O | L4 | AE3 | Oct |
| I-179 | O | L4 | AE3 | Ph |
| I-180 | O | L4 | AE3 | Tol |
| I-181 | O | L4 | AE3 | DMP |
| I-182 | O | L4 | AE3 | MES |
| I-183 | O | L4 | AE4 | AE4 |
| I-184 | O | L4 | AE4 | EHx |
| I-185 | O | L4 | AE4 | Oct |
| I-186 | O | L4 | AE4 | Ph |
| I-187 | O | L4 | AE4 | Tol |
| I-188 | O | L4 | AE4 | DMP |
| I-189 | O | L4 | AE4 | MES |
| I-190 | O | L4 | AE5 | AE5 |
| I-191 | O | L4 | AE5 | EHx |
| I-192 | O | L4 | AE5 | Oct |
| I-193 | O | L4 | AE5 | Ph |
| I-194 | O | L4 | AE5 | Tol |
| I-195 | O | L4 | AE5 | DMP |
| I-196 | O | L4 | AE5 | MES |
[table 8]
| XA | LA | R1A | R2A | |
| I-197 | O | L4 | AE7 | AE7 |
| I-198 | O | L4 | AE7 | EHx |
| I-199 | O | L4 | AE7 | Oct |
| I-200 | O | L4 | AE7 | Ph |
| I-201 | O | L4 | AE7 | Tol |
| I-202 | O | L4 | AE7 | DMP |
| I-203 | O | L4 | AE7 | MES |
| I-204 | O | L4 | AE9 | AE9 |
| I-205 | O | L4 | AE9 | EHx |
| I-206 | O | L4 | AE9 | Oct 20 --> |
| I-207 | O | L4 | AE9 | Ph |
| I-208 | O | L4 | AE9 | Tol |
| I-209 | O | L4 | AE9 | DMP |
| I-210 | O | L4 | AE9 | MES |
| I-211 | O | L4 | AE10 | AE10 |
| I-212 | O | L4 | AE10 | EHx |
| I-213 | O | L4 | AE10 | Oct |
| I-214 | O | L4 | AE10 | Ph |
| I-215 | O | L4 | AE10 | Tol |
| I-216 | O | L4 | AE10 | DMP |
| I-217 | O | L4 | AE10 | MES |
| I-218 | O | L4 | AE17 | AE17 |
| I-219 | O | L4 | AE17 | EHx |
| I-220 | O | L4 | AE17 | Oct |
| I-221 | O | L4 | AE17 | Ph |
| I-222 | O | L4 | AE17 | Tol |
| I-223 | O | L4 | AE17 | DMP |
| I-224 | O | L4 | AE17 | MES |
[table 9]
| XA | LA | R1A | R2A | |
| I-225 | S | L1 | AE2 | AE2 |
| I-226 | S | L1 | AE2 | EHx |
| I-227 | S | L1 | AE2 | Oct |
| I-228 | S | L1 | AE2 | Ph |
| I-229 | S | L1 | AE2 | Tol |
| I-230 | S | L1 | AE2 | DMP |
| I-231 | S | L1 | AE2 | MES |
| I-232 | S | L1 | AE3 | AE3 |
| I-233 | S | L1 | AE3 | EHx |
| I-234 | S | L1 | AE3 | Oct |
| I-235 | S | L1 | AE3 | Ph |
| I-236 | S | L1 | AE3 | Tol |
| I-237 | S | L1 | AE3 | DMP |
| I-238 | S | L1 | AE3 | MES |
| I-239 | S | L1 | AE4 | AE4 |
| I-240 | S | L1 | AE4 | EHx |
| I-241 | S | L1 | AE4 | Oct |
| I-242 | S | L1 | AE4 | Ph 21 --> |
| I-243 | S | L1 | AE4 | Tol |
| I-244 | S | L1 | AE4 | DMP |
| I-245 | S | L1 | AE4 | MES |
| I-246 | S | L1 | AE5 | AE5 |
| I-247 | S | L1 | AE5 | EHx |
| I-248 | S | L1 | AE5 | Oct |
| I-249 | S | L1 | AE5 | Ph |
| I-250 | S | L1 | AE5 | Tol |
| I-251 | S | L1 | AE5 | DMP |
| I-252 | S | L1 | AE5 | MES |
[table 10]
| XA | LA | R1A | R2A | |
| I-253 | S | L1 | AE7 | AE7 |
| I-254 | S | L1 | AE7 | EHx |
| I-255 | S | L1 | AE7 | Oct |
| I-256 | S | L1 | AE7 | Ph |
| I-257 | S | L1 | AE7 | Tol |
| I-258 | S | L1 | AE7 | DMP |
| I-259 | S | L1 | AE7 | MES |
| I-260 | S | L1 | AE9 | AE9 |
| I-261 | S | L1 | AE9 | EHx |
| I-262 | S | L1 | AE9 | Oct |
| I-263 | S | L1 | AE9 | Ph |
| I-264 | S | L1 | AE9 | Tol |
| I-265 | S | L1 | AE9 | DMP |
| I-266 | S | L1 | AE9 | MES |
| I-267 | S | L1 | AE10 | AE10 |
| I-268 | S | L1 | AE10 | EHx |
| I-269 | S | L1 | AE10 | Oct |
| I-270 | S | L1 | AE10 | Ph |
| I-271 | S | L1 | AE10 | Tol |
| I-272 | S | L1 | AE10 | DMP |
| I-273 | S | L1 | AE10 | MES |
| I-274 | S | L1 | AE17 | AE17 |
| I-275 | S | L1 | AE17 | EHx |
| I-276 | S | L1 | AE17 | Oct |
| I-277 | S | L1 | AE17 | Ph |
| I-278 | S | L1 | AE17 | Tol 22 --> |
| I-279 | S | L1 | AE17 | DMP |
| I-280 | S | L1 | AE17 | MES |
[table 11]
| XA | LA | R1A | R2A | |
| I-281 | S | L2 | AE2 | AE2 |
| I-282 | S | L2 | AE2 | EHx |
| I-283 | S | L2 | AE2 | Oct |
| I-284 | S | L2 | AE2 | Ph |
| 1-285 | S | L2 | AE2 | Tol |
| I-286 | S | L2 | AE2 | DMP |
| I-287 | S | L2 | AE2 | MES |
| I-288 | S | L2 | AE3 | AE3 |
| I-289 | S | L2 | AE3 | EHx |
| I-290 | S | L2 | AE3 | Oct |
| I-291 | S | L2 | AE3 | Ph |
| I-292 | S | L2 | AE3 | Tol |
| I-293 | S | L2 | AE3 | DMP |
| I-294 | S | L2 | AE3 | MES |
| I-295 | S | L2 | AE4 | AE4 |
| I-296 | S | L2 | AE4 | EHx |
| I-297 | S | L2 | AE4 | Oct |
| I-298 | S | L2 | AE4 | Ph |
| I-299 | S | I2 | AE4 | Tol |
| I-300 | S | L2 | AE4 | DMP |
| I-301 | S | L2 | AE4 | MES |
| I-302 | S | L2 | AE5 | AE5 |
| I-303 | S | L2 | AE5 | EHx |
| I-304 | S | L2 | AE5 | Oct |
| I-305 | S | L2 | AE5 | Ph |
| I-306 | S | L2 | AE5 | Tol |
| I-307 | S | L2 | AE5 | DMP |
| I-308 | S | L2 | AE5 | MES |
[table 12]
| XA | LA | R1A | R2A | |
| I-309 | S | L2 | AE7 | AE7 |
| I-310 | S | L2 | AE7 | EHx |
| I-311 | S | L2 | AE7 | Oct 23 --> |
| I-312 | S | L2 | AE7 | Ph |
| I-313 | S | L2 | AE7 | Tol |
| I-314 | S | L2 | AE7 | DMP |
| I-315 | S | L2 | AE7 | MES |
| I-316 | S | L2 | AE9 | AE9 |
| I-317 | S | L2 | AE9 | EHx |
| I-318 | S | L2 | AE9 | Oct |
| I-319 | S | L2 | AE9 | Ph |
| I-320 | S | L2 | AE9 | TOl |
| I-321 | S | L2 | AE9 | DMP |
| I-322 | S | L2 | AE9 | MES |
| I-323 | S | L2 | AE10 | AE10 |
| I-324 | S | L2 | AE10 | EHx |
| I-325 | S | L2 | AE10 | Oct |
| I-326 | S | L2 | AE10 | Ph |
| I-327 | S | L2 | AE10 | Tol |
| I-328 | S | L2 | AE10 | DMP |
| I-329 | S | L2 | AE10 | MES |
| I-330 | S | L2 | AE17 | AE17 |
| I-331 | S | L2 | AE17 | EHx |
| I-332 | S | L2 | AE17 | Oct |
| I-333 | S | L2 | AE17 | Ph |
| I-334 | S | L2 | AE17 | Tol |
| I-335 | S | L2 | AE17 | DMP |
| I-336 | S | L2 | AE17 | MES |
[table 13]
| XA | LA | R1A | R2A | |
| I-337 | S | L3 | AE2 | AE2 |
| I-338 | S | L3 | AE2 | EHx |
| I-339 | S | L3 | AE2 | Oct |
| I-340 | S | L3 | AE2 | Ph |
| I-341 | S | L3 | AE2 | Tol |
| I-342 | S | L3 | AE2 | DMP |
| I-343 | S | L3 | AE2 | MES |
| I-344 | S | L3 | AE3 | AE3 |
| I-345 | S | L3 | AE3 | EHx |
| I-346 | S | L3 | AE3 | Oct |
| I-347 | S | L3 | AE3 | Ph 24 --> |
| I-348 | S | L3 | AE3 | Tol |
| I-349 | S | L3 | AE3 | DMP |
| I-350 | S | L3 | AE3 | MES |
| I-351 | S | L3 | AE4 | AE4 |
| I-352 | S | L3 | AE4 | EHx |
| I-353 | S | L3 | AE4 | Oct |
| I-354 | S | L3 | AE4 | Ph |
| I-355 | S | L3 | AE4 | Tol |
| I-356 | S | L3 | AE4 | DMP |
| I-357 | S | L3 | AE4 | MES |
| I-358 | S | L3 | AE5 | AE5 |
| I-359 | S | L3 | AE5 | EHx |
| I-360 | S | L3 | AE5 | Oct |
| I-361 | S | L3 | AE5 | Ph |
| I-362 | S | L3 | AE5 | Tol |
| I-363 | S | L3 | AE5 | DMP |
| I-364 | S | L3 | AE5 | MES |
[table 14]
| XA | LA | R1A | R2A | |
| I-365 | S | L3 | AE7 | AE7 |
| I-366 | S | L3 | AE7 | EHx |
| I-367 | S | L3 | AE7 | Oct |
| I-368 | S | L3 | AE7 | Ph |
| I-369 | S | L3 | AE7 | Tol |
| I-370 | S | L3 | AE7 | DMP |
| I-371 | S | L3 | AE7 | MES |
| I-372 | S | L3 | AE9 | AE9 |
| I-373 | S | L3 | AE9 | EHx |
| I-374 | S | L3 | AE9 | Oct |
| I-375 | S | L3 | AE9 | Ph |
| I-376 | S | L3 | AE9 | Tol |
| I-377 | S | L3 | AE9 | DMP |
| I-378 | S | L3 | AE9 | MES |
| I-379 | S | L3 | AE10 | AE10 |
| I-380 | S | L3 | AE10 | EHx |
| I-381 | S | L3 | AE10 | Oct |
| I-382 | S | L3 | AE10 | Ph |
| I-383 | S | L3 | AE10 | Tol 25 --> |
| I-384 | S | L3 | AE10 | DMP |
| I-385 | S | L3 | AE10 | MES |
| I-386 | S | L3 | AE17 | AE17 |
| I-387 | S | L3 | AE17 | EHx |
| I-388 | S | L3 | AE17 | Oct |
| I-389 | S | L3 | AE17 | Ph |
| I-390 | S | L3 | AE17 | Tol |
| I-391 | S | L3 | AE17 | DMP |
| I-392 | S | L3 | AE17 | MES |
[table 15]
| XA | LA | R1A | R2A | |
| I-393 | S | L4 | AE2 | AE2 |
| I-394 | S | L4 | AE2 | EHx |
| I-395 | S | L4 | AE2 | Oct |
| I-396 | S | L4 | AE2 | Ph |
| I-397 | S | L4 | AE2 | Tol |
| I-398 | S | L4 | AE2 | DMP |
| I-399 | S | L4 | AE2 | MES |
| I-400 | S | L4 | AE3 | AE3 |
| I-401 | S | L4 | AE3 | EHx |
| I-402 | S | L4 | AE3 | Oct |
| I-403 | S | L4 | AE3 | Ph |
| I-404 | S | L4 | AE3 | Tol |
| I-405 | S | L4 | AE3 | DMP |
| I-406 | S | L4 | AE3 | MES |
| I-407 | S | L4 | AE4 | AE4 |
| I-408 | S | L4 | AE4 | EHx |
| I-409 | S | L4 | AE4 | Oct |
| I-410 | S | L4 | AE4 | Ph |
| I-411 | S | L4 | AE4 | Tol |
| I-412 | S | L4 | AE4 | DMP |
| I-413 | S | L4 | AE4 | MES |
| I-414 | S | L4 | AE5 | AE5 |
| I-415 | S | L4 | AE5 | EHx |
| I-416 | S | L4 | AE5 | Oct |
| I-417 | S | L4 | AE5 | Ph |
| I-418 | S | L4 | AE5 | Tol |
| I-419 | S | L4 | AE5 | DMP 26 --> |
| I-420 | S | L4 | AE5 | MES |
[table 16]
| XA | LA | R1A | R2A | |
| I-421 | S | L4 | AE7 | AE7 |
| I-422 | S | L4 | AE7 | EHx |
| I-423 | S | L4 | AE7 | Oct |
| I-424 | S | L4 | AE7 | Ph |
| I-425 | S | L4 | AE7 | Tol |
| I-426 | S | L4 | AE7 | DMP |
| I-427 | S | L4 | AE7 | MES |
| I-428 | S | L4 | AE9 | AE9 |
| I-429 | S | L4 | AE9 | EHx |
| I-430 | S | L4 | AE9 | Oct |
| I-431 | S | L4 | AE9 | Ph |
| I-432 | S | L4 | AE9 | Tol |
| I-433 | S | L4 | AE9 | DMP |
| I-434 | S | L4 | AE9 | MES |
| I-435 | S | L4 | AE10 | AE10 |
| I-436 | S | L4 | AE10 | EHx |
| I-437 | S | L4 | AE10 | Oct |
| I-438 | S | L4 | AE10 | Ph |
| I-439 | S | L4 | AE10 | Tol |
| I-440 | S | L4 | AE10 | DMP |
| I-441 | S | L4 | AE10 | MES |
| I-442 | S | L4 | AE17 | AE17 |
| I-443 | S | L4 | AE17 | EHx |
| I-444 | S | L4 | AE17 | Oct |
| I-445 | S | L4 | AE17 | Ph |
| I-446 | S | L4 | AE17 | Tol |
| I-447 | S | L4 | AE17 | DMP |
| I-448 | S | L4 | AE17 | MES |
Compound (I-1) is the such as compound shown in following formula (I-1).
[changing 17]
Dissolubility in a solvent and the lightness of color filter formed from the viewpoint of color solidification type resin combination, it is preferable that
Compound (I-1)～compound (I-42),
Compound (I-57)～compound (I-98),
Compound (I-113)～compound (I-154),
Compound (I-169)～compound (I-210),
Compound (I-225)～compound (I-266),
Compound (I-281)～compound (I-322),
Compound (I-337)～compound (I-378) and
Compound (I-393)～compound (I-434),
More preferably
Compound (I-1)～compound (I-42),
Compound (I-57)～compound (I-98),
Compound (I-113)～compound (I-154),
Compound (I-169)～compound (I-210),
Compound (I-225)～compound (I-266) and
Compound (I-281)～compound (I-322),
Particularly preferably
Compound (I-1)～compound (I-42)
Compound (I-57)～compound (I-98)
Compound (I-113)～compound (I-154) and
Compound (I-169)～compound (I-210).Most preferred compound (I-1), (I-2), (I-6), (I-8), (I-34), (I-57), (I-58), (I-62), (I-64), (I-90), (I-113), (I-114), (I-118), (I-120), (I-146), (I-169), (I-170), (I-174), (I-176) and (I-202).
The compound that compound (I) can pass through to make formula (IV) represent is (hereinafter sometimes referred to compound (IV).) and the compound that represents of formula (II) (hereinafter sometimes referred to compound (II).) react in the presence of base and manufacture.
