CN105384728B - Epoxy carboxylic acids' ester compounds and hardening thing containing its resin combination and the resin combination - Google Patents

Epoxy carboxylic acids' ester compounds and hardening thing containing its resin combination and the resin combination Download PDF

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CN105384728B
CN105384728B CN201510518594.XA CN201510518594A CN105384728B CN 105384728 B CN105384728 B CN 105384728B CN 201510518594 A CN201510518594 A CN 201510518594A CN 105384728 B CN105384728 B CN 105384728B
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methyl
compound
acrylate
acid
ester
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CN105384728A (en
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山本和义
内藤伸彦
锷本麻衣
土方大地
小渊香津美
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Priority claimed from JP2014169147A external-priority patent/JP6395505B2/en
Priority claimed from JP2015108279A external-priority patent/JP6437388B2/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/22—Esters containing nitrogen
    • C08F222/225—Esters containing nitrogen the ester chains containing seven or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Nonlinear Science (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Epoxy Resins (AREA)

Abstract

Project of the invention is to provide the few resin combination of a kind of transparency is excellent and refractive index is high compound, the curing shrinkage comprising the compound and the hardening thing with high marresistance/close adhesion and abundant hardness.The present invention provides: a kind of compound (A), which is to make the phenolic compounds as synthesized by phenolphthalein derivative and amido benzene derivative and epoxy resin obtained by epichlorohydrin reaction, react and obtain with (methyl) acrylic acid；Polycarboxylic compounds (B) obtained from one kind reacting the compound (A) with multi-anhydride (c)；Resin combination of the one kind containing the compound (A) or compound (B)；And a kind of resin combination comprising the compound (A), colorant (D) and adhesive resin (E).

Description

Epoxy carboxylic acids' ester compounds and contain its resin combination and the resin combination Hardening thing
Technical field
The present invention is high about refractive index and the transparency is excellent, heat resistance/solvent resistance is also excellent with particular configuration Compound and hardening thing comprising the resin combination of the compound and the resin combination.
Background technique
In recent years, positive Persisting exploitation is with active energy beam hardening, high heat resistance and high refractive index, and has the sense of the transparency Photosensitiveness material.It for photosensitive material, can be added mostly to assign other than high-fire resistance, high refractive index, also be assigned pair The close adhesion of substrate and the hardness of hardening thing, to additives such as the monomer of the dissolubility of alkali etc. and fillers.However, because of addition The grade additives can make refractive index reduction etc. and be difficult to show the characteristic of organic material, it is therefore desirable to improve the heat-resisting of resin itself Property and refractive index.
In patent document 1, discloses and use the reactant of o- phenyl phenol glycidol ether and (methyl) acrylic acid as optics Material.But resulting compound is (methyl) acrylate of simple function by this method, there is hardness/heat resistance of hardening thing Low anxiety.Moreover, liquid phase refractive index is 1.58 or so.
In patent document 2, discloses and use the terminal acrylate compound of the ethylene oxide adduct of 2- phenyl phenol as thoroughly Penetrate formula screen material.But the compound be simple function (methyl) acrylate, have hardness/heat resistance of hardening thing it is low it Anxiety.Moreover, liquid phase refractive index is 1.57 or so.
Patent document 3, which discloses, uses the resin combination comprising the amine ester compounds for deriving from phenyl phenol as optical lens Material.
Patent document 4 is disclosed using the amine ester compounds comprising deriving from phenyl phenol and with (methyl) acrylic acid of fluorene skeleton The resin combination of ester is as optical lens sheet material.
In patent document 5, though known use includes the tree with phenyl phenol skeleton and (methyl) acrylate of fluorene skeleton Oil/fat composition can have to the close adhesion of substrate and obdurability as optical lens sheet material because of the skeleton of its hard Problem.Moreover, also without record for because of carboxyl acid modified assigned close adhesion, developability etc. or because formed by alkaline developer Pattern.
Patent document 6 records the epoxy resin with bis- (4- alkylaryl) the benzyl first lactams skeletons of 2- alkyl -3,3-, and It is disclosed in the application of adhesive, coating, coating agent etc..Patent document 7 record containing the epoxy resin and carboxylic acids and/or sun from The resin combination of sub- polymerization catalyst, and glass is disclosed for instead of the purposes of material, adhesive, coating, coating agent etc..Specially Sharp document 8 also discloses the epoxy resin with bis- (4- alkylaryl) the benzyl first lactams skeletons of 2- alkyl -3,3-.
[existing technical literature]
[patent document]
[patent document 1] Japanese Unexamined Patent Publication 9-272707 bulletin
[patent document 2] Japanese Unexamined Patent Publication 5-065318 bulletin
[patent document 3] International Publication 2008/136262A1
[patent document 4] Japanese Unexamined Patent Publication 2010-265346 bulletin
[patent document 5] Japanese Unexamined Patent Publication 2008-094987 bulletin
[patent document 6] GB1158606A
[patent document 7] International Publication 2013/183735A1
[patent document 8] International Publication 2013/183736A1.
Summary of the invention
Invent the project to be solved
And a kind of resin itself with a high refractive index compound excellent the purpose of the present invention is to provide transparency include The resin combination of the compound and the hardening thing with high close adhesion and supply with sufficient hardness.
The means to solve the problem
The present inventor studies intensively to solve aforementioned problems, as a result, it has been found that containing unsaturated group with particular configuration Compound and resin combination containing the compound can solve aforementioned problems, complete the present invention then.
That is, the present invention is about making epoxy resin (a) shown in the following general formula (1) and in molecule have ethylene simultaneously not Epoxy carboxylic acids' ester compounds (A) obtained by saturation base is reacted with the compound (b) of carboxyl.
In general formula (1), R1Independently, for alkyl, carbon number 1 to 6 selected from hydrogen atom, carbon number 1 to 6 alkoxy appoint One, a indicate substituent R1Number, be 1 or 2.
In addition, the present invention is about aforementioned epoxy carboxylate compound (A), wherein the R of general formula (1)1For hydrogen atom, and in Having the compound (b) of ethylene unsaturated group and carboxyl in molecule simultaneously is (methyl) acrylic acid or cinnamic acid.
In addition, the present invention is about making obtained by aforementioned epoxy carboxylate compound (A) further reacts with multi-anhydride (c) Polycarboxylic compounds (B).