[changing 18]
(in formula, L, X, R1～R5And R7～R9The meaning identical with above-mentioned expression, R12Represent the alkyl of carbon number 1～20.)
R12The alkyl of the carbon number 1～20 represented can enumerate methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl etc..The wherein alkyl of the preferred carbon number 1～6 such as methyl, ethyl, propyl group, isopropyl, butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, hexyl.
Alkali can enumerate the organic base such as triethylamine, piperidines, and its consumption, relative to 1 mole compound (IV), is generally 0.1 mole～20 moles.
Compound (II) make consumption relative to 1 mole compound (IV), it is preferable that 2 moles～10 moles, more preferably 2 moles～4 moles.
The reaction of compound (IV) and compound (II) is generally implemented in the presence of the solvent, and solvent can enumerate the nitrile solvents such as acetonitrile；The alcoholic solvents such as methanol, ethanol, 2-propanol, n-butyl alcohol, 1-amylalcohol, 1-capryl alcohol；The ether solvents such as oxolane；The ketone solvents such as acetone；The ester solvents such as ethyl acetate；The aliphatic hydrocarbon solvents such as hexane；The aromatic hydrocarbon solvents such as toluene；The amide solvents such as the halogenated hydrocaron solvent such as dichloromethane, chloroform and N, N-dimethylformaldehyde, N-Methyl pyrrolidone.Preferred nitrile solvent, alcoholic solvent and aromatic hydrocarbon solvents, more preferably acetonitrile, methanol and toluene.Its consumption, relative to 1 mass parts compound (IV), is generally 1 mass parts～50 mass parts.
Reaction temperature is generally 0 DEG C～200 DEG C, it is preferable that 0 DEG C～150 DEG C.Response time is generally 0.5 hour～36 hours.
After reaction terminates, for instance, by the solvent of dissolved compound (I) and the reaction mixture obtained will be difficult to and will filter, it is possible to acquisition compound (I).
Compound (II) is noval chemical compound, and it can by making compound (hereinafter sometimes referred to compound (III)) represented by formula (III) and formylating agent reaction manufacture.
[changing 19]
(in formula, R1～R5Represent the meaning same as described above.)
Formylating agent can enumerate phosphoryl chloride phosphorus oxychloride.Its consumption is generally 1～5 mole relative to 1 mole compound (III).
The reaction of compound (III) and formylating agent is generally implemented in the presence of the solvent, and solvent can enumerate DMF.Its consumption is generally 1 mass parts～10 mass parts relative to 1 mass parts compound (III).
Reaction temperature is generally 0 DEG C～100 DEG C, and the response time is generally 0.5 hour～24 hours.
After reaction terminates, for instance can pass through hybrid reaction mixture and water, after neutralization, with water-fast organic solvent extraction such as ethyl acetate, the organic layer concentration that will obtain, thus obtaining compound (II).
Compound (III) is also noval chemical compound, and it can pass through to make the compound (hereinafter sometimes referred to compound (VI)) represented by formula (VI) and Boron tribromide reaction, is then hydrolyzed, thus manufacturing.
[changing 20]
(in formula, R1～R5Represent the meaning same as described above, R12Represent the alkyl of carbon number 1～4.)
The alkyl of carbon number 1～4 can enumerate methyl, ethyl, propyl group and butyl.
The consumption of Boron tribromide is generally 1～5 mole relative to 1 mole compound (VI).
The reaction of compound (VI) and Boron tribromide is generally implemented in a solvent, and solvent can enumerate the halogenated hydrocaron solvent such as dichloromethane.The consumption of solvent, relative to 1 mass parts compound (VI), is generally 1～50 mass parts.
Reaction temperature is generally-78 DEG C～50 DEG C, and the response time is generally 1～24 hour.
After reaction terminates, for instance can passing through hybrid reaction mixture and water, separatory after mixing, the organic layer concentration that will obtain, thus obtaining compound (III).
Compound (VI) such as can pass through to make compound (hereinafter sometimes referred to compound (VII)) that formula (VII) represents and the compound (hereinafter sometimes referred to compound (VIII)) that formula (VIII) represents to react under the existence of palladium catalyst and alkali, thus manufacturing.In addition, compound (VI) such as can also pass through to make compound (hereinafter sometimes referred to compound (IX)) that formula (IX) represents and the compound (hereinafter sometimes referred to compound (X)) that formula (X) represents to react in the presence of base, thus manufacturing.
[changing 21]
(in formula, R1～R5And R12Represent the meaning same as described above, X2And X3Represent halogen atom, methanesulfonyloxy group, tosyloxy or trifluorometanesulfonyloxy independently of one another.)
X2And X3The halogen atom represented can enumerate chlorine atom, bromine atoms and atomic iodine.
The reaction of compound (VII) and compound (VIII) can be implemented according to the ammonating process (such as J.Org.Chem.2003,68,1163-1164 etc.) of known aromatic halide.Concrete, can pass through by the palladium catalysts such as palladium (II), 2,8,9-triisopropyl-2,5, the alkali such as Phosphine ligands, potassium tert-butoxide such as 8,9-tetra-azepine-1-phospha bicyclo-[3.3.3] hendecanes, compound (VII), compound (VIII) and the mixing of toluene equal solvent, make reaction carry out.Reaction temperature is generally 50 DEG C～150 DEG C, and the response time is generally 0.5～24 hour.After reaction terminates, for instance can pass through hybrid reaction mixture and water, separating organic layer, the organic layer concentration that will obtain, thus obtaining compound (VI).
The reaction of compound (IX) and compound (X) can be implemented according to the alkylation (such as J.Org.Chem.2011,76,8015-8021 etc.) of known amines.Specifically, it is possible to by alkali such as triethylamine, sodium hydride, Feldalat NM, potassium hydroxide, sodium hydroxide, potassium tert-butoxides；Compound (IX)；Compound (X)；With dimethyl sulfoxide equal solvent, thus reacting.Reaction temperature is generally 0 DEG C～100 DEG C, and the response time is generally 0.5～72 hour.After reaction terminates, for instance can pass through hybrid reaction mixture and water, as required, mixing water-fast organic solvent in water, separate organic layer, the organic layer concentration that will obtain, thus obtaining compound (VI).
Compound (IV) is noval chemical compound, it can pass through to make compound (hereinafter sometimes referred to compound (XI)) that formula (XI) represents and the compound (hereinafter sometimes referred to compound (XII)) that formula (XII) represents to react in a solvent, thus manufacturing.
[changing 22]
(in formula, R7～R9、R11, L and X represent the meaning same as described above, R13Represent the alkyl of carbon number 1～4.)
R13The alkyl of the carbon number 1～4 represented can enumerate methyl, ethyl, propyl group and butyl.
The consumption of compound (XII) is relative to 1 mole compound (XI), it is preferable that 2～5 moles, more preferably 2～3 moles.
Solvent can enumerate the alcoholic solvents such as methanol, and its consumption is generally 1～100 mass parts relative to 1 mass parts compound (XI).
Reaction temperature is generally-20 DEG C～100 DEG C, and the response time is generally 1～72 hour.
After reaction terminates, for instance, as required, it is possible to by filtering after reactant mixture and water or methanol mixed, obtain compound (IV).
Compound (XII) such as can according to J.Med.Chem.2012, the known method manufacture such as method recorded in 55,3398-3413.
<coloring agent of the present invention>
The coloring agent of the present invention is (hereinafter sometimes referred to " coloring agent (A) ".) containing the compound (I) as effective ingredient.Coloring agent (A) can be only made up of compound (I), it is also possible to dyestuff beyond inclusion compound (I) and/or pigment.Coloring agent (A) is preferably except compound (I), possibly together with pigment.When being used alone compound (I), in coloring agent (A), the content ratio of compound (I) is generally 1～100 mass %, preferably 3～100 mass %, and when with compound (I) and other dyestuffs and/or pigment, in coloring agent (A), the content ratio of compound (I) is generally 3～70 mass %, it is preferable that 3～60 mass %.
Coloring agent (A) is useful as the coloring agent comprised in the painted curable resin composition used in the color filter of the devices such as liquid crystal indicator.
Dyestuff beyond compound (I) can be enumerated: is categorized as solvent (Solvent) in Colour Index (ColourIndex) (dyeing association of man (TheSocietyofDyersandColourists) is published), acid (acid), alkalescence (Basic), activity (reactive), directly (Direct), dispersion (Disperse), or the dye known recorded in the compound of reduction (Vat) and/or " dyeing handbook " (dyeing ノ mono-ト) (Se Ran Co., Ltd.).Additionally, specifically can enumerate azo dye, anthraquinone dye, kiton colors, ton dyestuff and phthalocyanine dye etc. according to chemical constitution.These dyestuffs may be used alone, two or more kinds can also be used.
More specifically, the dyestuff of following Colour Index (C.I.) number can be enumerated.C.I. solvent yellow 14,15,23,24,25,38,62,63,68,79,81,82,83,89,94,98,99,162；
nullC.I. Indian yellow 1、3、7、9、11、17、23、25、29、34、36、38、40、42、54、65、72、73、76、79、98、99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、212、214、220、221、228、230、232、235、238、240、242、243、251；
C.I. reactive yellow 2,76,116；
C.I. direct Huang 2,4,28,33,34,35,38,39,43,44,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129,132,136,138,141；
C.I. disperse yellow 51,54,76；
C.I. solvent orange 2,7,11,15,26,41,54,56,99；
C.I. acid orange 6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108,149,162,169,173；
C.I. reactive orange 16；
C.I. direct orange 26,34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107；
C.I. solvent red 24,49,90,91,111,118,119,122,124,125,127,130,132,143,145,146,150,151,155,160,168,169,172,175,181,207,218,222,227,230,245,247；
C.I. Xylene Red 73,80,91,92,97,138,151,211,274,289；
C.I. acid violet 34,102；
C.I. disperse violet 26,27；
C.I. solvent violet 11,13,14,26,31,36,37,38,45,47,48,51,59,60；
C.I. solvent blue 19 4,18,35,36,45,58,59,59:1,63,68,69,78,79,83,94,97,98,100,101,102,104,105,111,112,122,128,132,136,139；
C.I. acid blue 25,27,40,45,78,80,112；
C.I. sun blue 40；
C.I. disperse blue 1,14,56,60；
C.I. solvent green 1,3,5,28,29,32,33；
C.I. acid green 3,5,9,25,27,28,41；
C.I. Viride Nitens 1；
C.I. vat green 1 etc..
Pigment can enumerate known pigment, for instance being categorized as the pigment of pigment (pigment) in Colour Index (TheSocietyofDyersandColourists publication), they may be used alone, two or more kinds can also be used in combination.
Specifically, the yellow uitramarines such as C.I. pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,129,137,138,139,147,148,150,153,154,166,173,194,214 can be enumerated；
C.I. pigment orange 13, the orange pigments such as 31,36,38,40,42,43,51,55,59,61,64,65,71,73；
C.I. Pigment Red 9, the red pigments such as 97,105,122,123,144,149,166,168,176,177,180,192,209,215,216,224,242,254,255,264,265；
C.I. pigment blue 15,15:3,15:4,15:6, the blue pigments such as 60；
C.I. pigment violet 1, the violet pigments such as 19,23,29,32,36,38；
C.I. pigment Green 7, the viridine greens such as 36,58,59；
C.I. the brown such as pigment brown 23,25；And
C.I. the black pigment such as pigment black 1,7.
Preferred phthalocyanine color in viridine green, blue pigment, yellow uitramarine, more preferably at least one selected in the group being made up of halogenated copper phthalocyanine pigment and zinc halide phthalocyanine color, it is particularly preferred to by least one selected in C.I. pigment Green 7,36,58 and 59 groups constituted.These pigment is suitable to be used as green colourant, and by using the coloring agent comprising these pigment, the optimization transfiguration of transmitted spectrum is easy, can form light resistance and/or the good color filter of chemical-resistant in addition.
Pigment is also dependent on needing to implement the following processing: surface treatment that Colophonium processed, used the pigment derivative etc. being imported with acidic-group or basic group, grafting surface of pigments carried out based on macromolecular compound etc. process, process based on the micronized of sulfuric acid particles method etc., for going the deimpurity carrying out washing treatment based on organic solvent and/or water etc., the removal process etc. that ionic impurity is carried out based on ion exchange etc..The particle diameter of pigment is preferably generally uniform.Dispersion process is carried out, it is possible to form the dispersible pigment dispersion being homogeneously dispersed in the state among pigment dispersing agent solution by making pigment contain pigment dispersing agent.Pigment can separately process in dispersion, it is possible to multiple mixing is carried out dispersion process.
As pigment dispersing agent, surfactant etc., any one surfactant in cation system, anion system, nonionic system, both sexes can be enumerated.Specifically can enumerate the surfactants etc. such as Polyester, polyamines system, acrylic acid series.These pigment dispersing agents can be used singly or two or more kinds in combination.Pigment dispersing agent can enumerate commodity by name KP (Shin-Etsu Chemial Co., Ltd's system), FLORENE (Off ロ mono-レ Application) (Kyoeisha Chemical Co., Ltd.'s system), SOLSPERSE (ソ Le ス パ mono-ス) (registered trade mark) (Jie Likang Co., Ltd. (ゼ ネ カ (strain)) system), EFKA (registered trade mark) (BASF AG's system), AJISPER (ァ ジ ス パ mono-) (aginomoto fine techniques Co., Ltd. (tasteOff ァ ィ Application テ Network ノ (strain)) system), Disperbyk (BYK company (PVC ッ Network ケ ミ mono-society) system) etc..
When using pigment dispersing agent, it makes consumption relative to 100 mass parts pigment, it is preferable that below 100 mass parts, more preferably below more than 5 mass parts 50 mass parts.When making consumption in above-mentioned scope of pigment dispersing agent, has the tendency that can obtain the evenly dispersible pigment dispersion of dispersity.
<colored curable resin composition of the present invention>
The colored curable resin composition of the present invention comprises coloring agent (A), resin (hereinafter sometimes referred to " resin (B) ".), polymerizable compound is (hereinafter sometimes referred to " polymerizable compound (C) ".), polymerization initiator is (hereinafter sometimes referred to " polymerization initiator (D) ".) and solvent (hereinafter sometimes referred to " solvent (E) ".).Apart from these components, the colored curable resin composition of the present invention can also contain levelling agent.Apart from these components, the colored curable resin composition of the present invention can also contain polymerization initiation auxiliary agent.
In colored curable resin composition, the containing ratio of coloring agent (A) is generally below more than 1 mass % 70 mass % relative to the total amount of solids, preferably below more than 1 mass % 60 mass, more preferably below more than 5 mass % 60 mass %, it is particularly preferred to more than 5 mass % below 50 mass %.If the containing ratio of coloring agent (A) is in aforementioned range, it is easier to obtain desired light splitting and/or color depth.It addition, " total amount of solids " in this specification refers to the total amount of the component after removing solvent in the colored curable resin composition of the present invention.The content of the total amount of solids and each component relative to it, for instance the known analysis method such as liquid chromatograph, gas chromatogram can be passed through and measure.
<resin (B)>
Resin (B) the preferred bases soluble resin comprised in the colored curable resin composition of the present invention, more preferably has the addition polymer deriving from least one construction unit selected in the group being made up of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides.Such resin can enumerate following resin [K1]～[K6].
Resin [K1]: select the copolymer of at least one (a) (hereinafter sometimes referred to " (a) ") in the group of free unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides composition and the monomer (b) (hereinafter sometimes referred to " (b) ") of the cyclic ether structure and ethylenic unsaturated bond with carbon number 2～4.
Resin [K2]: (a), (b) and can with the copolymer of the monomer (c) (but differing with (a) and (b)) (below sometimes referred to as " (c) ") of (a) copolymerization.
Resin [K3]: the copolymer of (a) and (c).
Resin [K4]: the resin obtained by making the copolymer of (a) and (c) react with (b)
Resin [K5]: make the copolymer of (b) and (c) and (a) reaction and the resin that obtains
Resin [K6]: by making copolymer and (a) reaction of (b) and (c), and then the resin reacting with carboxylic acid anhydrides again and obtaining.