In addition, the present invention, about a kind of resin combination, which contains aforementioned epoxy carboxylate compound (A) Or polycarboxylic compounds (B).
The present invention also includes aforementioned epoxy carboxylate compound (A) and polycarboxylic acid again about aforementioned resin Close the reactive compounds (C) other than object (B).
In addition, the present invention is again about aforementioned resin, wherein above-mentioned reactive compounds (C) are selected from (poly-) ester (methyl) acrylate (C-1), amine ester (methyl) acrylate (C-2), epoxy (methyl) acrylate (C-3), (poly-) ether (first Base) acrylate (C-4), (methyl) alkyl acrylate or (methyl) acrylic acid alkylene carbonate (alkylene (meth) acrylate) (C-5), (methyl) acrylate (C-6) with aromatic rings, with alicyclic ring construction (methyl) acrylate (C-7), contain Compound (C-8), (methyl) acrylamide compound (C-9) and unsaturated polyester (UP) (C-10) institute of dimaleoyl imino are in groups One or more of compound.
In addition, the present invention is about aforementioned resin, wherein above-mentioned reactive compounds (C) are selected from amine ester (first Base) acrylate (C-2), (methyl) alkyl acrylate or (methyl) acrylic acid alkylene carbonate (C-5) and (first with aromatic rings Base) acrylate (C-6) compound one or more of in groups.
In addition, the present invention is about aforementioned resin, wherein refractive index (D line, 25 DEG C) is 1.52 to 1.72.
In addition, the present invention is about a kind of resin combination, containing above-mentioned epoxy carboxylic acids' ester compounds (A), colorant (D) and Adhesive resin (E).
Furthermore the present invention is about aforementioned resin, wherein foregoing colorants (D) are to mutter selected from dibenzo piperazine (xanthene) based dye, triarylmethane based dye, cyanine based dye, anthraquinone based dye, a kind or more of azo based dye.
Furthermore the present invention is about aforementioned resin, wherein aforementioned binder resin (E) is the insatiable hunger containing carboxyl With the copolymer of monomer and unsaturated carboxylate type.
In addition, a kind of hardening thing of the present invention about aforementioned resin.
In addition, the present invention is about a kind of colour filter with aforementioned hardening thing.
In addition, the present invention is about a kind of display element with aforementioned colour filter.
The effect of invention
It is of the invention comprising epoxy carboxylic acids' ester compounds (A) (for make epoxy resin (a) shown in aforementioned formula (1) in In molecule simultaneously there is ethylene unsaturated group to react with the compound (b) of carboxyl and obtain) resin combination or comprising polynary The resin combination of carboxylic acid compound (B) (being obtained to react epoxy carboxylic acids' ester compounds (A) with multi-anhydride (c)) Hardening thing, the not only balancing good of heat resistance, moisture-proof also has the transparency, performance high refractive index.Furthermore the hardening thing It is the excellent material of the mechanical properties such as obdurability, heat resistance, solvent resistance, in particular, being close adhesion, the scratch resistance to substrate Also material is used in excellent epithelium formation.It can develop due to the resin combination of the invention buck dissolubility caused by polybasic carboxylic acid, therefore It is also suitable for as the material for optics resist.For example, the hard conating of the display machine such as lens, optical disc, liquid crystal display, The optical applications such as the optical materials such as film, optical waveguide, and it is suitable for colour filter, the display element with colour filter.
Specific embodiment
Resin combination of the invention, comprising make aforementioned formula (1) (in general formula (1), R1Independently, for selected from hydrogen original Son, the alkyl of carbon number 1 to 6, carbon number 1 to 6 alkoxy any one, a indicate substituent R1Number, be 1 or 2) shown in Epoxy resin (a) in molecule there is ethylene unsaturated group to react with the compound (b) of carboxyl simultaneously obtained by epoxy carboxylic Ester compound (A) or polycarboxylic acid obtained by reacting epoxy carboxylic acids' ester compounds (A) further with multi-anhydride (c) It closes object (B).
R in general formula (1)1It is properly selected depending on used purposes.It can be mentioned, for example, hydrogen atoms, carbon number 1 to 6 The alkoxy and halogen atom of alkyl, carbon number 1 to 6.Wherein, from the point of view of by viewpoints such as the acquirements of material, most preferably R1It is all hydrogen original The compound of son.
A in the present invention indicates substituent R1Number, be 1 or 2.
The alkyl of carbon number 1 to 6 in the present invention can for straight chain, branched chain, it is cricoid any one.It is preferred that methyl, ethyl, third Base.
The alkoxy of carbon number 1 to 6 in the present invention can for straight chain, branched chain, it is cricoid any one.It is preferred that methoxyl group, second Oxygroup.
Halogen atom in the present invention can enumerate chlorine atom, bromine atom, iodine atom.
Epoxy resin (a) shown in general formula (1), such as can be obtained according to manufacturing method described in patent document 1.And And commercially available product (Japanese chemical drug trade name: WHR-EP: the R of general formula (1) also can be used1It is all hydrogen atom, epoxide equivalent is 266g/eq)。
For the present invention, in outstanding preferred epoxy (a) epoxide equivalent compared with the small person of 266g/ equivalent.The reason is that can incite somebody to action More ethylene unsaturated bond is directed into epoxy carboxylic acids' ester compounds (A) and polycarboxylic compounds (B), therefore can assign gained Hardening thing mechanical strength and become high-tenacity resin.
Epoxy carboxylic acids' ester compounds (A) of the invention are to make aforementioned epoxy resins (a) and have ethylene unsaturated simultaneously Base reacts (epoxy carboxylic acids' esterif iotacation step) with the compound (b) of carboxyl and obtains.Polycarboxylic compounds (B) of the invention are to make ring Oxycarboxylic acid ester compounds (A) further react with multi-anhydride (c) (sour addition step) and are obtained.
By aforementioned epoxy carboxylic esterification step, the second of the reactive group of active energy beam is imported in the skeleton of epoxy resin Alkene unsaturated group.Specifically, epoxy group and carboxyl react.This has the chemical combination of ethylene unsaturated group and carboxyl simultaneously Object (b) it can be mentioned, for example: (methyl) acrylic compounds, crotonic acid, alpha-cyano cinnamic acid, cinnamic acid make have unsaturation simultaneously Compound obtained by base is reacted with the compound of hydroxyl with saturation or unsaturated dibasic acid etc..
Above-mentioned makes obtained by there is unsaturated group to react with the compound of hydroxyl with saturation or unsaturated dibasic acid simultaneously Compound etc., it can be mentioned, for example: make in 1 molecule with 1 hydroxyl (methyl) acrylate derivative and saturation or not Monounsaturated dicarboxylic acid acid anhydride carries out half esters obtained by reaction with same mole.For example, making (methyl) Hydroxyethyl Acrylate, (methyl) propylene (methyl) dihydroxypropyl alkyl esters such as sour hydroxy propyl ester, (methyl) hydroxy butyl acrylate, with maleic anhydride, succinic anhydride, phthalein Saturations or the unsaturated dibasic acids such as acid anhydrides, the part hydrogenation perhydro-compound of anhydride phthalic acid, trihemellitic acid acid anhydride, benzenetetrahydride Compound obtained by reaction.
In above compound, if considering the stability of epoxy resin (a) and compound (b) reacted, preferred compound (b) For monocarboxylic acid.And with monocarboxylic acid and when polybasic carboxylic acid, preferably the ratio of mole/polybasic carboxylic acid mole of monocarboxylic acid be 15 with On.As compound (b), for the point of the sensitivity to active energy beam when becoming resin combination, preferred (first Base) acrylic acid or cinnamic acid.
Epoxy resin (a) and the adding proportion of compound (b) are suitably changed depending on purposes in this reaction.Also that is, complete When the epoxy group in portion is through carboxylic esterification, because unreacted epoxy group is not present, therefore the preservation of epoxy carboxylic acids' ester compounds (A) is stable Property it is high.At this point, sclerous reaction becomes reactivity caused by the double bond merely with importing.
In epoxy carboxylic acids' esterif iotacation step when remaining epoxy group, the addition ratio of epoxy resin (a) and compound (b) Example, preferably with respect to 1 equivalent of epoxy group of epoxy resin (a), the carboxyl of compound (b) is 0.90 to 1.20 equivalent.If in this Range, then the epoxy group of remained unreacted or unreacted epoxy group be not less, thus in sour addition step will not gelatinization, tree The preservation stability of rouge is good.The additive amount of compound (b) thus range when, the remaining epoxy group of compound (a) institute is few, resin Stability improve.
On the other hand, the additive amount of compound (b) is reduced and the epoxy group of remained unreacted, can will be led whereby Reaction caused by the unsaturated bond entered is reacted with caused by remaining epoxy group (for example, polymerization caused by light cationic catalyst Reaction or heat polymerization etc.) plyability it is used in hardening purposes.At this point, reaching to the close adhesion of metal material etc. It improves, the attenuating of curing shrinkage.But the preservation or manufacturing condition of epoxy carboxylic acids' ester compounds need to be noticed.
When residual epoxy base, relative to 1 equivalent of epoxy group of epoxy resin (a), add the carboxyl 0.20 of compound (b) to 0.90 equivalent.As long as the effect of composite hardening can be played within the scope of this.Moreover, need to be noticed subsequent anti-when residual epoxy base Gelatinization and epoxy carboxylic acids' ester compounds (A) in answering through when stability.Furthermore through aftermentioned sour addition step used as When polycarboxylic compounds (B), preferably non-residual epoxy base.It also, can be anti-with the carboxyl of importing that is, when remaining the epoxy group of volume It answers and saves stability and particularly deteriorate.
Epoxy carboxylic acids' esterif iotacation step is solvent-free or enables its reaction after being diluted with solvent.When using solvent, the solvent is only Reaction is not particularly limited without influence.It can be mentioned, for example the fragrance such as toluene, dimethylbenzene, ethylo benzene, durol for the solvent Family hydrocarbon solvent, the fatty families hydrocarbon solvent such as hexane, octane, decane belong to petroleum ether, the unleaded vapour of the mixture of above-mentioned person Oil, solvent naphtha, ester series solvent, ether series solvent, ketone series solvent etc..
Ester series solvent can be enumerated: the acetic acid alkyl ester class such as ethyl acetate, propyl acetate, butyl acetate；The ring-types such as gamma-butyrolacton Esters；Ethylene glycol single methyl ether acetic acid esters, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, Triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, fourth two Single or poly- alkylene glycols monoalky lether monoacetate class such as alcohol monomethyl ether monoacetate；Glutaric acid dialkyl, succinic acid dioxane Polybasic carboxylic acids alkyl ester class such as ester, adipic acid dialkyl etc..
Ether series solvent can be enumerated: the alkyl ethers such as Anaesthetie Ether, ethyl-butyl ether；Ethylene glycol dimethyl ether, ethylene glycol two Ethylether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol Anaesthetie Ether etc. Glycol ethers；Ring-type ethers such as tetrahydrofuran etc..
Ketone series solvent can enumerate acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, different Buddhist ketone etc..
In addition, the solvent as epoxy carboxylic acids' esterif iotacation step, can be used aftermentioned reactive compounds (C) etc..The equal solvent It can be used alone or as a mixture.At this point, can be directly using as resin combination of the invention.
In epoxy carboxylic acids' esterif iotacation step, also it can be used catalyst to promote to react.Relative to the total amount of reactant, this is urged The usage amount of agent is 0.1 to 10 quality % of addition or so.The catalyst it can be mentioned, for example: triethylamine, benzyldimethylamine, 2,4, Triethyl ammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, antimony triphenyl, methyl triphenyl Basic catalysts such as antimony, sad chromium, zirconium caprylate etc..
The reaction temperature of epoxy carboxylic acids' esterif iotacation step is 60 to 150 DEG C.Moreover, the reaction time preferably 5 to 60 hours.Epoxy The thermal polymerization inhibitor of carboxylic esterification step, such as can be used: Hydroquinone monomethylether, 2- methylnaphthohydroquinone, quinhydrones, diphenyl bitter taste Hydrazine, diphenylamine, 3,5- di-t-butyl -4- hydroxy-methylbenzene etc..
Epoxy carboxylic acids' esterif iotacation step, it is appropriate to sample, while with the acid value of sample (according to JIS K5601-2-1:1999) at It is terminal for 3mgKOH/g or less, preferably as 2mgKOH/g time point below.