(a) can enumerate acrylic acid, methacrylic acid, butenoic acid, neighbour, to unsaturated monocarboxylic acids such as vinyl benzoic acids；
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2, the unsaturated dicarboxylic acids such as 3,6-tetrahydrophthalic acid, dimethyl tetrahydro phthalic acid, Isosorbide-5-Nitrae-cyclohexene dicarboxylic acid；
Methyl-5-norborene-2,3-dicarboxylic acids, 5-carboxyl bicyclo-[2.2.1] hept-2-ene", 5,6-dicarboxyl bicyclo-[2.2.1] hept-2-ene"s, 5-carboxyl-5-methyl bicyclic [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl bicyclo-[2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicyclic [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl bicyclo-[2.2.1] hept-2-ene" etc. have the bicyclo-unsaturated compound of carboxyl；
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic acid acid anhydride, 4-vinylphthalic acid acid anhydride, 3,4,5,6-tetrabydrophthalic anhydride, 1,2, the unsaturated dicarboxylic acid anhydrides such as 3,6-tetrabydrophthalic anhydrides, dimethyl tetrahydro phthalic anhydride, 5,6-dicarboxyl bicyclo-[2.2.1] hept-2-ene" acid anhydrides；
Unsaturated list [(methyl) acryloxyalkyl] ester of the polybasic carboxylic acid of succinic acid list [2-(methyl) acryloyl-oxyethyl] ester, phthalic acid list [2-(methyl) acryloyl-oxyethyl] ester etc. more than 2 yuan；
The equivalent a part of α-(hydroxymethyl) acrylic acid contains the unsaturated acrylate of hydroxyl and carboxyl.
Wherein, the deliquescent angle in aqueous alkali from copolyreaction and the resin that obtains, it is preferable that acrylic acid, methacrylic acid and maleic anhydride.
B () refers to the polymerizable compound that the cyclic ether structure (such as oxirane ring, oxetanes ring, oxolane ring etc.) with carbon number 2～4 and ethylenic unsaturated bond close.B () preferably has the cyclic ether structure of carbon number 2～4 and the monomer of (methyl) acryloxy.Additionally; in this specification; " (methyl) acrylic acid " represents at least one in the group of acrylic acid and methylpropanoic acid composition, and " (methyl) acryloyl group " and " (methyl) acrylate " also illustrates that the identical meaning.
B () can enumerate containing Oxyranyle and the monomer (b1) (below sometimes referred to as " (b1) ") of ethylenic unsaturated bond, the monomer (b2) (below sometimes referred to as " (b2) ") containing oxetanylmethoxy and ethylenic unsaturated bond and the monomer (b3) (below sometimes referred to as " (b3) ") containing tetrahydrofuran base with ethylenic unsaturated bond.
(b1) straight-chain can be enumerated or monomer (b1-1) (below sometimes referred to as " (b1-1) ") that the unsaturated aliphatic hydrocarbon containing side chain contains epoxidized structure, and ester ring type unsaturated hydrocarbons contains the monomer (b1-2) (below sometimes referred to as " (b1-2) ") of epoxidized structure.
(b1-1) preferably there is the monomer of glycidyl and ethylenic unsaturated bond.null(b1-1) (methyl) glycidyl acrylate can specifically be enumerated、(methyl) propenoic acid beta-methylglycidyl esters、(methyl) propenoic acid beta-ethyl glycidyl ester、Glycidyl vinyl ether、Adjacent vinyl benzene methyl glycidyl ether、Between vinyl benzene methyl glycidyl ether、To vinyl benzene methyl glycidyl ether、Alpha-Methyl neighbour's vinyl benzene methyl glycidyl ether、Vinyl benzene methyl glycidyl ether between Alpha-Methyl、Alpha-Methyl is to vinyl benzene methyl glycidyl ether、2，Double; two (glycidoxypropyl methyl) styrene of 3-、2，Double; two (glycidoxypropyl methyl) styrene of 4-、2，Double; two (glycidoxypropyl methyl) styrene of 5-、2，Double; two (glycidoxypropyl methyl) styrene of 6-、2，3，4-tri-(glycidoxypropyl methyl) styrene、2，3，5-tri-(glycidoxypropyl methyl) styrene、2，3，6-tri-(glycidoxypropyl methyl) styrene、3，4，5-tri-(glycidoxypropyl methyl) styrene and 2，4，6-tri-(glycidoxypropyl methyl) styrene.
(b1-2) VCH list oxide can be enumerated, 1, 2-epoxy-4-vinyl cyclohexane is (such as, CELLOXIDE (セ ロ キ サ ィ De) (registered trade mark) 2000, Daicel Co., Ltd. ((strain) ダ ィ セ Le) makes), (methyl) acrylic acid 3, 4-epoxycyclohexanecarboxylate is (such as, CYCLOMER (サ ィ Network ロ マ mono-) A400, Daicel Co., Ltd. system), (methyl) acrylic acid 3, 4-epoxycyclohexanecarboxylate is (such as, CYCLOMERM100, Daicel Co., Ltd. system), the compound that formula (1) represents, and the compound that formula (2) represents.
[changing 23]
(in formula, RaAnd RbRepresenting the alkyl of hydrogen atom or carbon number 1～4 independently of one another, the hydrogen atom that this alkyl comprises can be optionally substituted by a hydroxyl group.XaAnd XbRepresent singly-bound, *-R independently of one anotherc-, *-Rc-O-, *-Rc-S-or *-Rc-NH-。RcRepresent the alkylidene of carbon number 1～6.* the bonding position with O is represented.)
Ra、RbThe alkyl that carbon number is 1～4 can enumerate: methyl, ethyl, propyl group, isopropyl, normal-butyl, sec-butyl, the tert-butyl group.Ra、RbThe alkyl that hydrogen atom is optionally substituted by a hydroxyl group can enumerate methylol, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxyl 1-Methylethyl, 2-hydroxyl-1-Methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl.
RaAnd RbEach independent, the hydroxy alkyl of preferred hydrogen atom, the alkyl of carbon number 1～4 or carbon number 14, more preferably the alkyl of hydrogen atom or carbon number 1～4, specifically preferred hydrogen atom, methyl, ethyl, methylol, 1-ethoxy or 2-ethoxy, more preferably hydrogen atom or methyl.
RcThe alkylidene of carbon number 1～6 can enumerate straight-chain or the alkylidene containing side chain, the concrete methylene enumerated, ethylidene, propane-1,3-bis-base, butane-Isosorbide-5-Nitrae-two base, pentane-1,5-bis-base and hexane-1, the straight-chain alkylidene of 6-bis-base；Propane-1,2-bis-base etc. is containing branched alkylidene.
XaAnd XbEach independent, it is preferable that singly-bound, *-Rc-or *-Rc-O-, more preferably singly-bound or *-Rc-O-, specifically preferred singly-bound, methylene, ethylidene, *-CH2-O-or *-CH2CH2-O-, more preferably singly-bound or *-CH2CH2-O-.It addition, * represents the position being bonded with O in previously described formula.
The compound that formula (1) represents can the compound that represents of enumerative (1-1)～formula (1-15), wherein, the compound that preferred formula (1-1), formula (1-3), formula (1-5), formula (1-7), formula (1-9) and formula (1-11)～formula (1-15) represent, the compound that more preferably formula (1-1), formula (1-7), formula (1-9) and formula (1-15) represent.
[changing 24]
[changing 25]
[changing 26]
[changing 27]
[changing 28]
[changing 29]
[changing 30]
[changing 31]
The compound that formula (2) represents can the compound that represents of enumerative (2-1)～formula (2-15), wherein, the compound that preferred formula (2-1), formula (2-3), formula (2-5), formula (2-7), formula (2-9) and formula (2-11)～formula (2-15) represent, the compound that more preferably formula (2-1), formula (2-7), formula (2-9) and formula (2-15) represent.
[changing 32]
[changing 33]
[changing 34]
[changing 35]
[changing 36]
[changing 37]
[changing 38]
[changing 39]
Compound that formula (1) represents and the compound that formula (2) represents can individually use, it is also possible to and the compound that the compound represented by formula (1) and formula (2) represent.And when with them, the ratio (compound that formula (1) represents: the compound that formula (2) represents) of compound that formula (1) represents and the compound that formula (2) represents is with mole for benchmark, preferably 5: 95～95: 5, more preferably 10: 90～90: 10, it is preferred that 20: 80～80: 20, further more preferably 30: 70～70: 30 particularly preferably 40: 60～60: 40.
(b2) more preferably there is the monomer of oxetanylmethoxy and (methyl) acryloxy.(b2) 3-methyl-3-methacryloxymethyl oxetanes can be enumerated, 3-methyl-3-acryloyloxymethyl oxetanes, 3-ethyl-3-methacryloxymethyl oxetanes, 3-ethyl-3-acryloyl group oxygen ylmethyl oxetanes, 3-methyl-3-methacryloxyethyl oxetanes, 3-methyl-3-acryloyl group oxygen base Ethyloxetane, 3-ethyl-3-methacryloxyethyl oxetanes and 3-ethyl-3-acryloyl group oxygen base Ethyloxetane.
(b3) more preferably there is the monomer of tetrahydrofuran base and (methyl) acryloxy.(b3) acrylic acid tetrahydro furfuryl ester (such as VISCOAT (PVC ス U one ト) V#150, Osaka Organic Chemical Industry Co., Ltd. manufactures) and methacrylic acid tetrahydro furfuryl ester can be enumerated.
From the angle that the reliabilities such as the thermostability of the color filter obtained, chemical proofing are higher, (b) preferred (b1), angle from the excellent storage stability of colored curable resin composition, it is preferable that (b1) is (b1-2).
C () can enumerate (methyl) acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) 2-ethylhexyl acrylate, (methyl) dodecylacrylate, (methyl) lauryl acrylate, (methyl) stearyl acrylate acid esters, (methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) acrylic acid 2-methyl cyclohexyl, (methyl) acrylic acid three ring [5.2.1.02,6] last of the ten Heavenly stems-8 base ester (in the art, its popular name is " (methyl) acrylate bicyclopentyl ester ".Additionally, also referred to as " (methyl) acrylic acid tricyclodecyl ester ".), (methyl) acrylic acid three ring [5.2.1.02,6] last of the ten Heavenly stems-8-base ester (in the art, its popular name is " (methyl) acrylate dicyclopentenyl ester ".), (methyl) acrylic acid two cyclopentyloxy ethyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid adamantane esters, (methyl) allyl acrylate, (methyl) acrylic acid propargyl ester, (methyl) phenyl acrylate, (methyl) acrylic acid naphthyl ester, (methyl) acrylate such as (methyl) benzyl acrylate；
(methyl) acrylate containing hydroxyl such as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester；
The dicarboxylic diesters such as ethyl maleate., DEF, diethyl itaconate；
nullBicyclo-[2.2.1] hept-2-ene"、5-methyl bicyclic [2.2.1] hept-2-ene"、5-ethyl bicyclo-[2.2.1] hept-2-ene"、5-hydroxyl bicyclo-[2.2.1] hept-2-ene"、5-hydroxymethyl bicyclo-[2.2.1] hept-2-ene"、5-(2 '-ethoxy) bicyclo-[2.2.1] hept-2-ene"、5-methoxyl group bicyclo-[2.2.1] hept-2-ene"、5-ethyoxyl bicyclo-[2.2.1] hept-2-ene"、5，6-dihydroxy bicyclo-[2.2.1] hept-2-ene"、5，6-bis-(hydroxymethyl) bicyclo-[2.2.1] hept-2-ene"、5，6-bis-(2 '-ethoxy) bicyclo-[2.2.1] hept-2-ene"、5，6-dimethoxy bicyclo-[2.2.1] hept-2-ene"、5，6-diethoxy bicyclo-[2.2.1] hept-2-ene"、5-hydroxy-5-methyl base bicyclo-[2.2.1] hept-2-ene"、5-hydroxyl-5-ethyl bicyclo-[2.2.1] hept-2-ene"、5-hydroxymethyl-5-methyl bicyclic [2.2.1] hept-2-ene"、5-tert-butoxycarbonyl bicyclo-[2.2.1] hept-2-ene"、5-cyclohexyloxy carbonyl bicyclo-[2.2.1] hept-2-ene"、5-phenyloxycarbonyl bicyclo-[2.2.1] hept-2-ene"、5，Double; two (tert-butoxycarbonyl) bicyclo-[2.2.1] hept-2-ene" of 6-、5，The bicyclo-unsaturated compounds such as double; two (cyclohexyl oxygen base carbonyl) bicyclo-[2.2.1] hept-2-ene"s of 6-；
The dicarbonyl imides compounds such as N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide, N-succinimido-3-maleimidobenzoyl ester, N-succinimido-4-malimidobutanoate, N-succinimido-6-maleimidohexanoic acid ester, N-succinimido-3-maleimidopropionic acid ester, N-(9-acridinyl) maleimide；
Styrene, α-methyl styrene, a methyl styrene, p-methylstyrene, vinyltoluene, to the aromatic compound containing vinyl such as methoxy styrene；The nitrile containing vinyl such as acrylonitrile, methacrylonitrile；The halogenated hydrocarbon such as vinyl chloride, vinylidene chloride；The amide containing vinyl such as acrylamide, Methacrylamide；The esters such as vinyl acetate；The alkadienes such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene；Deng.
Wherein, from the viewpoint of copolymerization and thermostability, it is preferable that the aromatic compound containing vinyl, dicarbonyl imides compound, bicyclo-unsaturated compound.Specifically optimization styrene, vinyltoluene, (methyl) benzyl acrylate, (methyl) acrylic acid three ring [5.2.1.02,6] last of the ten Heavenly stems-8-base ester, N-phenylmaleimide, N-N-cyclohexylmaleimide, N-benzyl maleimide and bicyclo-[2.2.1] hept-2-ene".
In resin [K1], derive from the ratio of each construction unit, relative to the entire infrastructure unit constituting resin [K1],
Preferably
Derive from the construction unit of (a): 2～60 moles of %
Derive from the construction unit of (b): 40～98 moles of %,
More preferably
Derive from the construction unit of (a): 10～50 moles of %
Derive from the construction unit of (b): 50～90 moles of %.
If the ratio of the construction unit of resin [K1] is in above-mentioned scope, the storage stability of colored curable resin composition, developability when forming colored pattern and the solvent resistance of color filter obtained tend to excellence.
Resin [K1] is referred to such as, and method and the document of quoting of document record described in document " Polymer Synthesizing laboratory method " (Polymer Synthesizing method) (the 1st edition the 1st the printing distribution on March 1st, 1972 of the big Jin Longhangzhu sale room Co., Ltd.'s same people of chemistry (the chemical same people of sale room (strain))) manufacture.
Specifically, following methods is enumerated: (a) and (b) of ormal weight, polymerization initiator and solvent etc. are loaded in reaction vessel, for instance by replacing oxygen with nitrogen, under de-oxidizing environment, limit stirring, limit heating and thermal insulation.It addition, polymerization initiator used herein and solvent etc. are not particularly limited, it is possible to use normally used material in this field.Polymerization initiator is such as, azo-compound (2 can be enumerated, 2 '-azodiisobutyronitrile, 2,2 '-azo two (2,4-methyl pentane nitrile) etc.) or organic peroxide (benzoyl peroxide etc.), as long as solvent can dissolve the solvent of each monomer, the solvent of the colored curable resin composition of the present invention described later can be enumerated.
The copolymer obtained, it is possible to directly use reacted solution, it is possible to use concentration or the solution after dilution, it is possible to use by the solid (powder body) that the methods such as precipitation again obtain.Particularly, in this polymerization, the solvent comprised in the colored curable resin composition of the application of the invention is as solvent, can being directly used in by reacted solution in the preparation of colored curable resin composition of the present invention, therefore the manufacturing process of the colored curable resin composition of the present invention can simplify.
Resin [in K21, derive from the ratio of each construction unit, relative to the entire infrastructure unit constituting resin [K2],
Preferably
Derive from the construction unit of (a): 2～45 moles of %
Derive from the construction unit of (b): 2～95 moles of %
Derive from the construction unit of (c): 1～65 mole of %,
More preferably
Derive from the construction unit of (a): 5～40 moles of %
Derive from the construction unit of (b): 5～80 moles of %
Derive from the construction unit of (c): 5～60 moles of %.
If the ratio of the construction unit of resin [K2] is in above-mentioned scope, the storage stability of colored curable resin composition, developability when forming colored pattern and the solvent resistance of color filter, thermostability and the mechanical strength that obtain are tended to more excellent.
Resin [K2], for instance, it is possible to use the method manufacture same with the manufacture method of the resin [K1] recorded.
In resin [K3], derive from the ratio of each construction unit, relative to the entire infrastructure unit constituting resin [K3],
Preferably
Derive from the construction unit of (a): 2～60 moles of %
Derive from the construction unit of (c): 40～98 moles of %,
More preferably
Derive from the construction unit of (a): 10～50 moles of %
Derive from the construction unit of (c): 50～90 moles of %.
Resin [K3], for instance, it is possible to use the method manufacture same with the manufacture method of the resin [K1] recorded.