Secondly, illustrating sour addition step.Sour addition step, so that the hydroxyl as caused by epoxy carboxylic acids' esterif iotacation step and more First acid anhydrides (c) reaction, obtains being imported with via ester bond for the purpose of the polycarboxylic compounds (B) of carboxyl.
Multi-anhydride (c), as long as the compound with acid anhydrides construction in molecule is not particularly limited.It is preferred that for example, alkali The excellent succinic anhydride such as property aqueous development, heat resistance, hydrolytic resistance, anhydride phthalic acid, tetrahydro anhydride phthalic acid, hexahydro anhydride phthalic acid, Itaconic anhydride, 3- methyl-tetrahydro anhydride phthalic acid, 4- methyl-hexahydro anhydride phthalic acid, trihemellitic acid acid anhydride or maleic anhydride.
Sour addition step, also can by the reaction solution in aforementioned epoxy carboxylic esterification step add multi-anhydride (c) and It carries out.The additive amount of multi-anhydride (c) is suitably changed depending on purposes.
However, the resist by polycarboxylic compounds used in resin combination of the invention (B) as alkali developable In use, addition makes the solid point acid value of last resulting polycarboxylic compounds (B) (according to JIS K5601-2-1:1999) As 40 to the 100mgKOH/g, multi-anhydrides (c) preferably as 60 to 90mgKOH/g calculating meters.Solid divides acid value Compared with this range hour, the alkaline aqueous solution developability of resin combination is significantly reduced, and worst situation is that can not develop.Moreover, When solid divides acid value to be more than this upper limit, multi-anhydride (c) is superfluous, unreacted multi-anhydride (c) residual for reflecting point In composition, developability become excessively high and have become can not formed patterns situation.
In sour addition step, in order to promote reaction, it is preferable to use catalyst.Relative to the total amount of reactant, the catalysis The usage amount of agent preferably adds 0.1 to 10 quality % or so.The catalyst it can be mentioned, for example: triethylamine, benzyldimethylamine, 2,4, Triethyl ammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, triphenylphosphine, antimony triphenyl, methyl triphenyl Antimony, sad chromium, zirconium caprylate etc..
The reaction temperature of sour addition step is 60 to 150 DEG C.Moreover, the reaction time preferably 5 to 60 hours.
Sour addition step is solvent-free or enables its reaction after being diluted with solvent.When using solvent, as long as the solvent not shadow Reaction is rung to be not particularly limited.Moreover, when the carboxylic esterification step of preceding step is manufactured using solvent, if not to sour addition The solvent that step impacts then can not also remove solvent and be supplied to sour addition step.
The solvent can enumerate solvent identical with carboxylic esterification step.
The solvent of other acid addition steps, can be used aftermentioned reactive compounds (C) etc..The equal solvent can be independent or mixed It closes and uses.At this point, can be directly using as resin combination of the invention.The thermal polymerization inhibitor of sour addition step can be used Person identical as aforementioned epoxy carboxylic esterification step.Sour addition step, can suitably be sampled, at the same with the acid value of reactant at For view purpose purposes setting acid value positive and negative 10% range point as terminal.
In the manner described above, high refractive index and transparent excellent the compound of the present invention (A) or (B) can be obtained.
Resin combination of the invention contains the compound of the present invention (A) or (B), but also optionally can contain compound (A) other reactive compounds (C) or except (B).
Reactive compounds (C) in the present invention indicate can be because of compound that active energy beam is reacted.Concrete example It can enumerate: (poly-) ester (methyl) acrylate (C-1), amine ester (methyl) acrylate (C-2), epoxy (methyl) acrylate (C-3), (poly-) ether (methyl) acrylate (C-4), (methyl) alkyl acrylate, (methyl) acrylic acid alkylene carbonate (C-5), have (methyl) acrylate (C-6) of aromatic rings, contains maleimide at (methyl) acrylate (C-7) with alicyclic ring construction Compound (C-8), (methyl) acrylamide compound (C-9) and unsaturated polyester (UP) (C-10) of base etc., but be not limited to This.
Resin combination of the invention can (poly-) ester (methyl) acrylate (C-1), it can be mentioned, for example caprolactones Modified (methyl) acrylic acid 2- hydroxy methacrylate, ethylene oxide and/or epoxy pronane modification phthalandione (methyl) acrylate, epoxy second Alkane is modified simple functions (poly-) esters (methyl) such as succinic acid (methyl) acrylate, caprolactone modification (methyl) tetrahydrofurfuryl acrylate Esters of acrylic acid；Hydroxyl trimethylace tonitric ester neopentyl glycol two (methyl) acrylate, caprolactone modification hydroxyl trimethylace tonitric Two (poly-) esters (methyl) such as ester neopentyl glycol two (methyl) acrylate, epoxychloropropane modified phthalandione two (methyl) acrylate Esters of acrylic acid；In the 6-caprolactone, gamma-butyrolacton, δ-penta of trimethylolpropane or 1 mole of glycerol, 1 mole of addition or more The mono-, di- of triol obtained by the annular lactones compound such as ester or three (methyl) acrylate.
It can enumerate again: 6-caprolactone, γ-in new penta tetrol or 1 mole of two-trimethylolpropanes, 1 mole of addition or more Mono-, di-, three or four (methyl) acrylate of triol obtained by the annular lactones compound such as butyrolactone, δ-valerolactone；Yu Erxin Three obtained by the annular lactones compounds such as 6-caprolactone, gamma-butyrolacton, the δ-valerolactone of penta 1 mole of tetrol, 1 mole of addition or more List (methyl) acrylate of the polyalcohols such as triol, tetrol, pentol or six alcohol of the list of alcohol or poly- (methyl) acrylate is poly- (methyl) acrylate.
It can also further enumerate: (poly-) ethylene glycol, (poly-) propylene glycol, (poly-) tetramethylene glycol, (poly-) butanediol, 3- first The diol components such as base -1,5- pentanediol, hexylene glycol and maleic acid, good fortune horse acid, succinic acid, adipic acid, phthalandione, isophathalic acid, hexahydro The polyacids such as phthalandione, tetrahydro phthalandione, dimer acid, decanedioic acid, azelaic acid, 5- sodium sulfonated isophthalic acid；And the acid anhydrides with foregoing Reactant polyester polyol (methyl) acrylate；Acid anhydrides comprising foregoing glycols ingredient and polyacid and foregoing with (methyl) acrylate of annular lactone modified poly ester glycol of 6-caprolactone, gamma-butyrolacton, δ-valerolactone etc. etc. it is multifunctional (poly-) ester (methyl) esters of acrylic acid etc., but not limited to this.
It can be that at least there is (a first with amine ester (methyl) acrylate (C-2) of resin combination of the invention Base) acryloxy hydroxy compounds (C-2- first) reacted with isocyanate compound (C-2- second) obtained by (methyl) propylene The general designation of acid esters.
At least concrete example of the hydroxy compounds (C-2- first) with (methyl) acryloxy, it can be mentioned, for example: (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) third Olefin(e) acid 4- hydroxy methacrylate, cyclohexanedimethanol list (methyl) acrylate, polyethyleneglycol (methyl) acrylate, polypropylene glycol Single (methyl) acrylate, new penta tetrol three (methyl) acrylate, (methyl) acrylic acid 2- hydroxyl -3- benzene oxygen propyl ester etc. are various (methyl) acrylate compounds with hydroxyl；Above-mentioned (methyl) acrylate compounds and 6-caprolactone with hydroxyl Ring-opening reaction object etc..
The concrete example of isocyanate compound (C-2- second), it can be mentioned, for example: paraphenylene diisocyanate, isophthalic diisocyanate Ester, p-xylene diisocyanate, meta-xylene diisocyanate, 2,4 toluene diisocyanate, 2,6- toluene diisocyanate The aromatic diisocyanates classes such as acid esters, 4,4 '-methyl diphenylene diisocyanates, naphthalene diisocyanate；Different two isocyanide of Buddhist ketone Acid esters, hexamethylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanates, hydrogenated xylene diisocyanate, drop ice Piece alkene diisocyanate, the diisocyanates constructed from the aliphatic such as amino acid diisocyanate or alicyclic ring；Isocyanate-monomer The polyisocyanate such as isocyanates body through trimerizing of more than one biuret body or above-mentioned diisocyanate cpd；It will Above-mentioned isocyanate compound and foregoing polyols compound pass through polyisocyanate obtained by amine esterification etc..
It can make with epoxy (methyl) acrylate (C-3) of resin combination of the invention containing 1 or more The general designation of (methyl) acrylate obtained by the epoxy resin of epoxy group is reacted with (methyl) acrylic acid.As epoxy (methyl) third The concrete example of the epoxy resin of the raw material of olefin(e) acid ester can be enumerated: quinhydrones diglycidyl ether, catechol diglycidyl ether, The phenyl diglycidyl ether such as resorcinol diglycidyl ether；Bisphenol-A-type epoxy resin, bisphenol-Ftype epoxy resin, bis-phenol-S The biphenol type epoxies such as the epoxide of bis- (4- the hydroxy phenyl) -1,1,1,3,3,3- hexafluoropropane of type epoxy resin, 2,2- Close object；A Hydrogenated Bisphenol A-A type epoxy resin, A Hydrogenated Bisphenol A-F type epoxy resin, A Hydrogenated Bisphenol A-S type epoxy resin, hydrogenation 2,2- The A Hydrogenated Bisphenol As type ring oxygen compounds such as the epoxide of bis- (4- hydroxy phenyl) -1,1,1,3,3,3- hexafluoropropane；Bromination is double The halogenated bisphenols type ring oxygen compounds such as phenol-A type epoxy resin, brominated bisphenol-F type epoxy resin；Cyclohexanedimethanol two shrinks The ester ring type 2-glycidyl ether compounds such as glycerol ether compound；1,6 hexanediol diglycidylether, 1,4- butanediol two contract The aliphatic diglycidylethers compounds such as water glycerin ether, diethylene glycol diglycidyl glycerin ether；More sulphur diglycidyl ethers etc. are more Sulphur (polysulfide) type 2-glycidyl ether compound；Phenol phenolic resin varnish type epoxy resin, cresol novolak type epoxy tree Rouge, three hydroxy phenyl methane type epoxy resin, bicyclopentadiene phenol-type epoxy resin, connection phenol-type epoxy resin, bisphenol-a type phenol Novolac type epoxy resin, the epoxy resin containing naphthalene skeleton, hetero ring type epoxy resin etc..
Can be with (poly-) ether (methyl) acrylate (C-4) of resin combination of the invention, it can be mentioned, for example (first Base) acrylate, butoxy ethyl, butoxytriglycol (methyl) acrylate, epoxychloropropane modified (methyl) acrylic acid fourth Ester, (methyl) acrylic acid dicyclopentenyl oxygroup ethyl ester, (methyl) acrylic acid 2- ethoxy ethyl ester, ethyl carbitol (methyl) propylene Simple functions (poly-) ether (first such as acid esters, (methyl) phenoxyethyl acrylate, Nonylphenoxy polyethylene glycol (methyl) acrylate Base) esters of acrylic acid.
It can also enumerate: polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, polytetramethylene glycol two Alkylene glycols two (methyl) esters of acrylic acid such as (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate；Ring The copolymer of oxidative ethane and propylene oxide, the copolymer of propylene glycol and tetrahydrofuran, poly- isoprene, the poly- isoprene of hydrogenation, The multi-hydroxies compounds such as the hydrocarbon systems polyalcohols such as polybutadiene diol, hydrogenated polybutadiene diol and (methyl) acrylic acid are derivative Made of multifunctional (methyl) acrylate class；There are 1 mole or more of ethylene oxide, epoxy third in 1 mole of neopentyl glycol addition Two (methyl) acrylate of the glycol of the cyclic ethers such as alkane, epoxy butane.
It can also enumerate: two (methyl) acrylate of the alkylene oxide modifier of the bisphenols such as bisphenol-A, Bisphenol F, bisphenol S；Hydrogen Change alkylene oxide modifier two (methyl) acrylate of the A Hydrogenated Bisphenol As classes such as bisphenol-A, A Hydrogenated Bisphenol A F, A Hydrogenated Bisphenol A S；In 1 mole The cyclic ether compounds such as ethylene oxide, propylene oxide, the epoxy butane of trimethylolpropane or 1 mole of glycerol addition or more and obtain Triol mono-, di- or three (methyl) acrylate.