Resin [K4] can pass through to obtain the copolymer of (a) and (c), and make the cyclic ether position of the carbon number 2～4 that (b) have add to carboxylic acid that (a) contain and/or carboxylic acid anhydrides are thus manufacturing.Specifically, it is possible to be carried out as follows manufacture.First, with the copolymer of method manufacture (a) and (c) same with the manufacture method being recited as resin [K1].Now, it is preferable that the ratio of the construction unit in each source is identical with the ratio of the material enumerated in resin [K3].Then, the cyclic ether compound deriving from the carbon number 2～4 that the carboxylic acid of (a) and/or a part for carboxylic acid anhydrides have with (b) in aforementioned copolymer is made to react.Continue the copolymer manufacturing (a) with (c), in flask, atmosphere is replaced into air by nitrogen, the catalysts (such as three (dimethylaminomethyl) phenol etc.) of (b), carboxylic acid or carboxylic acid anhydrides and cyclic ether compound and polymerization inhibitor (such as hydroquinone etc.) etc. are inserted in flask, such as by 60～130 DEG C, react 1～10 hour, it is possible to make resin [K4].
Relative to (a) 100 moles, the consumption of (b) preferably 5～80 moles, more preferably 10～75 moles.The storage stability that comprises the colored curable resin composition by the consumption of (b) adjusts the resin obtained within the scope of this, developability when forming pattern, the balance of the solvent resistance of pattern, thermostability, mechanical strength and sensitivity that obtains are tended to better.The angle that high from the reactivity at cyclic ether position, unreacted (b) is difficult to remain considers, uses (b) preferably (b1), more preferably (b1-1) in resin [K4].
Relative to total amount 100 mass parts of (a), (b) and (c), the consumption of catalyst preferably 0.001～5 mass parts.Relative to total amount 100 mass parts of (a), (b) and (c), the consumption of aforementioned polymerization inhibitor preferably 0.001～5 mass parts.
The reaction conditions such as the Adding Way of each reagent, reaction temperature and response time can consider that the caloric value etc. that manufacture equipment or polymerization cause suitably adjusts.It addition, with polymerizing condition likewise it is possible to consider manufacture equipment, be polymerized the caloric value etc. caused, suitably adjust Adding Way, reaction temperature.
When manufacturing resin [K5], the first stage obtains the copolymer of (b) and (c) in the same manner as the manufacture method of above-mentioned resin [K1].As described above, the copolymer obtained can directly use reacted solution, it is possible to use concentration or the solution after dilution, it is possible to use by the material that the methods such as precipitation again obtain as solid (powder body).In first stage, relative to the total molal quantity of the entire infrastructure unit of the copolymer constituting aforementioned (b) and (c), derive from the ratio of construction unit of (b) and (c) respectively
Preferably
Derive from the construction unit of (b): 5～95 moles of %
Derive from the construction unit of (c): 5～95 moles of %,
More preferably
Derive from the construction unit of (b): 10～90 moles of %
Derive from the construction unit of (c): 10～90 moles of %.
Further, second stage, same with the manufacture method of resin [K4] when, by making the cyclic ether position deriving from (b) that the copolymer of the carboxylic acid of (a) or carboxylic acid anhydrides and (b) and (c) has react, thus obtaining resin [K5].
In second stage, relative to (b) 100 moles, with the consumption of (a) of the copolymer reaction of aforementioned (b) and (c) preferably 5～80 moles.The angle that high from the reactivity at cyclic ether position, unreacted (b) is difficult to remain considers, (b) used in resin [K5] preferred (b1), more preferably (b1-1).
Resin [K6] is the resin obtained by making resin [K5] react with carboxylic acid anhydrides further, it is in particular, it is possible to the hydroxyl reacting by making to derive from the cyclic ether position of (b) and the carboxylic acid of (a) or carboxylic acid anhydrides and producing reacts with carboxylic acid anhydrides and manufactures.
Carboxylic acid anhydrides can enumerate maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic acid acid anhydride, 4-vinylphthalic acid acid anhydride, 3,4,5,6-tetrabydrophthalic anhydride, 1,2,3,6-tetrabydrophthalic anhydrides, dimethyl tetrahydro phthalic anhydride and 5,6-dicarboxyl bicyclo-[2.2.1] hept-2-ene" acid anhydrides.Relative to the consumption 1 mole of (a), the consumption of carboxylic acid anhydrides preferably 0.5～1 mole.
Resin (B) can enumerate (methyl) acrylic acid 3,4-expoxycyclohexyl methyl ester/(methyl) acrylic copolymer, (methyl) acrylic acid 3, the resins [K1] such as 4-epoxy radicals three ring [5.2.1.02,6] ester in the last of the ten Heavenly stems/(methyl) acrylic copolymer；(methyl) glycidyl acrylate/(methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) glycidyl acrylate/styrene/(methyl) acrylic copolymer, (methyl) acrylic acid 3, 4-epoxy radicals three ring [5.2.1.02, 6] ester in the last of the ten Heavenly stems/(methyl) acrylic acid/N-N-cyclohexylmaleimide copolymer, (methyl) acrylic acid 3, 4-epoxy radicals three ring [52.1.02, 6] ester in the last of the ten Heavenly stems/(methyl) acrylic acid/vinyl toluene copolymer, the resins [K2] such as 3-methyl-3-(methyl) acryloyloxymethyl oxetanes/(methyl) acrylic/styrene copolymer；The resins [K3] such as (methyl) benzyl acrylate/(methyl) acrylic copolymer, styrene/(methyl) acrylic copolymer, (methyl) benzyl acrylate/(methyl) acrylic acid tricyclodecyl ester/(methyl) acrylic copolymer；(methyl) glycidyl acrylate is made to add to the resin obtained on (methyl) benzyl acrylate/(methyl) acrylic copolymer, (methyl) glycidyl acrylate is made to add to the resin obtained on (methyl) acrylic acid tricyclodecyl ester/styrene/(methyl) acrylic copolymer, (methyl) glycidyl acrylate is made to add to the resins [K4] such as the resin that obtains on (methyl) acrylic acid tricyclodecyl ester/(methyl) benzyl acrylate/(methyl) acrylic copolymer；The resins [K5] such as the resin make resin that the copolymer reaction of (methyl) acrylic acid and (methyl) acrylic acid tricyclodecyl ester/(methyl) glycidyl acrylate obtains, making (methyl) acrylic acid and (methyl) acrylic acid tricyclodecyl ester/styrene/(methyl) glycidyl acrylate copolymer reaction obtain；Make the resins [K6] such as the resin that the resin that the copolymer reaction of (methyl) acrylic acid and (methyl) acrylic acid tricyclodecyl ester/(methyl) glycidyl acrylate obtains is obtained by reacting further with tetrabydrophthalic anhydride.
The one selected in the group that resin (B) is constituted preferably from resin [K1], resin [K2] and resin [K3], the one more preferably selected from the group that resin [K1] and resin [K2] are constituted.If these resins, the developability of colored curable resin composition is excellent.From the viewpoint of the stickiness of colored pattern and substrate, it is preferred that resin [K1].
The weight average molecular weight of the polystyrene conversion of resin (B) is generally 3,000～100, and 000, it is preferable that 5,000～50,000, more preferably 5,000～35,000, it is preferred that 5,000～30,000, it is particularly preferred to 6,000～30,000.Molecular weight is in above-mentioned scope, and hardness of film improves, and residual film ratio is also high, for the favorable solubility of the developer solution in unexposed portion, the tendency that the exploring degree of colored pattern is improved.
The molecular weight distribution [weight average molecular weight (Mw)/number-average molecular weight (Mn)] of resin (B) preferably 1.1～6, more preferably 1.2～4.
The acid number of resin (B), it is no matter acid number or solution acid number all preferably 20～170mg-KOH/g, the more preferably 30～170mg-KOH/g of solid constituent conversion, wherein preferred 40～170mg-KOH/g, more preferably below 150mg-KOH/g, it is preferred that below 135mg-KOH/g.Herein, acid number refers to the measured value neutralizing the potassium hydroxide amount (mg) required for 1g resin (B), for instance can try to achieve by carrying out titration with potassium hydroxide aqueous solution.
Relative to the total amount of solid constituent, content preferably 7～65 mass % of resin (B), wherein preferred 10～60 mass %, wherein preferred 13～60 mass %, wherein preferred 17～55 mass %.If the content of resin (B) is in above-mentioned scope, there is the tendency that being formed easily of colored pattern, the exploring degree of colored pattern and residual film ratio improve.
<polymerizable compound (C)>
Polymerizable compound (C) is the living radical utilizing polymerization initiator to produce and/or compound that is sour and that can be polymerized, include, for example the polymerizable compound with ethylenic unsaturated bond, it is preferable that there is the compound of (methyl) acrylate structural.Polymerizable compound (C) preferably has the polymerizable compound of more than 3 ethylenic unsaturated bonds, more preferably has the polymerizable compound of more than 5～6 ethylenic unsaturated bonds.
The polymerizable compound with 1 ethylenic unsaturated bond can enumerate nonyl phenyl carbitol acrylate, acrylic acid 2-hydroxyl-3-phenoxy propyl ester, 2-ethylhexyl carbitol acrylate, HEA, NVP, above-mentioned (a), (b) and (c).There is the polymerizable compound of 2 ethylenic unsaturated bonds and can enumerate 1,6-hexanediol two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 2,2'-ethylenedioxybis(ethanol). two (methyl) acrylate, two (acrylyl oxy-ethyl) ethers of bisphenol-A and 3-methyl pentanediol two (methyl) acrylate.nullThere is the polymerizable compound of more than 3 ethylenic unsaturated bonds，Trimethylolpropane tris (methyl) acrylate can be enumerated、Tetramethylolmethane three (methyl) acrylate、Tetramethylolmethane four (methyl) acrylate、Dipentaerythritol five (methyl) acrylate、Dipentaerythritol six (methyl) acrylate、Tripentaerythritol eight (methyl) acrylate、Tripentaerythritol seven (methyl) acrylate、Tetrapentaerythritol ten (methyl) acrylate、Tetrapentaerythritol nine (methyl) acrylate、Three (2-(methyl) acrylyl oxy-ethyl) chlorinated isocyanurates、Glycol-modified tetramethylolmethane four (methyl) acrylate、Glycol-modified dipentaerythritol six (methyl) acrylate、Propylene glycol modified tetramethylolmethane four (methyl) acrylate、Propylene glycol modified dipentaerythritol six (methyl) acrylate、Caprolactone modification tetramethylolmethane four (methyl) acrylate and caprolactone modification dipentaerythritol six (methyl) acrylate.
Preferred dipentaerythritol five (methyl) acrylate and dipentaerythritol six (methyl) acrylate in them.
Total amount relative to solid constituent, in the colored curable resin composition of the present invention, the content of polymerizable compound (C) is generally 5～65 mass %, it is preferable that 7～65 mass %, more preferably 10～60 mass %, preferred 13～60 mass % further, it is particularly preferred to 17～55 mass %.With quality for benchmark, the content ratio (resin (B): polymerizable compound (C)) of resin (B) and polymerizable compound (C) is generally 20: 80～80: 20, it is preferable that 35: 65～80: 20.If the content of polymerizable compound (C) is in aforementioned range, residual film ratio and the chemical proofing of color filter when colored pattern is formed tend to improve.
<polymerization initiator (D)>
Polymerization initiator (D), as long as the effect that can pass through light and/or heat produces living radical, acid etc., thus causing the compound of polymerization, is not particularly limited, it is possible to use known polymerization initiator.
Polymerization initiator (D) can enumerate O-acyl group oxime compound, alkyl phenones compound, triaizine compounds, acylphosphine oxide and united imidazole etc..
O-acyl group oxime compound is the compound with the structure that formula (d1) represents.Below, * represents bonding position.
[changing 40]
nullO-acyl group oxime compound can enumerate N-benzoyloxy-1-(4-phenylsulfartyl phenyl)-1-butanone-2-imines、N-benzoyloxy-1-(4-phenylsulfartyl phenyl)-1-octanone-2-imines、N-benzoyloxy-1-(4-phenylsulfartyl 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-dioxolyl methoxyl group) 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 and N-benzoyloxy-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-3-cyclopenta-1-acetone-2-imines.The commercially available products such as IRGACURE (イ Le ガ キ ュ ア) (registered trade mark) OXE01, OXE02 (above for BASF AG's system), N-1919 (ADEKA Corp.'s system) can be used.At least one selected in the group that especially preferred 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-acetone-2-imines are constituted, more preferably N-benzoyloxy-1-(4-phenylsulfartyl phenyl)-1-octanone-2-imines.
Alkyl phenones compound is the compound with structure shown in formula (d2) or structure shown in formula (d3).Additionally, the phenyl ring in these structures can also have substituent group.
[changing 41]
There is the compound of structure shown in formula (d2), 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)-1-acetone, 2-dimethylamino-1-(4-morphlinophenyl)-2-benzyl-1-butanone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone can be enumerated.The commercially available products such as IRGACURE369,907,379 (above for BASF AG's system) can be used.
There is the compound of structure shown in formula (d3), can enumerate, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2-hydroxy-2-methyl-1-(4-(2-hydroxyl-oxethyl) phenyl)-1-acetone, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(the 4-isopropenyl phenyl) oligomer of-1-acetone, α, α-diethoxy acetophenone and benzyl dimethyl ketal etc..
Considering from the angle of sensitivity, alkyl phenones compound preferably has the compound of structure shown in formula (d2).
nullTriaizine compounds can enumerate 2，Double; two (the trichloromethyl)-6-(4-methoxyphenyl)-1 of 4-，3，5 triazines、2，Double; two (the trichloromethyl)-6-(4-methoxyl group naphthyl)-1 of 4-，3，5 triazines、2，Double; two (the trichloromethyl)-6-piperonyl-1 of 4-，3，5-triazine、2，Double; two (the trichloromethyl)-6-(4-methoxyl-styrene)-1 of 4-，3，5-triazine、2，Double; two (the trichloromethyl)-6-(2-(5-methylfuran-2-base) vinyl)-1 of 4-，3，5-triazine、2，Double; two (the trichloromethyl)-6-(2-(furan-2-base) vinyl)-1 of 4-，3，5-triazine、2，Double; two (the trichloromethyl)-6-(2-(4-diethylamino-2-aminomethyl phenyl) vinyl)-1 of 4-，3，5-triazine and 2，Double; two (trichloromethyl)-6-(2-(3 of 4-，4-Dimethoxyphenyl) vinyl)-1，3，5-triazine.
Acylphosphine oxide can enumerate 2,4,6-trimethylbenzoyldiphenyl oxides.
United imidazole can the compound that represents of enumerative (d4).
[changing 42]
(in formula, R51～R56Expression can have the aromatic radical of the carbon number 6～10 of substituent group.)
Aryl as carbon number 6～10, for instance phenyl, tolyl, xylyl, ethylphenyl and naphthyl can be enumerated, it is preferable that phenyl.Substituent group can enumerate halogen atom and the alkoxyl of carbon number 1～4.Halogen atom include, for example fluorine atom, chlorine atom, bromine atoms, atomic iodine etc., it is preferable that chlorine atom.The alkoxyl of carbon number 1～4 can enumerate methoxyl group, ethyoxyl, propoxyl group and butoxy, it is preferable that methoxyl group.
United imidazole specifically can enumerate 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2,3-Dichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline is (referring for example to Japanese Patent Laid-Open 6-75372 publication, Japanese Patent Laid-Open 6-75373 publication etc..), 2,2 '-bis-(2-chlorphenyls)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-four (alkoxyl phenyl) bisglyoxaline, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-four (dialkoxy phenyl) bisglyoxaline, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-four (tri-alkoxy phenyl) bisglyoxaline is (referring for example to Japan Patent examined patent publication 48-38403 publication, Japanese Patent Laid-Open No. Sho 62-174204 publication etc..) and 4,4 ', 5, the imidazolium compounds (such as with reference to Japanese Patent Laid-Open 07-010913 publication etc.) that 5 '-position phenyl is replaced by alkoxy carbonyl group.Wherein, it is preferable that the compound shown in following formula and their mixture.
[changing 43]
Other polymerization initiator can enumerate the benzoin compounds such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether；Benzophenone, methyl o-benzoylbenzoate, 4-phenyl benzophenone, 4-benzoyl-4 '-methyl phenylbenzene thioether, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone cpd such as benzophenone, 2,4,6-tri-methyl benzophenones；The naphtoquinone compounds such as 9,10-phenanthrenequione, 2-ethyl-anthraquinone, camphorquinone；10-butyl-2-chloro-acridine ketone, benzil, phenyl glyoxilic acid methyl ester, titanocenes compound etc..Preferably they cause auxiliary agent (particularly amine polymerization causes auxiliary agent) combination to use with described later polymerization.