It can further enumerate again: have 1 mole or more of epoxy in 1 mole of new penta tetrol or two-trimethylolpropane additions The mono-, di- of the triol of the cyclic ether compounds such as ethane, propylene oxide, epoxy butane, three or four (methyl) acrylate；It rubs in 1 Your two new penta tetrol additions have six alcohol of the cyclic ether compounds such as 1 mole or more of ethylene oxide, propylene oxide, epoxy butane Multifunctional (poly-) ether (methyl) esters of acrylic acid such as 3 or even 6 function (methyl) acrylate etc..
It can be with (methyl) alkyl acrylate or (methyl) acrylic acid alkylene carbonate (C- of resin combination of the invention 5), it can be mentioned, for example (methyl) 2-ethyl hexyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) decyl acrylate, (methyl) propylene The simple functions such as dodecyl gallate (methyl) esters of acrylic acid.
It can also enumerate: ethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, 1,4- butanediol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 2- methyl-1, 8- ethohexadiol two (methyl) acrylate, 1,9- nonanediol two (methyl) acrylate, 1,10- decanediol two (methyl) acrylic acid Two (methyl) esters of acrylic acid of the hydrocarbon glycol of ester.
It can also enumerate: list (methyl) acrylate, two (methyl) acrylate or three (methyl) third of trimethylolpropane List (methyl) acrylate of olefin(e) acid ester (hereinafter, with multifunctional persons such as two functions of " poly- " general designation, trifunctional, tetrafunctionals), glycerol Or single or poly- (first of single or poly- (methyl) acrylate of poly- (methyl) acrylate, new penta tetrol, two-trimethylolpropanes Base) acrylate, two new penta tetrols the list of polyalcohols or poly- such as triols, tetrol, six alcohol such as single or poly- (methyl) acrylate (methyl) esters of acrylic acid.
It can further enumerate again: (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) third (methyl) acrylic compounds etc. containing hydroxyl such as olefin(e) acid 4- hydroxybutyl.
Example can be enumerated with (methyl) acrylate (C-6) with aromatic rings of resin combination of the invention Such as: (methyl) phenyl acrylate, (methyl) benzyl acrylate, 2- phenyl phenol the terminal acrylate of ethylene oxide adduct add At the simple functions such as object (for example, NIPPON PHARMACEUTICAL CO., LTD OPP-1) (methyl) esters of acrylic acid；Bisphenol-A two (methyl) Two (methyl) esters of acrylic acid such as acrylate, Bisphenol F two (methyl) acrylate etc., but not limited to this.
It can be enumerated with (methyl) acrylate (C-7) with alicyclic ring construction of resin combination of the invention Such as: (methyl) cyclohexyl acrylate, (methyl) acrylic acid ring pentyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid Dicyclopentenyl ester etc. has simple function (methyl) esters of acrylic acid of alicyclic ring construction；The hydrogenation such as hydrogenated bisphenol A, A Hydrogenated Bisphenol A F is double Two (methyl) acrylate of phenols；Tristane dihydroxymethyl two (methyl) acrylate etc. has the multifunctional of ring-shaped structure Property (methyl) esters of acrylic acid；Four chaff ester of (methyl) acrylic acid is equal to ester ring type (methyl) propylene with oxygen atom etc. in construction Acid esters etc., but not limited to this.
Moreover, can with for the compound with (methyl) acryloyl group of resin combination of the invention, Other than above compound, also can be used for example: (methyl) acrylate copolymer is reacted with (methyl) glycidyl acrylate Poly- (methyl) acrylate copolymers such as the reactant of object or (methyl) glycidyl acryiate polymer and (methyl) acrylic acid (methyl) acrylate；(methyl) dimethylaminoethyl acrylate etc. has (methyl) acrylate of amido；Three (methyl) The cyamelides such as acrylyl oxy-ethyl isocyanuric acid ester base (methyl) acrylate；(methyl) with silicone matrix Acrylate；Polybutadiene (methyl) acrylate, melamine (methyl) acrylate etc..
Moreover, can be enumerated with the compound (C-8) containing dimaleoyl imino of resin combination of the invention Such as: N- normal-butyl maleimide, N- hexyl maleimide, 2- Mailed Ethyl-ethyl carbonate ester, the Malaysia 2- acyl Monofunctional aliphatics' maleimides such as iminoethyl-propyl carbonate, N- ethyl-(2- Mailed Ethyl) amine formic acid esters Class；The ester ring types simple function maleimide such as N- N-cyclohexylmaleimide；N, N- hexa-methylene bismaleimide, poly- third The aliphatic bismaleimide amines such as bis- (the 3- maleimide propyl) ethers of glycol-, bis- (2- Mailed Ethyl) carbonic esters； The ester ring types bismaleimide such as 1,4- dimaleimide hexamethylene, different Buddhist ketone diamine ester bis- (n-ethylmaleimide)； Maleimide compound obtained by maleimide acetic acid and polytetramethylene glycol are esterified, maleimidohexanoic acid with The carboxyl maleimide derivative of maleimide compound formed by the esterification of the tetraoxane addition product of new penta tetrol etc. (poly-) ester (poly-) maleimide compound obtained by object and various (poly-) alcohol are esterified etc., but not limited to this.
Can be with (methyl) acrylamide compound (C-9) of resin combination of the invention, it can be mentioned, for example propylene Mono-functionals (methyl) acrylic amides such as morpholide, N- isopropyl (methyl) acrylamide；Di-2-ethylhexylphosphine oxide (methyl) acryloyl Multifunctional (methyl) acrylic amide such as amine etc..
Can with the unsaturated polyester (UP) (C-10) of resin combination of the invention, it can be mentioned, for example: good fortune horse dimethyl phthalate, The good fortune fumaric ester class such as good fortune horse diethyl phthalate；The reactant of esterification of the multi-unsaturated carboxylic acids and polyalcohol such as maleic acid, good fortune horse acid.
Reactive compounds workable for resin combination of the invention (C), preferably (C-2), (C-5) and (C-6), especially It is preferred that (C-5).
In resin combination of the invention comprising reactive compounds (C), the compound of the present invention (A) or (B) and anti- The use ratio of answering property compound (C) is (A) or (B): (C)=5:95 to 95:5 (unit is quality %), preferably (A) or (B): (C)=20:80 to 80:20 (unit is quality %).