The polymerization initiator producing acid include, for example: salt, nitrobenzyl tosylate class, the benzoin toluenesulfonic acid salts etc. such as 4-hydroxyphenyl dimethyl sulfonium tosilate, 4-hydroxyphenyl dimethyl sulfonium hexafluoro antimonate, 4-acetoxyl group phenyl dimethyl sulfonium tosilate, 4-acetoxyl group phenyl methyl benzyl sulfonium hexafluoro antimonate, triphenylsulfonium tosilate, triphenylsulfonium hexafluoro antimonate, diphenyl iodine tosilate, diphenyl iodine hexafluoro antimonate.
Polymerization initiator (D) preferably produces the polymerization initiator of living radical; more preferably at least one selected in the group being made up of alkyl phenones compound, triaizine compounds, acylphosphine oxide, O-acyl group oxime compound and united imidazole is comprised, it is preferred that comprise O-acyl group oxime compound.
Total amount 100 mass parts relative to resin (B) and polymerizable compound (C), the content of polymerization initiator (D) is generally 0.1～40 mass parts, preferably 0.1～30 mass parts, more preferably 1～30 mass parts, it is particularly preferred to 1～20 mass parts.
<polymerization causes auxiliary agent>
Polymerization causes auxiliary agent to be the compound used to promote to have been caused the polymerization of polymerizable compound (C) of polymerization by polymerization initiator (D), or sensitizer.When the colored curable resin composition of the present invention comprises polymerization initiation auxiliary agent, generally use with polymerization initiator (D) combination.
Polymerization cause auxiliary agent can enumerate amine system polymerization cause auxiliary agent, alkoxy anthracene system polymerization cause auxiliary agent, thiaxanthone system polymerization cause auxiliary agent and carboxylic serials polymerization cause auxiliary agent.
The polymerization of amine system causes auxiliary agent can enumerate the alkanolamines such as triethanolamine, methyl diethanolamine, triisopropanolamine；The Aminobenzoates such as 4-dimethylaminobenzoic acid methyl ester, EDMAB, 4-dimethylaminobenzoic acid isopentyl ester, benzoic acid-2-dimethylamino ethyl ester, 4-dimethylaminobenzoic acid-2-Octyl Nitrite；N, N-dimethyl-p-toluidine, 4,4 '-bis-(dimethylamino) benzophenone (common name Michler's keton), 4,4 '-bis-(diethylamino) benzophenone and 4,4 '-bis-(ethylmethylamino) benzophenone etc., wherein, it is preferable that 4, the alkyl amino benzophenone such as 4 '-bis-(diethylamino) benzophenone.Wherein, it is preferable that alkyl amino benzophenone, it is preferable that 4,4 '-bis-(diethylamino) benzophenone.The commercially available products such as EAB-F (Baotugu Chemical Industrial Co., Ltd's system) can be used.
The polymerization of alkoxy anthracene system causes auxiliary agent can enumerate 9,10-dimethoxy anthracenes, EDMO, 9,10-diethoxy anthracenes, 2-ethyl-9,10-diethoxy anthracene, 9,10-dibutoxy anthracenes and 2-ethyl-9,10-dibutoxy anthracene etc..
The polymerization of thiaxanthone system causes auxiliary agent can enumerate ITX, ITX, 2,4-diethyl thioxanthones, 2,4-bis-clopenthixal ketones and 1-chlorine 4 propoxythioxanthone.
Carboxylic serials polymerization causes auxiliary agent can enumerate thiophenyl acetic acid, methylphenyl-sulfanyl acetic acid, ethylthiophenyl acetic acid, ethyl methyl benzene ethyl thioglycollic acid, dimethyl benzene ethyl thioglycollic acid, Methoxv-phenylsulfanvl acetic acid, dimethoxyphenylthio acetic acid, chlorophenylsulfanyl acetic acid, dichloro-benzenes ethyl thioglycollic acid, N-phenylglycine, phenoxyacetic acid, naphthylthio acetic acid, N-naphthyl glycine and naphthoxyacetic acid etc..
When using polymerization to cause auxiliary agent, relative to total amount 100 mass parts of resin (B) and polymerizable compound (C), polymerization causes content preferably 0.1～30 mass parts of auxiliary agent, more preferably 1～20 mass parts.If polymerization causes the content of auxiliary agent within the scope of this, it is possible to form colored pattern under more high sensitivity, the productivity ratio of color filter is tended to improve.
In the present invention, the compound in molecule with sulfydryl (-SH) can comprise mercaptan compound.
nullWhat have 1 sulfydryl in molecule include, for example 2-sulfydryl azoles、2-thyroidan、2-mercaptobenzimidazole、2-mercaptobenzothiazole、2-mercaptobenzooxazole、2-mercaptonicotinic acid、2-mercaptopyridine、2-sulfydryl-3-pyridine alcohol、Pyrithione、4-Amide-6-hydroxy-2-mercaptopyrimidine、4-Amide-6-hydroxy-2-mercaptopyrimidine、4-amino-2-mercapto phenyl formic pyrimidine、6-amino-5-nitroso-group-2-paper substrate、4，5-diaminourea-6-hydroxyl-2-mercaptopyrimidine、4，6-diaminourea-2-mercaptopyrimidine、2，4-diaminourea-6-mercaptopyrimidine、4，6-dihydroxy-2-mercaptopyrimidine、4，6-dimethyl-2-mercaptopyrimidine、4-hydroxyl-2-sulfydryl-6-methylpyrimidine、4-hydroxyl-2-sulfydryl-6-propyl group pyrimidine、2-sulfydryl-4-methylpyrimidine、2-mercaptopyrimidine、2-paper substrate、3，4，5，6-tetrahydropyrimidine-2-mercaptan、4，5-diphenyl-imidazole-2-mercaptan、2-mercaptoimidazole、2-sulfydryl-1-Methylimidazole.、4-amino-3-diazanyl-5-sulfydryl-1，2，4-triazole、3-amino-5-sulfydryl-1，2，4-triazole、2-methyl-4H-1，2，4-triazole-3-mercaptan、4-methyl-4H-1，2，4-triazole-3-mercaptan、3-sulfydryl-1H-1，2，4-triazole-3-mercaptan、2-amino-5-sulfydryl-1，3，4-thiazole、5-amino-1，3，4-thiazol-2-thiol、2，5-dimercapto-1，3，4-thiazole、(furan-2-base) methyl mercaptan、2-sulfydryl-5-thiazolidone、2-mercaptothiazoline、2-sulfydryl-4 (3H)-quinazoline、1-phenyl-1H-TETRAZOLE-5-mercaptan、2-quinoline thiol、2-sulfydryl-5-tolimidazole、2-sulfydryl-5-nitrobenzimidazole、6-amino-2-mercapto phenyl formic benzothiazole、The chloro-2-mercaptobenzothiazole of 5-、6-ethyoxyl-2-mercaptobenzothiazole、Nitrocaptax、2-mercaptonaphthalene imidazoles、2-mercaptonaphthalene azoles、3-sulfydryl-1，2，4-triazole、4-amino-6-sulfydryl pyrazolo [2，4-d] pyridine、2-amino-6-purine mercaptan、Ismipur、4-sulfydryl-1H-pyrazolo [2，4-d] pyrimidine etc..
The compound in molecule with more than 2 sulfydryls can enumerate ethanthiol, the last of the ten Heavenly stems two sulfur alcohol, 1, double, two (methyl mercapto) benzene of 4-, butanediol double, two (3-thiopropionate), butanediol double, two (3-thioglycollate), ethylene glycol bis (3-thioglycollate), trimethylolpropane tris (3-thioglycollate), butanediol double, two (3-thiopropionate), trimethylolpropane tris (3-thiopropionate), trimethylolpropane tris (3-thioglycollate), tetramethylolmethane four (3-thiopropionate), tetramethylolmethane four (3-thioglycollate), trihydroxyethyl three (3-thiopropionate), tetramethylolmethane four (3-mercaptobutylate), 1, double, two (3-sulfydryl butoxy) butane of 4-etc..
There is in the preferred molecule of mercaptan compound the compound of 1 sulfydryl.
Relative to 100 mass parts polymerization initiators (D), the content of mercaptan compound preferably 0.5～20 mass parts, more preferably 1～15 mass parts.If the content of mercaptan compound is within the scope of this, then there is sensitivity to uprise, have the tendency that developability improves in addition.
<solvent (E)>
Solvent (E) is not limited, it is possible to be used alone solvent usually used in this field or combine two or more use.The concrete ester solvent enumerated (comprises-COO-in molecule, do not comprise the solvent of-O-), ether solvents (in molecule, comprise-O-, do not comprise the solvent of-COO-), ether-ether solvent (comprising the solvent of-COO-and-O-in molecule), ketone solvent (in molecule, comprise-CO-, do not comprise the solvent of-COO-), alcoholic solvent (comprising OH in molecule, do not comprise the solvent of-O-,-CO-and-COO-), aromatic hydrocarbon solvents, amide solvent and dimethyl sulfoxide.
Ester solvent, can enumerate methyl lactate, ethyl lactate, butyl lactate, 2-hydroxy-methyl isobutyl acid, ethyl acetate, butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl n-butyrate., butyl butyrate, methyl pyruvate, ethyl pyruvate, Propyl 2-oxopropionate, methyl acetoacetate, ethyl acetoacetate, adnoral acetate and gamma-butyrolacton.
Ether solvents can enumerate glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxyl group-n-butyl alcohol, 3-methoxyl group-3-methyl butanol, oxolane, Pentamethylene oxide., 1, 4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol MEE, diethylene glycol dipropyl ether, dibutyl ethylene glycol ether, methyl phenyl ethers anisole, ethyl phenyl ether, methylanisole.
nullEther-ether solvent can enumerate methoxy menthyl acetate、Ethyl methoxyacetate、Methoxy acetic acid butyl ester、Ethoxy acetate、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-ethoxypropanoate、2-ethoxyl ethyl propionate、2-methoxyl group-2 Methylpropionic acid methyl ester、2-ethyoxyl-2 Methylpropionic acid ethyl ester、3-methoxybutyl acetate、3-methyl-3-methoxybutyl acetate、Propylene glycol monomethyl ether acetate、Dihydroxypropane single-ether acetate、Propylene glycol propyl ether acetate、Ethylene glycol monomethyl ether acetate、Ethylene glycol monoethyl ether acetate、Diethylene glycol ether acetate alone、Diethylene glycol monobutyl ether acetate、And dipropylene glycol methyl ether acetate.
Ketone solvent can enumerate 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, dipropyl ketone, 4-methyl-2 pentanone, Ketocyclopentane, Ketohexamethylene, isophorone etc..
Alcoholic solvent can enumerate methanol, ethanol, propanol, butanol, hexanol, Hexalin, ethylene glycol, propylene glycol and glycerol.
Aromatic hydrocarbon solvents can enumerate benzene,toluene,xylene and sym-trimethylbenzene. etc..
Amide solvent can enumerate N, N '-dimethyl Methanamide, N,N-dimethylacetamide and N-Methyl pyrrolidone.
These solvents can use in two or more combination.
From coating, drying property, the boiling point more than 120 DEG C under preferred 1atm in above-mentioned solvent, the organic solvent of less than 210 DEG C.Wherein, preferred propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxyl ethyl propionate, glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetic acid 3-methoxy butyl acrylate, 3-methoxyl group-n-butyl alcohol, 4-hydroxy-4-methyl-2-pentanone, N, dinethylformamide and N-Methyl pyrrolidone, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, acetic acid 3-methoxy butyl acrylate, 3-methoxyl group-n-butyl alcohol, 3-ethoxyl ethyl propionate, 4-hydroxy-4-methyl-2-pentanone, N, dinethylformamide and N-Methyl pyrrolidone.
Relative to the total amount of colored curable resin composition, the content of solvent (E), it is generally 70～95 mass %, it is preferable that 75～92 mass %, more preferably 75～90 mass %.If the content of solvent (E) is in above-mentioned scope, flatness during coating becomes good, and forming colour saturation during color filter in addition will not be not enough, thus display characteristic tends to well.
<levelling agent>
Levelling agent can be enumerated silicone-based surfactant, fluorine system surfactant and have the silicone-based surfactant of fluorine atom.Their side chain can have polymerizable group.
Silicone-based surfactant can enumerate in molecule the surfactant with siloxane bond.nullConcrete enumerates eastern beautiful silicone (ト mono-レ シ リ U one Application) DC3PA、Same SH7PA、Same DC11PA、Same SH21PA、Same SH28PA、Same SH29PA、Same SH30PA、Same SH8400 (Dong Li DOW CORNING Co., Ltd. (レ ダ ウ U one ニ Application グ (strain)) system)、KP321、KP322、KP323、KP324、KP326、KP340、KP341 (Shin-Etsu Chemial Co., Ltd's system)、TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF-4446、TSF4452 and TSF4460 (steps Co., Ltd of figure new high-tech material Japan (モ メ Application テ イ Block パ Off ォ mono-マ Application ス マ テ リ ア Le ズ ジ ヤ パ Application contract commercial firm) system).
Fluorine system surfactant can enumerate in molecule the surfactant with fluorocarbon chain.Concrete enumerated FLUORAD (Off ロnullOne De) (registered trade mark) FC430、Same FC431 (Sumitomo 3M Co., Ltd. (Sumitomo ス リ mono-エ Si (strain)) system)、MEGAFAC (メ ガ Off ア ッ Network) (registered trade mark) F142D、Same F171、Same F172、Same F173、Same F177、Same F183、Same F554、Same P30、Same RS-718-K (DIC (strain) system)、EFTOP (エ Off ト Star プ) (registered trade mark) EF301、Same EF303、Same EF351、Same EF352 (Mitsubishi Materials electronization becomes Co., Ltd.'s (Rhizoma Sparganii マ テ リ ア Le chemical conversion (strain)) system)、SURFLON (サ mono-Off ロ Application) (registered trade mark) S381、Same S382、Same SC101、Same SC105 (Asahi Glass Co., Ltd's system) and E5844 (Co., Ltd. great Jin fine chemistry industry institute ((strain) ダ イ キ Application Off ア イ Application ケ ミ カ Le institute) system).
The silicone-based surfactant with fluorine atom can enumerate in molecule the surfactant with siloxane bond and fluorocarbon chain.Specifically can enumerate MEGAFAC (registered trade mark) R08, same to BL20, same to F475, with F477 and same F443 (Dainippon Ink Chemicals's system).
Total amount relative to colored curable resin composition, the content of levelling agent is generally below more than 0.0005 mass % 0.6 mass %, preferably below more than 0.001 mass % 0.5 mass, more preferably below more than 0.001 mass % 0.2 mass %, preferred below more than 0.002 mass % 0.1 mass % further, it is particularly preferred to more than 0.005 mass % 0.07 mass %.If the content of levelling agent is in aforementioned range, the flatness of color filter just can become good.
<other components>
The colored curable resin composition of the present invention can as required, containing additives well-known in the art such as filler, other macromolecular compound, adhesion promotor, antioxidant, light stabilizer, chain-transferring agents.
<manufacture method of colored curable resin composition>
The colored curable resin composition of the present invention such as can be prepared by mixed colorant (A), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E) and levelling agent as required, polymerization initiation auxiliary agent and other components.Except coloring agent (A), further can hybrid pigment and/or dyestuff.Preferred pigments mixes with part or all of solvent (E) in advance, uses ball mill etc. to make it disperse until the mean diameter of pigment is about less than 0.2 μm, uses with the state of dispersible pigment dispersion.At this point it is possible to as required mixing aforesaid pigments dispersant, resin (B) part or all.
Preferred compound (I) be dissolved in advance solvent (E) part or all in prepare solution.Further, it is preferable to this solution of sieved filter that aperture is about 0.01～1 μm.
Preferably filter mixed colored curable resin composition with the sieves in about 0.01～10 μm of aperture.
<manufacture method of color filter>
The method being manufactured colored pattern by the colored curable resin composition of the present invention can enumerate photoetching process, ink-jet method, print process etc..Wherein, it is preferable that photoetching process.Photoetching process is to coat on substrate by colored curable resin composition so that it is dry formation coloring compositions nitride layer, the method developed by this coloring compositions nitride layer of photomask exposure.In photoetching process, do not use photomask and/or do not develop during by exposing, it is possible to forming the painted film of the solidfied material as above-mentioned coloring compositions nitride layer.The colored pattern formed like this, painted film are the color filters of the present invention.
The film thickness of the color filter produced is not particularly limited, and for suitably to adjust according to purpose and/or purposes, can be generally 0.1～30 μm, it is preferable that 0.1～20 μm, more preferably 0.5～6 μm.
As substrate, the glass plates such as quartz glass, borosilicate glass, alumina silicate glass, the surface soda-lime glass scribbling silica dioxide coating can be used；The resin plates such as Merlon, polymethyl methacrylate, polyethylene terephthalate, silicon, define the substrate of aluminum, silver, silver/copper/palldium alloy thin film etc. on aforesaid substrate.On these substrates, it is possible to form other color-filter layer, resin bed, transistor, circuit etc..
Photoetching process and the formation of each colour element that causes can carry out under known or usual device, condition.For example, it is possible to be carried out as follows manufacture.
First, substrate is coated with colored curable resin composition, removes the volatile ingredients such as solvent, the dry composition layer obtaining smoothing by heat drying (preliminary drying) and/or drying under reduced pressure.For example there are spin-coating method, gap coating, gap spin-coating method etc. as coating process.Temperature when being thermally dried preferably 30～120 DEG C, more preferably 50～110 DEG C.Additionally, preferably 10 seconds～60 minutes heat time heating time, more preferably 30 seconds～30 minutes.When carrying out drying under reduced pressure, it is preferable that carry out under the pressure of 50～150Pa, under the temperature range of 20～25 DEG C.The film thickness of coloring compositions nitride layer is not particularly limited, it is possible to suitably select according to the film thickness of target filter.
Then, coloring compositions nitride layer exposes by being used for forming the photomask of target coloration pattern.Pattern on this photomask is not particularly limited, it is possible to use suitable in the pattern of intended applications.The light source used in exposure preferably produces the light source of the light of 250～450nm wavelength.It is, for example possible to use cut off the not enough light filter of 350nm wavelength region to cut off this light less than 350nm, or use obtain that 436nm is neighbouring, 408 neighbouring, the band pass filter of wavelength region near 365nm, optionally obtain these optical wavelength.The concrete example of light source can enumerate finsen lamp, light emitting diode, metal halide lamp and Halogen light.In order to whole plane of exposure being irradiated equably parallel rays and making photomask and form the position of substrate of coloring compositions nitride layer and position exactly, it is preferred to use the exposure device such as mask aligner and stepper.Contact developer solution by the coloring compositions nitride layer after making exposure and develop, thus forming colored pattern on substrate.By developing, the unexposed portion in coloring compositions nitride layer is dissolved in developer solution and is removed.The aqueous solution of the alkali compoundss such as the preferred potassium hydroxide of developer solution, sodium bicarbonate, sodium carbonate, tetramethyl ammonium hydroxide.The concentration of alkali compounds preferably 0.01～10 mass %, more preferably 0.02～5 mass %.Developer solution can not comprise surfactant.Developing method can be any one in paddle paddling process, infusion process and spraying process.During development, substrate can skewed at any angle further.Preferably washing after development.
Preferably the colored pattern obtained is carried out further after bake.After bake temperature preferably 150～250 DEG C, more preferably 160～235 DEG C.Preferably 1～120 minute after bake time, more preferably 10～60 minutes.
After forming color-filter layer, for instance except pixel and/or pixel electrode, black matrix" (Block テ Star Network マ ト リ Network ス), pad (ス パ mono-サ mono-), protective layer, contact hole cambium layer etc. can be set.
The color filter formed by the colored curable resin composition of the present invention is as being useful for display device (such as liquid crystal indicator, organic el device, Electronic Paper etc.) and the color filter of solid-state imager.
[embodiment]
Then enumerate embodiment, the present invention is specifically described further." % " and " part " in example is as long as no special record, it is simply that quality % and mass parts.
In following synthesis example, the structure of compound is with NMR (JMM-ECA-500, Jeol Ltd.'s system) or mass spectrograph (LC:Agilent system 1200 type, MASS；Agilent LC/MSD6130 type) confirm.
The weight average molecular weight (Mw) of the polystyrene conversion of resin and the mensuration of number-average molecular weight (Mn) carry out under the following conditions according to GPC method.
Device: HLC-8120GPC (TOSOH Co., Ltd (ソ mono-(strain)) system)
Chromatographic column: TSK-GELG2000HXL
Column temperature: 40 DEG C
Solvent: oxolane
Flow velocity: 1.0mL/ divides
Analyze the solid component concentration of sample: 0.001～0.01 mass %
Sample size: 50 μ L
Detector: RI
Calibration standard material: PSKSTANDARDPOLYSTYRENEF-40, F-4, F-288, A-2500, A-500 (TOSOH Co., Ltd's system)
Using the ratio (Mw/Mn) of the weight average molecular weight of polystyrene conversion obtained above and number-average molecular weight as molecular weight distribution.
Embodiment 1
Double; two (3-amino-4-hydroxyphenyl) sulfone 4.98 parts of mixing 2,2-and methanol 28.1 parts.Below 10 DEG C, in the mixture obtained, it is slowly added 3-ethyoxyl-3-iminopropanoate hydrochloride 8.18 parts while stirring.By stirred below 7 hours at 10 DEG C for the mixture that obtains, at room temperature stirring 24 hours, stir 24 hours at 60 DEG C.After the reactant mixture obtained is cooled to room temperature, filters and obtain the crystallization precipitated out.The crystallization obtained with methanol washing, drying under reduced pressure at 60 DEG C, obtain the compound 6.77 parts that formula (pt1) represents.
[changing 44]
<qualification of the compound that formula (pt1) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+473
ExactMass:472
Mixing 2,4 15.2 parts/triethylamines of dimethylaniline 12.7 parts and DMF 47.3 parts, stir at 50 DEG C.Keep the temperature of this mixture while 50～60 DEG C, add the bromo-1-octene of 8-24.9 parts, then, stir 65 hours at 60 DEG C.This mixture is let cool to room temperature, adds 500 parts of water and toluene 300 parts, separation of methylbenzene layer.After toluene layer is washed 3 times with saturated sodium-chloride water solution 500 parts, solvent is distilled off with Rotary Evaporators.The residue obtained with purification by column chromatography, obtains the compound 4.33 parts that formula (pt2-1) represents.
[changing 45]
<qualification of the compound that formula (pt2-1) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+232
ExactMass:231
Under nitrogen atmosphere, the compound that hybrid (pt2-1) represents 10.9 parts, 3-bromoanisole 8.81 parts, palladium (II) 0.318 part, potassium tert-butoxide 7.94 parts, 2,8,9-triisopropyl-2,5,8,9-tetra-azepine-1-phospha bicyclo-[3.3.3] hendecane (1.0M toluene solution) 0.806 part and toluene 123 parts, stir 6 hours at 100 DEG C.The mixture obtained is let cool to room temperature, joins in 250 parts of water.After the mixture being filtrated to get, separation of methylbenzene layer.Toluene layer is washed with saturated sodium bicarbonate aqueous solution, dried with magnesium sulfate, filter.After filtrate being distilled off with Rotary Evaporators, the residue obtained with purification by column chromatography, obtain the compound 1.26 parts that formula (pt3-1) represents.
[changing 46]
<qualification of the compound that formula (pt3-1) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+338
ExactMass:337
Under nitrogen atmosphere, the compound that hybrid (pt3-1) represents 1.26 parts and dichloromethane 15.0 parts.This mixed liquor is maintained at 15～23 DEG C, the Boron tribromide (1.0M dichloromethane solution) of the amount of the molal quantitys such as the compound that addition and formula (pt3-1) represent.Then, this mixed liquor is at room temperature stirred 8 hours.The mixture obtained is added in frozen water 25.0 parts, separate dichloromethane layer.Wash dichloromethane layer with 25.0 parts of water, dry with magnesium sulfate, filter.Solvent in the liquid that obtains is distilled off with Rotary Evaporators.The residue obtained with purification by column chromatography, obtains the compound 0.983 part that formula (pt4-1) represents.
[changing 47]
<qualification of the compound that formula (pt4-1) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+324
ExactMass:323
The compound that hybrid (pt4-1) represents 4.10 parts and DMF 9.44 parts.This mixture is cooled down to less than 10 DEG C with frozen water mixing bath.While stirring this mixture, dripped phosphoryl chloride phosphorus oxychloride 3.83 parts with 35 minutes.Remove frozen water mixing bath, this mixture is warming up to room temperature.Then, this mixture is stirred 1 hour at 65～70 DEG C.This mixture is let cool to room temperature, joins in the mixture of toluene 69.4 parts and 40.0 parts of water.While stirring this mixture, add 48% sodium hydrate aqueous solution 7.60 parts.Stand this mixture, remove toluene solution layer.This toluene solution is washed with 38.0 parts of water.This toluene solution is washed with saturated sodium-chloride water solution 51.6 parts.After 0.600 part of magnesium sulfate this toluene solution dry, filter.After adding active hargil 2.50 parts in this filtrate, filter.Solvent in filtrate is distilled off with Rotary Evaporators.With this residue of purification by column chromatography, obtain the compound 1.52 parts that formula (pt5-1) represents.
[changing 48]
<qualification of the compound that formula (pt5-1) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+352
ExactMass:351
Compound 1.00 parts, piperidines 0.0400 part and the toluene 10.4 parts that the compound that addition formula (pt5-1) represents in the reaction possess Dean-Stark water knockout drum 1.50 parts, formula (pt1) represent.This mixture is stirred 7 hours at 100～110 DEG C.This mixture is let cool to room temperature.In this mixture, add methanol 9.50 parts, stir 30 minutes.Through being filtrated to get precipitate.This precipitate is washed with the mixture of toluene 2.60 parts He methanol 4.75 parts.Then, this precipitate is washed with methanol 7.13 parts.This precipitate dry.DMF 8.97 parts is added in this precipitate.28.5 parts of water is dripped in the solution obtained.2.85 parts of sodium chloride is added in this mixture.Through being filtrated to get precipitate.This precipitate is washed with 9.00 parts of water.Then, this precipitate is washed with methanol 7.13 parts.This precipitate dry obtains the compound 1.81 parts that formula (I-34) represents.
[changing 49]
<qualification of the compound that formula (I-34) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+1047
ExactMass:1046
Embodiment 2
Except replace the bromo-1-octane of 8-in embodiment 1 with allyl bromide, bromoallylene, implement operation similarly to Example 1, obtain the compound that formula (pt2-2), formula (pt3-2) and formula (pt4-2) represent.
[changing 50]
<qualification of each compound>
The compound that formula (pt2-2) represents
(mass spectral analysis) ionizes mode=FSI+:m/z=[M+H]+162
ExactMass:161
The compound that formula (pt3-2) represents
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+268
ExactMass:267
The compound that formula (pt4-2) represents
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+254
ExactMass:253
The compound that hybrid (pt4-2) represents 35.4 parts and DMF 85.9 parts.This mixture is cooled down to less than 10 DEG C with frozen water mixing bath.While stirring this mixture, dripped phosphoryl chloride phosphorus oxychloride 42.9 parts with 1 hour.Remove frozen water mixing bath, this mixture is warming up to room temperature.Then, this mixture is stirred 1 hour at 60 DEG C.This mixture is let cool to room temperature, joins in the mixture of 500 parts of water and toluene 243 parts.48% sodium hydrate aqueous solution 84.0 parts is added in this mixture.Stand this mixture, it is thus achieved that toluene solution layer.Wash this toluene solution 2 times with 500 parts of water, wash this toluene solution 1 time with saturated sodium bicarbonate aqueous solution 552 parts, wash this toluene solution 1 time with saturated sodium-chloride water solution 680 parts.After 7.00 parts of magnesium sulfate this toluene solution dry, filter.After adding active hargil 70.0 parts in this filtrate, filter.The solvent of this filtrate is distilled off with Rotary Evaporators after, obtain the compound 34.9 parts that formula (pt5-2) represents.
[changing 51]
<qualification of the compound that formula (pt5-2) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+282
ExactMass:281
Compound 27.8 parts, piperidinyl-1 .00 part and the toluene 97.0 parts that the compound that addition formula (pt5-2) represents in the reaction flask possess Dean-Stark water knockout drum 34.4 parts, formula (pt1) represent.This mixture is stirred 24 hours at 100～110 DEG C.This mixture is let cool to room temperature, solvent is distilled off with Rotary Evaporators.In the residue obtained, add methanol 88.7 parts, stir whole night.Through being filtrated to get precipitate.This precipitate dry.With this precipitate of purification by column chromatography, obtain the compound 22.2 parts that formula (I-6) represents.
[changing 52]
<qualification of the compound that formula (I-6) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+907
ExactMass:906
Embodiment 3
In resorcinol 138 parts, add 2-DEHA 64.5 parts, remove at 150 DEG C～155 DEG C and stir this mixture 18 hours while generating water.After letting cool, in reactant mixture, add toluene 250 parts, wash 3 times with 500 parts of warm water.In this toluene solution, add anhydrous magnesium sulfate 20.0 parts, after stirring, filter.The solvent of filtrate is distilled off, obtains comprising the residue 113 parts that the compound represented with formula (pt4-3-1) is main constituent.
[changing 53]
<qualification of the compound that formula (pt4-3-1) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+222
ExactMass:221
The compound that hybrid (pt4-3-1) represents 10.1 parts and 5.22 parts of water, stir at 80 DEG C.Then, while adding allyl iodide (Tokyo HuaCheng Industry Co., Ltd's system) 7.60 parts, after stirring 3 hours at 80 DEG C, 48% sodium hydrate aqueous solution 1.83 parts is added.Stir 24 hours while making the backflow of this mixture.After letting cool, use 10% sodium hydrate aqueous solution to regulate the pH to 5 of reactant mixture, add toluene 200 parts, stirring, extracting toluene layer.Wash methylbenzene extraction liquid 2 times with 600 parts of water, add anhydrous magnesium sulfate 30.0 parts, after stirring, filter.Solvent in filtrate is distilled off, obtains residue.With this residue of purification by column chromatography, obtain comprising the residue 1.33 parts that the compound represented with formula (pt4-3-2) is main constituent.
[changing 54]
<qualification of the compound that formula (pt4-3-2) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+262
ExactMass:261
Except compound except representing by formula (pt4-3-2) replaces the compound that the formula (pt4-1) in embodiment 1 represents, implement operation similarly to Example 1, obtain formula (pt5-3) and compound that formula (I-2) represents.
[changing 55]
<qualification of each compound>
The compound that formula (pt5-3) represents
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+290
ExactMass:289
The compound that formula (I-2) represents
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+923
ExactMass:922
Embodiment 4
Mixing 3-amino-phenol 218.0 parts, sodium bicarbonate 352.8 parts and DMF 1510 parts.While the mixture that stirring obtains, at 50 DEG C～55 DEG C, dripped allyl bromide, bromoallylene 532.4 parts with 5 hours.The mixture that obtains is stirred 20 hours at 50 DEG C～55 DEG C.After letting cool, in this mixture, add 6000 parts of water and toluene 3468 parts, stirring.Stand this mixture, obtain toluene solution layer.The toluene solution saturated sodium bicarbonate aqueous solution obtained 6618 parts washs 2 times, adds anhydrous magnesium sulfate 100 parts, stirring, filters.After adding active hargil 500 parts in the filtrate obtained, stirring, filter.Solvent in the solution that obtains is distilled off, obtains 362.1, the mixture of the compound that contained (pt4-4) represents.
[changing 56]
<qualification of the compound that formula (pt4-4) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+190
ExactMass:189
Mixing comprises compound 353.3 parts and the DMF 1068 parts of the compound that the formula (pt4-4) obtained represents, is cooled to less than 10 DEG C.While stirring, at 2 DEG C～9 DEG C, the mixture obtained, dripped phosphoryl chloride phosphorus oxychloride 533.6 parts with 3 hours.After the mixture obtained is adjusted to room temperature, stir 16 hours at 60 DEG C.Let cool the mixture obtained, and join in the mixture of 5046 parts of ice and toluene 3017 parts.While the mixture that stirring obtains, add 48% sodium hydrate aqueous solution 1505 parts, stand, obtain toluene solution layer.The toluene solution saturated sodium bicarbonate aqueous solution 5758 obtained washs 2 times, adds anhydrous magnesium sulfate 87 parts, stirring, filters.After adding active hargil 435 parts in the solution obtained, stirring, filter, obtain solution (1) and residue.In the residue obtained, add toluene 3017 parts, filter, obtain solution (2).Merging solution (1) and solution (2), solvent being distilled off thus obtaining residue.In this residue, add methanol 413 parts, solvent is distilled off, obtains 279.0 parts of the mixture of the compound that contained (pt5-4) represents.
[changing 57]
<qualification of the compound that formula (pt5-4) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+218
ExactMass:217
134.6 parts of the mixture of the compound that the compound that addition formula (pt1) represents in the reaction possess Dean-Stark water knockout drum 133.4 parts, contained (pt5-4) represent, piperidines 5.52 parts and toluene 1014 parts, mixing.The mixture that obtains is stirred 9 hours at 102 DEG C～104 DEG C.This mixture is stirred 12 hours at 100 DEG C.After letting cool the mixture obtained, filter, obtain residue.The residue obtained with 451 parts of washings of toluene, followed by methanol 412 parts washing, dry at 120 DEG C.The residue obtained is added in DMF 1888 parts, is heated to 110 DEG C, obtains solution.10 DEG C of solution obtained stirred below 1 hour, obtain mixture.The mixture being filtrated to get, washs residue with DMF 472 parts, followed by methanol 396 parts washing.This residue dry at 120 DEG C.In the residue obtained, add DMF 1529 parts, be heated to 110 DEG C, obtain solution.Let cool the solution obtained to room temperature, filter, obtain residue.The residue obtained with 472 parts of washings of DMF, followed by methanol 396 parts washing, dry at 120 DEG C, obtain the compound 143.6 parts that formula (I-1) represents.