Resin combination of the invention is easily hardened by active energy beam.Wherein, the tool of active energy beam Body example can be enumerated: the electromagnetic waves such as ultraviolet light, luminous ray, infrared ray, X-ray, gamma-rays, laser, alpha ray, β ray, electronics Particles beams such as beam etc..If considering the purposes that is suitble to of the present invention, in above-mentioned active energy beam, preferably ultraviolet light, laser, can Light-exposed line or electron beam.
The refractive index (D line, 25 DEG C) of resin combination of the invention can be easily adjusted.Refractive index (D line, 25 DEG C) is 1.52 to 1.72 range person is widely used as optical material.
The hardening thing of resin combination of the invention, which refers to, enables it to resin combination irradiation active energy beam of the invention Hardening person.
So that for the purpose of resin combination of the invention is fit for various uses, it also can be in resin combination with 90 mass % Other compositions are added for the upper limit.Other compositions can be suitably used: polymerization initiator, solvent, nonreactive compound, inorganic Filler, organic filler, silane coupling agent, tackifiers, defoaming agent, levelling agent, plasticiser, antioxidant, ultraviolet radiation absorption Agent, fire retardant, dyestuff etc..Workable other compositions illustrated below.
It can be mentioned, for example: benzoin, benzoin methyl ether, benzoin ethyl ether, benzene are even for free radical type Photoepolymerizationinitiater initiater The benzoin class such as relation by marriage propyl ether, benzoin isobutyl ether；Acetophenone, 2,2- diethoxy -2- phenyl acetophenone, 1,1- dichloro-benzenes Ethyl ketone, 2- hydroxy-2-methyl-phenyl-propane-1- ketone, diethoxy acetophenone, 1- hydroxycyclohexylphenylketone, 2- methyl-1- The acetophenones such as [4- (methylsulfany) phenyl] -2- morpholinyl-propane -1- ketone；2- ethyl hydrazine, 2- tert-butyl anthraquinone, 2- chlorine The Anthraquinones such as anthraquinone, 2- amyl anthraquinone；The sulphur such as 2,4- diethyl thioxanthone, 2- isopropyl thioxanthone, 2- chlorothiaxanthenone Miscellaneous anthrone (thioxanthone) class；The contracting such as 2,2- dimethoxy -2- phenyl acetophenone, phenyl (α, alpha, alpha-dimethyl oxy-benzyl) ketone Aldehydes；The hexichol first such as benzophenone, 4,4 '-thiobis (2- methyl-1,3- benzenediol), 4,4 '-bis- methylamino benzophenone Ketone；2,4,6- trimethylbenzoyldiphenyl oxide, bis- (2,4,6- trimethylbenzoyl)-phenylphosphine oxides The existing general free radical type photoreaction initiators such as equal phosphine oxides class.
In addition, also can and with the peroxide of the induction heat such as the azo initiators such as azobis isobutyronitrile, benzoyl peroxide base Compound system free radical type initiator etc..Initiator can be used alone a kind, and also two or more may be used.
Solvent can enumerate solvent identical with aforementioned carboxylic acid's esterif iotacation step and aforementioned sour addition step.The equal solvent can be independent Or it is used in mixed way.
Nonreactive compound is the oligomer or resin of low or anergy the liquid of reactivity or solid-like, can Enumerate: (methyl) alkyl acrylate copolymer, epoxy resin, liquid polybutadiene, bicyclopentadiene derivative, saturated polyester are low Polymers, xylene resin, polyamine ester polymer, ketone resin, dially phthalate polymer (diallyl phthalate Resin, DAP resin), Petropols, rosin resin, fluorine system oligomer, poly- silicon oxygen system oligomer etc., but not limited to this.
It can be mentioned, for example silica, silica, calcium carbonate, calcium silicates, magnesium carbonate, magnesia, oxidations for inorganic filler Titanium, zirconium oxide, talcum, kaolinton, calcined clay, zinc oxide, zinc sulfate, aluminium hydroxide, aluminium oxide, glass, mica, sulfuric acid Barium, white alumina (alumina white), zeolite, silica balloon (silica balloon), glass balloon (glass Balloon) etc..In the equal inorganic fillers, it can be also coupled by addition silane coupling agent, titanate esters system coupling agent, aluminium system Agent, zirconate system coupling agent etc. and the methods of enable its reaction and there are the functional groups such as halogen radical, epoxy group, hydroxyl, mercapto.
It can be mentioned, for example benzoguanamine resin, polysilicone, low density polyethylene (LDPE), high-density polyethylenes for organic filler Alkene, polyolefin resin, ethylene/acrylic acid copolymer, polystyrene, acrylic copolymer, plexiglass, fluorine Resin, nylon 12, nylon 6/66, phenol resin, epoxy resin, amine ester resin, polyimide resin etc..
It can be mentioned, for example γ-glycidoxypropyltrimewasxysilane or γ-chloropropyl trimethoxies for silane coupling agent The silane coupling agents such as base silane, bis- (two (tritriacontyl)) the phosphite ester titanate esters of four (2,2- diene propoxy methyl -1- butyl), Bis- (dioctylphyrophosphoric acid esters) stretch the titanate esters such as ethyl titanate esters system coupling agent；The coupling of the aluminium systems such as acetyl alkoxy aluminum-diisopropoxide Agent；Zirconiums coupling agents such as acetylacetone,2,4-pentanedione/zirconium misfit object etc..
Tackifiers in resin combination of the invention, defoaming agent, levelling agent, plasticiser, antioxidant, ultraviolet can be used Light absorbers, fire retardant and dyestuff, as long as known used user, it can be in the hardenability, the resin spy that do not undermine resin combination Property range used without special system limit.
For obtaining resin combination of the invention, as long as above-mentioned each ingredient is mixed, mixed sequence, method It is not particularly limited.
Resin combination of the invention also includes containing the compound of the present invention (A), colorant (D) and adhesive resin (E) colored resin composition.
In colored resin composition of the invention, in 100 mass parts of whole solids point of colored resin composition, this hair The content ratio of bright compound (A) is usually 0.5 to 99 mass parts, preferably 5 to 50.