[changing 58]
<qualification of the compound that formula (I-1) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+779
ExactMass:778
Embodiment 5
Mixing 3-amino-phenol 18.0 parts, sodium bicarbonate 38.2 parts and DMF 113 parts.While stirring, at 70 DEG C～75 DEG C, the mixture obtained, added the bromo-1-butylene of 4-49.8 parts with 1 hour.The mixture that obtains is stirred 24 hours at 70 DEG C～75 DEG C.The mixture that obtains is stirred 20 hours at 90 DEG C.After letting cool the mixture obtained, add 495 parts of water and toluene 82.4 parts, stirring, stand, obtain toluene solution layer.The toluene solution saturated sodium bicarbonate aqueous solution obtained 546 parts washs 2 times, adds anhydrous magnesium sulfate 8.25 parts, stirring, filters.After adding active hargil 41.2 parts in the liquid obtained, stirring, filter.After this filtrate being distilled off solvent with Rotary Evaporators, obtain 32.3 parts of the mixture of the compound that contained (pt4-5) represents.
[changing 59]
<qualification of the compound that formula (pt4-5) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+218
ExactMass:217
Mixing comprises 32.2 parts of mixture and the DMF 95.3 parts of the compound that the formula (pt4-5) obtained represents.While stirring, at-5 DEG C～4 DEG C, the mixture obtained, added phosphoryl chloride phosphorus oxychloride 49.7 parts with 1 hour.After the mixture obtained is adjusted to room temperature, stir 18 hours at 60 DEG C.After letting cool the mixture obtained, join in the mixture of 402 parts of ice and toluene 351 parts.While the mixture that stirring obtains, it is slowly added 48% sodium hydrate aqueous solution and is neutralized, after standing, obtain toluene solution layer.The toluene solution saturated sodium bicarbonate aqueous solution obtained 447 parts washs 2 times, adds anhydrous magnesium sulfate 6.75 parts, stirring, filters.After adding active hargil 33.8 parts in the liquid obtained, stir 30 minutes, filter, obtain filtrate (3) and residue.In the residue obtained, add toluene 117 parts, filter, obtain filtrate (4).Merging filtrate (3) and filtrate (4), be distilled off solvent.Methanol 238 parts is added in the residue obtained.Solvent in the solution that obtains is distilled off, obtains 26.6 parts of the mixture of the compound that contained (pt5-5) represents.
[changing 60]
<qualification of the compound that formula (pt5-5) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+246
ExactMass:245
26.0 parts of the mixture of the compound that the compound that addition formula (pt1) represents in the reaction flask possess Dean-Stark water knockout drum 22.3 parts, contained (pt5-5) represent, piperidines 0.920 part and toluene 169 parts, mixing.The mixture that obtains is stirred 1.5 hours at 105 DEG C～110 DEG C.In the mixture obtained, add toluene 130 parts, stir 21 hours at 100 DEG C.After letting cool the mixture obtained, filter.The residue obtained with toluene 151 parts, 138 parts of washings of methanol successively.The dry residue obtained at 120 DEG C.
The residue obtained is added in DMF 217 parts, stirs at 100 DEG C, obtain solution.Let cool the solution obtained to room temperature, filter.The residue obtained with 94.4 parts of washings of DMF, followed by methanol 79.2 parts washing, dry at 120 DEG C.The residue obtained with purification by column chromatography, obtains the compound 25.0 parts that formula (I-8) represents.
[changing 61]
<qualification of the compound that formula (I-8) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+835
ExactMass:834
Synthesis example 1
In the 1L flask possess reflux cooler, Dropping funnel and blender, flow into nitrogen in right amount, be replaced into nitrogen atmosphere, add propylene glycol monomethyl ether acetate 371 parts, heat while stirring to 85 DEG C.Then, 54 parts of acrylic acid, acrylic acid 3,4-epoxy radicals three ring [5.2.1.0 were dripped with 4 hours2,6] decane-8 or/and 225 parts of the mixture of 9-base ester, vinyltoluene (admixture of isomeric compound) 81 parts, propylene glycol monomethyl ether acetate 80 parts mixed solution.On the other hand, dripping polymerization initiator 2 with 5 hours, 2 '-azo double; two (2,4-methyl pentane nitrile) 30 parts is dissolved in solution formed by 160 parts of propylene glycol methyl ether acetates.After initiator solution completion of dropwise addition, after being maintained at synthermal lower 4 hours, it is cooled to room temperature, obtains the solution of the copolymer (resin B 1) of Type B viscosity (23 DEG C) 246mPa s, solids 37.5%, solution acid number 43mg-KOH/g.The weight average molecular weight Mw of the resin B 1 obtained is 10600, molecular weight distribution is 2.01.
Synthesis example 2
In the flask possessing reflux cooler, Dropping funnel and blender, pass into the nitrogen of adequate flow to obtain nitrogen atmosphere, add propylene glycol monomethyl ether acetate 100 parts, heat while stirring to 85 DEG C.Then, in this flask, about 5 hours droppings methacrylic acid 19 parts, acrylic acid 3,4-epoxy radicals three ring [5.2.1.0 are spent with a pump2,6] decane-8 base ester and acrylic acid 3,4-epoxy radicals three ring [5.2.1.02,6] mixture (containing ratio with molar ratio computing for 50: 50) 171 parts of decane-9-base ester is dissolved in the solution in propylene glycol monomethyl ether acetate 40 parts.On the other hand, using other Dropping funnel to spend about 5 hours and drip polymerization initiator 2 in flask, 2 '-azo double; two (2,4-methyl pentane nitrile) 26 parts is dissolved in the solution in 120 parts of propylene glycol methyl ether acetates.After the completion of dropwise addition of polymerization initiator, keep about 3 hours at the same temperature, be then cooled to room temperature, obtain the solution of the copolymer (resin B 2) of solid constituent 43.5%.The weight average molecular weight Mw of the resin B 2 obtained is 8000, and molecular weight distribution is 1.98, and the acid number of solids conversion is 53mgKOH/g.
[changing 62]
[preparation of colored curable resin composition]
Embodiment 6
Mix following compound and obtain colored curable resin composition:
[changing 63]
Polymerization initiator (D): the mixture (CHEMCURE-TCDM of the compound that following formula represents；
Cambridge company (ケ Application Block リ ッ ジ society) system；United imidazole) 5.86 parts；
[changing 64]
[changing 65]
Embodiment 7
Compound except representing by formula (I-34) is implemented operation similarly to Example 6, is obtained colored curable resin composition except replacing the compound that the formula (I-6) in embodiment 6 represents.
Comparative example 1
Mix following compound and obtain colored curable resin composition:
[changing 66]
Polymerization initiator (D): the mixture (CHEMCURE-TCDM of the compound that following formula represents；
Cambridge company system；United imidazole) 5.86 parts；
[changing 67]
[changing 68]
[film thickness determination]
DEKTAK3 (ULVAC Corp's system) is used to measure film thickness.
Comparative example 2
[making of painted coated film and the dipping evaluation in NMP]
With spin-coating method glass substrate (Fagle (the イ mono-グ Le) XG at 2 inch square；Corning Incorporated's (U one ニ Application グ society) system) colored curable resin composition that upper coating comparative example 1 obtains, then, at 100 DEG C, preliminary drying forms coloring compositions nitride layer after 3 minutes.After cooling, use exposure machine (TME-150RSK；Topcon Co., Ltd (ト プ U Application (strain)) make) under atmospheric atmosphere with 150mJ/cm2Light exposure (365nm benchmark) exposure.Then, at 230 DEG C, the after bake of 30 minutes is carried out, thus obtaining painted coated film.Measure the film thickness of this painted coated film.This painted coated film be impregnated in the NMP of 23 DEG C 5 minutes.Use colour examining machine (OSP-SP-200；OLYMPUS Co., Ltd. system) measure this painted coated film impregnate in NMP before and after aberration (Δ Eab*).Aberration (Δ Eab*) is more big, and display coloring agent is more big to the stripping quantity in NMP by painted coated film.
Embodiment 8
Except colored curable resin composition except obtaining by embodiment 6 replaces the colored curable resin composition that the comparative example 1 in comparative example 2 obtains, implement the operation same with comparative example 2, obtain painted coated film, similarly impregnated in NMP, measure the aberration (Δ Eab*) before and after dipping.Result is shown in table 17.
Embodiment 9
Except colored curable resin composition except obtaining by embodiment 7 replaces the colored curable resin composition that the comparative example 1 in comparative example 2 obtains, implement the operation same with comparative example 2, obtain painted coated film, similarly impregnated in NMP, measure the aberration (Δ Eab*) before and after dipping.Result is shown in table 17.
[table 17]
| Aberration (Δ Eab*) | |
| Embodiment 8 | 0.4 |
| Embodiment 9 | 0.4 |
| Comparative example 2 | 15.8 |
Represent that the compound of the result display present invention of 17 is few from painted coated film to the stripping quantity of NMP.
Embodiment 10
Mixing
Use ball mill to make pigment fully dispersed, obtain dispersible pigment dispersion,
Mix following compound, obtain colored curable resin composition:
Embodiment 11～embodiment 18
Except replacing the C.I. pigment Green 7 in embodiment 10 with the pigment shown in table 18, beyond the compound replacing formula (I-6) to represent with the compound shown in table 18, implement operation similarly to Example 10, obtain colored curable resin composition.
[table 18]
| Material | Compound | |
| Embodiment 11 | C.I. pigment green 36 | The compound that formula (I-6) represents |
| Embodiment 12 | C.I. naphthol green 58 | The compound that formula (I-6) represents |
| Embodiment 13 | C.I. pigment Green 7 | The compound that formula (I-34) represents |
| Embodiment 14 | C.I. pigment green 36 | The compound that formula (I-34) represents |
| Embodiment 15 | C.I. naphthol green 58 | The compound that formula (I-34) represents |
| Embodiment 16 | C.I. pigment Green 7 | The compound that formula (I-2) represents |
| Embodiment 17 | C.I. pigment green 36 | The compound that formula (I-2) represents |
| Embodiment 18 | C.I. naphthol green 58 | The compound that formula (1-2) represents |
Embodiment 19
[making of colored pattern]
With the spin-coating method glass substrate (EagleXG at 2 inch square；Corning Incorporated's system) go up the colored curable resin composition that coating Examples 10 obtains, then, at 100 DEG C, preliminary drying forms coloring compositions nitride layer after 3 minutes.After cooling, will be formed with being set to 200 μm between the substrate of coloring compositions nitride layer and quartz glass photomask, with exposure machine (TME-150RSK；Topcon Co., Ltd's system), under atmospheric environment, use 80mJ/cm2Light exposure (365nm benchmark) be exposed.Additionally, photomask uses the mask being formed with 100 μm of lines and space pattern.Coloring compositions nitride layer after exposure be impregnated in the aqueous solution comprising nonionic system surfactant 0.12% and potassium hydroxide 0.04% 70 seconds at 25 DEG C, development, washing.This painted coated film is carried out the after bake of 30 minutes, thus obtaining colored pattern at 230 DEG C.
Embodiment 20～embodiment 27
Except replacing, with the colored curable resin composition shown in table 19, the colored curable resin composition that the embodiment 10 in embodiment 19 obtains, implement operation similarly to Example 19, obtain colored pattern.
[table 19]
Embodiment 28
Double; two (3-amino-4-hydroxyphenyl) 10.0 parts of the propane of mixing 2,2-and methanol 51.0 parts, add 3-ethyoxyl-3-iminopropanoate hydrochloride 18.2 parts while stirring below 5 DEG C.Then, reactant mixture is stirred below 13 hours at 10 DEG C, at room temperature stirring 24 hours, stir 24 hours at 60 DEG C.Above-mentioned reactant mixture is cooled to room temperature.Solvent in this reactant mixture is distilled off with Rotary Evaporators.The residue obtained with purification by column chromatography, obtains the compound 6.46 parts that formula (pt1-b) represents.
[changing 69]
<formula (pt1-b)) represent the qualification of compound>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+451
ExactMass:450
Compound 26.5 parts, piperidinyl-1 .00 part and the toluene 97.0 parts that the compound that addition formula (pt5-1) represents in the reaction flask possess Dean-Stark water knockout drum 43.0 parts, formula (pt1-b) represent.This mixture is stirred 24 hours at 100～110 DEG C.This mixture is let cool to room temperature, solvent is distilled off with Rotary Evaporators.The residue obtained with purification by column chromatography, obtains the compound 3.29 parts that formula (I-90) represents.
[changing 70]
<qualification of the compound that formula (I-90) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+1026
ExactMass:1025
Embodiment 29
Compound except representing by formula (pt5-2) is implemented operation similarly to Example 28, is obtained the compound that formula (I-62) represents except replacing the compound that the formula (pt5-1) in embodiment 28 represents.
[changing 71]
<qualification of the compound that formula (I-62) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+885
ExactMass:884
Embodiment 30
Compound except representing by formula (pt5-3) is implemented operation similarly to Example 28, is obtained the compound that formula (I-58) represents except replacing the compound that the formula (pt5-1) in embodiment 28 represents.
[changing 72]
<qualification of the compound that formula (I-58) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+901
ExactMass:900
Embodiment 31
Compound except representing by formula (pt5-4) is implemented operation similarly to Example 28, is obtained the compound that formula (I-57) represents except replacing the compound that the formula (pt5-1) in embodiment 28 represents.
[changing 73]
<qualification of the compound that formula (I-57) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+757
ExactMass:756
Embodiment 32
Compound except representing by formula (pt5-5) is implemented operation similarly to Example 28, is obtained the compound that formula (I-64) represents except replacing the compound that the formula (pt5-1) in embodiment 28 represents.
[changing 74]
<qualification of the compound that formula (I-64) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+813
ExactMass:812
Embodiment 33
Double; two (3-amino-4-hydroxyphenyl) fluorenes 5.02 parts of mixing 9,9-and methanol 30.0 parts, add 3-ethyoxyl-3-iminopropanoate hydrochloride 6.10 parts while stirring below 5 DEG C.Then, reactant mixture is only stirred 14 hours below 10 DEG C, at room temperature only stir 24 hours, only stir at 60 DEG C 24 hours.Above-mentioned reactant mixture is cooled to room temperature.Solvent in this reactant mixture is distilled off with Rotary Evaporators.The residue obtained with purification by column chromatography, obtains the compound 2.33 parts that formula (pt1-c) represents.
[changing 75]
<qualification of the compound that formula (pt1-c) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+573
ExactMass:572
Compound except representing by formula (pt1-c) is implemented operation similarly to Example 28, is obtained the compound that formula (I-146) represents except replacing the compound that the formula (pt1-b) in embodiment 28 represents.
[changing 76]
<qualification of the compound that formula (I-146) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+1148
ExactMass:1147
Embodiment 34
Except the compound that the compound that represents by formula (pt1-c) replaces compound that the formula (pt1-b) in embodiment 28 represents, formula (pt5-1) in the compound replacement embodiment 28 that represents with formula (pt5-2) represents, implement operation similarly to Example 28, obtain the compound that formula (I-118) represents.
[changing 77]
<qualification of the compound that formula (I-118) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+1007
ExactMass:1006
Embodiment 35
Except the compound that the compound that represents by formula (pt1-c) replaces compound that the formula (pt1-b) in embodiment 28 represents, formula (pt5-1) in the compound replacement embodiment 28 that represents with formula (pt5-3) represents, implement operation similarly to Example 28, obtain the compound that formula (I-114) represents.
[changing 78]
<qualification of the compound that formula (I-114) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+1024
ExactMass:1022
Embodiment 36
Except the compound that the compound that represents by formula (pt1-c) replaces compound that the formula (pt1-b) in embodiment 28 represents, formula (pt5-1) in the compound replacement embodiment 28 that represents with formula (pt5-4) represents, implement operation similarly to Example 28, obtain the compound that formula (I-113) represents.
[changing 79]
<qualification of the compound that formula (I-113) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+879
ExactMass:878
Embodiment 37
Except the compound that the compound that represents by formula (pt1-c) replaces compound that the formula (pt1-b) in embodiment 28 represents, formula (pt5-1) in the compound replacement embodiment 28 that represents with formula (pt5-5) represents, implement operation similarly to Example 28, obtain the compound that formula (I-120) represents.
[changing 80]
<qualification of the compound that formula (I-120) represents>
(mass spectral analysis) ionizes mode=ESI+:m/z=[M+H]+935
ExactMass:934
Embodiment 38
Except replacing, beyond double; two (3-amino-4-hydroxyphenyl) propane in 2,2-in embodiment 28, implementing operation similarly to Example 28, obtaining the compound that formula (pt1-d) represents with double; two (3-amino-4-hydroxyphenyl) methane.
[changing 81]
Compound except representing by formula (pt1-d) is implemented operation similarly to Example 28, is obtained the compound that formula (I-202) represents except replacing the compound that formula (pt1-b) represents.
[changing 82]
Embodiment 39
Except the compound that the compound that represents by formula (pt1-d) replaces compound that the formula (pt1-b) in embodiment 28 represents, formula (pt5-1) in the compound replacement embodiment 28 that represents with formula (pt5-2) represents, implement operation similarly to Example 28, obtain the compound that formula (I-174) represents.
[changing 83]
Embodiment 40
Except the compound that the compound that represents by formula (pt1-d) replaces compound that the formula (pt1-b) in embodiment 28 represents, formula (pt5-1) in the compound replacement embodiment 28 that represents with formula (pt5-3) represents, implement operation similarly to Example 28, obtain the compound that formula (I-170) represents.
[changing 84]
Embodiment 41
Except the compound that the compound that represents by formula (pt1-d) replaces compound that the formula (pt1-b) in embodiment 28 represents, formula (pt5-1) in the compound replacement embodiment 28 that represents with formula (pt5-4) represents, implement operation similarly to Example 28, obtain the compound that formula (I-169) represents.
[changing 85]
Embodiment 42
Except the compound that the compound that represents by formula (pt1-d) replaces compound that the formula (pt1-b) in embodiment 28 represents, formula (pt5-1) in the compound replacement embodiment 28 that represents with formula (pt5-5) represents, implement operation similarly to Example 28, obtain the compound that formula (I-176) represents.
[changing 86]
[preparation of colored curable resin composition]
Embodiment 43～embodiment 49
Except replacing, with compound shown in table 20, the compound that the formula (I-6) in embodiment 6 represents, implement operation similarly to Example 6, obtain colored curable resin composition.
[table 20]
| Compound | |
| Embodiment 43 | The compound that formula (I-2) represents |
| Embodiment 44 | The compound that formula (I-90) represents |
| Embodiment 45 | The compound that formula (I-62) represents |
| Embodiment 46 | The compound that formula (I-58) represents |
| Embodiment 47 | The compound that formula (I-146) represents |
| Embodiment 48 | The compound that formula (I-118) represents |
| Embodiment 49 | The compound that formula (I-114) represents |
Embodiment 50～embodiment 55
Except replace the coumarin 6 in comparative example 1 with compound shown in table 21, implement the operation same with comparative example 1, obtain colored curable resin composition.
[table 21]
| Compound | |
| Embodiment 50 | The compound that formula (I-1) represents |
| Embodiment 51 | The compound that formula (I-8) represents |
| Embodiment 52 | The compound that formula (I-57) represents |
| Embodiment 53 | The compound that formula (I-64) represents |
| Embodiment 54 | The compound that formula (I-113) represents |
| Embodiment 55 | The compound that formula (I-120) represents |
[making of painted coated film and the dipping evaluation in NMP]
Embodiment 56～embodiment 68
Except replacing, with colored curable resin composition shown in table 22, the colored curable resin composition that the comparative example 1 in comparative example 2 obtains, implement the operation same with comparative example 2, obtain painted coated film, similarly impregnated in NMP, measure the aberration (Δ Eab*) before and after dipping.Result is shown in table 22.
[table 22]
| Colored curable resin composition | Aberration (Δ Eab*) | |
| Embodiment 56 | The colored curable resin composition that embodiment 43 obtains | 3.4 |
| Embodiment 57 | The colored curable resin composition that embodiment 44 obtains | 3.7 |
| Embodiment 58 | The colored curable resin composition that embodiment 45 obtains | 4.0 |
| Embodiment 59 | The colored curable resin composition that embodiment 46 obtains | 4.4 |
| Embodiment 60 | The colored curable resin composition that embodiment 47 obtains | 6.1 |
| Embodiment 61 | The colored curable resin composition that embodiment 48 obtains | 6.8 |
| Embodiment 62 | The colored curable resin composition that embodiment 49 obtains | 7.6 |
| Embodiment 63 | The colored curable resin composition that embodiment 50 obtains | 1.6 |
| Embodiment 64 | The colored curable resin composition that embodiment 51 obtains | 2.3 |
| Embodiment 65 | The colored curable resin composition that embodiment 52 obtains | 4.7 |
| Embodiment 66 | The colored curable resin composition that embodiment 53 obtains | 3.9 |
| Embodiment 67 | The colored curable resin composition that embodiment 54 obtains | 4.9 |
| Embodiment 68 | The colored curable resin composition that embodiment 55 obtains | 5.5 |
[preparation of colored curable resin composition]
Embodiment 69～embodiment 87
Except replacing the C.I. pigment Green 7 in embodiment 10 with the pigment shown in table 23, beyond the compound replacing formula (I-6) to represent with compound shown in table 23, implement operation similarly to Example 10, obtain colored curable resin composition.
[table 23]
| Material | Compound | |
| Embodiment 69 | C.I. naphthol green 59 | The compound that formula (I-6) represents |
| Embodiment 70 | C.I. naphthol green 59 | The compound 70 that formula (I-34) represents--> |
| Embodiment 71 | C.I. naphthol green 59 | The compound that formula (I-2) represents |
| Embodiment 72 | C.I. pigment Green 7 | The compound that formula (I-1) represents |
| Embodiment 73 | C.I. pigment green 36 | The compound that formula (I-1) represents |
| Embodiment 74 | C.I. naphthol green 58 | The compound that formula (I-1) represents |
| Embodiment 75 | C.I. naphthol green 59 | The compound that formula (I-1) represents |
| Embodiment 76 | C.I. pigment Green 7 | The compound that formula (I-8) represents |
| Embodiment 77 | C.I. pigment green 36 | The compound that formula (I-8) represents |
| Embodiment 78 | C.I. naphthol green 58 | The compound that formula (I-8) represents |
| Embodiment 79 | C.I. naphthol green 59 | The compound that formula (I-8) represents |
| Embodiment 80 | C.I. pigment Green 7 | The compound that formula (I-90) represents |
| Embodiment 81 | C.I. pigment green 36 | The compound that formula (I-90) represents |
| Embodiment 82 | C.I. naphthol green 58 | The compound that formula (I-90) represents |
| Embodiment 83 | C.I. naphthol green 59 | The compound that formula (I-90) represents |
| Embodiment 84 | C.I. pigment Green 7 | The compound that formula (I-146) represents |
| Embodiment 85 | C.I. pigment green 36 | The compound that formula (I-146) represents |
| Embodiment 86 | C.I. naphthol green 58 | The compound that formula (I-146) represents |
| Embodiment 87 | C.I. naphthol green 59 | The compound that formula (I-146) represents |
[making of colored pattern]
Embodiment 88～embodiment 106
Except replacing, with the colored curable resin composition shown in table 24, the colored curable resin composition that the embodiment 10 in embodiment 19 obtains, implement operation similarly to Example 19, obtain colored pattern.
[table 24]
| Colored curable resin composition | |
| Embodiment 88 | The colored curable resin composition that embodiment 69 obtains |
| Embodiment 89 | The colored curable resin composition that embodiment 70 obtains |
| Embodiment 90 | The colored curable resin composition that embodiment 71 obtains |
| Embodiment 91 | The colored curable resin composition that embodiment 72 obtains |
| Embodiment 92 | The colored curable resin composition that embodiment 73 obtains |
| Embodiment 93 | The colored curable resin composition that embodiment 74 obtains |
| Embodiment 94 | The colored curable resin composition that embodiment 75 obtains |
| Embodiment 95 | The colored curable resin composition that embodiment 76 obtains |
| Embodiment 96 | The colored curable resin composition that embodiment 77 obtains |
| Embodiment 97 | The colored curable resin composition that embodiment 78 obtains |
| Embodiment 98 | The colored curable resin composition that embodiment 79 obtains |
| Embodiment 99 | The colored curable resin composition that embodiment 80 obtains |
| Embodiment 100 | The colored curable resin composition that embodiment 81 obtains |
| Embodiment 101 | The colored curable resin composition that embodiment 82 obtains |
| Embodiment 102 | The colored curable resin composition 71 that embodiment 83 obtains--> |
| Embodiment 103 | The colored curable resin composition that embodiment 84 obtains |
| Embodiment 104 | The colored curable resin composition that embodiment 85 obtains |
| Embodiment 105 | The colored curable resin composition that embodiment 86 obtains |
| Embodiment 106 | The colored curable resin composition that embodiment 87 obtains |
The compound of the known present invention is useful as the colored curable resin composition material of the few color filter of the coloring agent stripping quantity that can be formed from painted coated film to NMP.
Industrial applicability
The present invention can provide the colored curable resin composition of the color filter that the coloring agent stripping quantity formed from painted coated film to NMP is few.Therefore, this colored curable resin composition the color filter formed is suitable in the display devices such as liquid crystal indicator.
Claims (11)
1. the compound that formula (I) represents,
[changing 1]
In formula, L represents divalent alkyl or the sulfonyl of carbon number 1～20；
X represents oxygen atom or sulphur atom；
R1Expression can have the thiazolinyl of the carbon number 2～20 of substituent group or can have the cycloalkenyl group of carbon number 3～20 of substituent group, constitutes-the CH of this thiazolinyl or cycloalkenyl group2-can by oxygen atom ,-N (R10)-or carbonyl substituted；
R2Represent 1 valency alkyl of hydrogen atom or carbon number 1～20；
R3～R9Represent hydrogen atom, 1 valency alkyl of carbon number 1～20, halogen atom, cyano group, nitro, carbamoyl, sulfamoyl ,-SO independently of one another3M、-CO2M, hydroxyl, formoxyl or amino；
R2～R9In the aforesaid alkyl represented ,-CH2-can by oxygen atom, sulphur atom ,-N (R11)-, sulfonyl or carbonyl substituted, hydrogen atom can by halogen atom, cyano group, nitro, carbamoyl, sulfamoyl ,-SO3M、-CO2M, hydroxyl, formoxyl or amino replace；
R10And R11Represent 1 valency alkyl of hydrogen atom or carbon number 1～20 independently of one another, be respectively present multiple R10And R11Time, they each other can be identical or different；
M represents hydrogen atom or alkali metal atom.
2. compound as claimed in claim 1, R1For having the thiazolinyl of the carbon number 2～16 of substituent group or can have the cycloalkenyl group of carbon number 3～16 of substituent group.
3. compound as claimed in claim 1 or 2, R1For having the thiazolinyl of the carbon number 2～10 of substituent group or can have the cycloalkenyl group of carbon number 3～10 of substituent group.
4. the compound as according to any one of claims 1 to 3, R2Aryl for the thiazolinyl of carbon number 2～10, the alkyl of carbon number 3～10, the cycloalkenyl group of carbon number 3～10 or carbon number 6～15.
5. a coloring agent, it contains in Claims 1 to 4 the compound described in any one.
6. coloring agent as claimed in claim 5, it contains pigment further.
7. a colored curable resin composition, it contains the coloring agent described in claim 5 or 6, resin, polymerizable compound, polymerization initiator and solvent.
8. a color filter, its colored curable resin composition described in claim 7 is formed.
9. a liquid crystal indicator, it comprises the color filter described in claim 8.
10. the compound that formula (II) represents,
[changing 2]
In formula, R1For having the thiazolinyl of the carbon number 2～20 of substituent group or can have the cycloalkenyl group of carbon number 3～20 of substituent group, constitute-the CH of this thiazolinyl or cycloalkenyl group2-can by oxygen atom ,-N (R10)-or carbonyl substituted；
R2Represent 1 valency alkyl of hydrogen atom or carbon number 1～20；
R3～R5Represent hydrogen atom, 1 valency alkyl of carbon number 1～20, halogen atom, cyano group, nitro, carbamoyl, sulfamoyl ,-SO independently of one another3M、-CO2M, hydroxyl, formoxyl or amino；
R2～R5In the aforementioned alkyl represented ,-CH2-can by oxygen atom, sulphur atom ,-N (R11)-, sulfonyl or carbonyl substituted, hydrogen atom can by halogen atom, cyano group, nitro, carbamoyl, sulfamoyl ,-SO3M、-CO2M, hydroxyl, formoxyl or amino replace；
R10And R11Represent 1 valency alkyl of hydrogen atom or carbon number 1～20 independently of one another, be respectively present multiple R10And R11Time, they each other can be identical or different；
M represents hydrogen atom or alkali metal atom.
11. the compound that formula (III) represents,
[changing 3]
In formula, R1For having the thiazolinyl of the carbon number 2～20 of substituent group or can have the cycloalkenyl group of carbon number 3～20 of substituent group, constitute-the CH of this thiazolinyl or cycloalkenyl group2-can by oxygen atom ,-N (R10)-or carbonyl substituted；
R2Represent 1 valency alkyl of hydrogen atom or carbon number 1～20；
R3～R5Represent hydrogen atom, 1 valency alkyl of carbon number 1～20, halogen atom, cyano group, nitro, carbamoyl, sulfamoyl ,-SO independently of one another3M、-CO2M, hydroxyl, formoxyl or amino；
R2～R5In the aforesaid alkyl represented ,-CH2-can by oxygen atom, sulphur atom ,-N (R11)-, sulfonyl or carbonyl substituted, hydrogen atom can by halogen atom, cyano group, nitro, carbamoyl, sulfamoyl ,-SO3M、-CO2M, hydroxyl, formoxyl or amino replace；
R10And R11Represent 1 valency alkyl of hydrogen atom or carbon number 1～20 independently of one another, be respectively present multiple R10And R11Time, they each other can be identical or different；
M represents hydrogen atom or alkali metal atom.
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| WO2019142955A1 (en) * | 2018-01-19 | 2019-07-25 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter comprising black matrix, column spacer or black column spacer manufactured by using same, and display device comprising same color filter |
| KR102513131B1 (en) * | 2018-09-18 | 2023-03-23 | 후지필름 가부시키가이샤 | Composition, film, optical filter, solid-state imaging device, infrared sensor, optical filter manufacturing method, camera module, compound, and dispersion composition |
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| CN103360791A (en) * | 2012-04-10 | 2013-10-23 | 住友化学株式会社 | Colorant dispersion liquid |
| CN103576454A (en) * | 2012-07-31 | 2014-02-12 | 住友化学株式会社 | Colored curable resin composition |
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| JP2006154740A (en) | 2004-07-14 | 2006-06-15 | Fuji Photo Film Co Ltd | Photosensitive composition, pattern forming material, photosensitive laminate, pattern forming apparatus and method of pattern formation |
| KR101127095B1 (en) * | 2009-12-11 | 2012-03-22 | 고려대학교 산학협력단 | Coumarin derivatives and highly efficient coumarin-containing dyes for dye-sensitized solar cell |
| US9296728B2 (en) * | 2012-01-20 | 2016-03-29 | Regents Of The University Of Minnesota | Therapeutic compounds |
| TWI570190B (en) * | 2012-02-13 | 2017-02-11 | 住友化學股份有限公司 | Colored curable resin composition |
| CN102816452B (en) * | 2012-07-10 | 2015-01-07 | 浙江龙盛集团股份有限公司 | Benzothiazole dye monomeric compound and disperse dye |
| JP2016518316A (en) * | 2013-03-15 | 2016-06-23 | セルジーン アビロミクス リサーチ， インコーポレイテッド | MK2 inhibitors and their use |
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| CN103172626A (en) * | 2011-12-26 | 2013-06-26 | 住友化学株式会社 | Dye compound |
| JP2013173726A (en) * | 2012-01-24 | 2013-09-05 | Harima Chemicals Inc | Coumarin derivative |
| CN103360791A (en) * | 2012-04-10 | 2013-10-23 | 住友化学株式会社 | Colorant dispersion liquid |
| CN103576454A (en) * | 2012-07-31 | 2014-02-12 | 住友化学株式会社 | Colored curable resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20160079692A (en) | 2016-07-06 |
| KR102407625B1 (en) | 2022-06-10 |
| TW201629052A (en) | 2016-08-16 |
| JP2016124970A (en) | 2016-07-11 |
| JP6480728B2 (en) | 2019-03-13 |
| CN105732604B (en) | 2020-12-29 |
| TWI694997B (en) | 2020-06-01 |
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