The purposes of visual colour filter of colorant (D) of the invention etc. and properly select color, material.Specifically, Toner can enumerate pigment, dyestuff and natural pigment, and above-mentioned colorant can be used alone or two or more is applied in combination.Wherein, For obtaining the point of brightness, the pixel high to when excitation purity, it is preferably selected from pigment and formed at least 1 organized of dyestuff Kind.
The preferred concrete example of above-mentioned organic pigment can be enumerated: colorant indexes entitled C.I. in (colour index) (C.I.) Paratonere (pigment red) 166, C.I. paratonere 177, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 254, C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58, C.I. pigment blue 15: 6, C.I. pigment blue 80, C.I. face Material Huang 83, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 180, C.I. pigment yellow 211, C.I. pigment tangerine 38, C.I. pigment Violet 23 etc..The preferred concrete example of inorganic pigment can be enumerated: carbon black, titanium are black etc..
Pigment is also preferably mordant pigment, specifically, can enumerate: triarylmethane based dye, dibenzo piperazine are muttered based dye Color lake (laking) person is carried out through isopolyacid (isopoly acid) or heteropoly acid (heteropoly acid).Triaryl first Methane series mordant pigment is for example disclosed in Japanese Unexamined Patent Publication 2011-186043 bulletin etc..It is that mordant pigment is for example taken off that dibenzo piperazine, which is muttered, It is shown in Japanese Unexamined Patent Publication 2010-191304 bulletin etc..
Based dye, triarylmethane based dye, cyanine based dye, anthraquinone system moreover, the above-mentioned preferred dibenzo piperazine of dyestuff is muttered Dyestuff, azo based dye etc..More specifically, it can enumerate: Japanese Unexamined Patent Publication 2010-32999 bulletin, Japanese Unexamined Patent Publication 2010- No. 254964 bulletins, Japanese Unexamined Patent Publication 2011-138094 bulletin, International Publication No. No. 10/123071 brochure, Japanese Unexamined Patent Publication 2011-116803 bulletin, Japanese Unexamined Patent Publication 2011-117995 bulletin, Japanese Unexamined Patent Publication 2011-133844 bulletin, Japan are special Open organic dyestuff described in 2011-174987 bulletin etc..
Pigment and dyestuff in the present invention can use individually or be used in mixed way two or more.
In the present invention, also pigment can be passed through recrystallization method, reprecipitation method, solvent ablution, sublimed method, heating in vacuum Method the methods of will be somebody's turn to do combination and refine and use.Moreover, pigment also can optionally be used its particle surface with resin modification. Moreover, organic pigment can grind (salt milling) processing by so-called salt miniaturize use for primary particle.The side of salt mill Method can be used for example, the revealed method of Japanese Unexamined Patent Publication 08-179111 bulletin.
When using pigment in the present invention as colorant, needed for visual and with dispersing agent, dispersing aid.Above-mentioned dispersing agent can Using for example: the dispersing agent appropriate such as cationic system, anionic system, nonionic system, but preferred polymers dispersing agent.It is specific and Speech, can enumerate acrylic acid series copolymer, Polyurethane, polyester, polyethyleneimine, polyallylamine etc..
The grade dispersing agents can be obtained by commercial system.For example, dispersant containing acrylic can be enumerated: Disperbyk- 2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (the above are BYK corporations) etc.； Amine ester system dispersant can be enumerated: Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (the above are BYK corporations), (Lubrizol share is limited by Solsperse76500 Corporation) etc.；Polyethyleneimine amine system dispersing agent can be enumerated: Solsperse24000 (Lubrizol limited liability company system) etc.； Polyester dispersant can be enumerated: Ajisper PB821, Ajisper PB822, Ajisper PB880, Ajisper PB881 (with Upper is Ajinomoto Fine-Techno limited liability company system) etc..
Moreover, above-mentioned pigment derivative is specific enumerable: copper phthalein green element, diketopyrrolo-pyrrole, quinoline yellow (quinophthalone) sulfonic acid etc..
100 mass of whole solids point for the content of colorant (D), relative to colored resin composition of the invention Part, colorant is usually 0.01 to 70 mass parts, more preferably preferred 0.5 to 50 mass parts, and in 1.0 to 40 mass parts It is more preferable in range.
In order to colorant (D) dispersion when dispersion stability, the present invention in adhesive resin (E) play dispersing agent, point The effect of dissipating auxiliary agent.Moreover, adhesive resin (E) is dissolved in when colored resin composition is used for photo-engraving process with colorant (D) Alkaline-based developer used in development treatment step when manufacturing colour filter is ideal.In order to form good fine pattern, Adhesive resin (E) is ideal with the sufficient hardening characteristics of Photoepolymerizationinitiater initiater, photopolymerization monomer etc. to have.Moreover, The constituent materials such as adhesive resin (E) selection and color material compound, Photoepolymerizationinitiater initiater, photopolymerization monomer, dispersible pigment dispersion Intermiscibility it is good, and colored resin composition will not occur be precipitated, agglutination etc. persons.Colored resin composition is used with ink-jet method When, because in alkali-soluble and having no special requirements, as long as therefore the selection adhesive resin good with the intermiscibility of other constituent materials (E).
Known resin can be used in adhesive resin (E), be preferably exemplified below with 1 or more carboxyl or hydroxyl Ethylene unsaturated monomer or other copolymerizable ethylene unsaturated monomers with aromatic hydrocarbyl, aliphatic alkyl Deng copolymer.Moreover, also can be used has epoxy group person and further addition propylene in the side chain of above-mentioned resin or end etc. The Epocryl of acid esters.Monomer of above-mentioned resin etc. individually can also combine two or more.
The aforementioned unsaturated monomer containing carboxyl that the raw material as adhesive resin can be used, it can be mentioned, for example: propylene The unsaturated monocarboxylics class such as acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, ethylacrylic acid, cinnamic acid；Maleic acid, Malaysia The unsaturated dicarboxylics such as acid anhydrides, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid (acid anhydride) class；3 yuan with On unsaturated polybasic carboxylic acid (acid anhydride) class, 2- (methyl) acryloyl-oxyethyl hexahydro phthalandione, 2- methacryloxyethyl- 2- hydroxypropyl phthalate ester and 2- acryloyl-oxyethyl -2- hydroxyethyl phthalandione etc..The equal ethylene insatiable hunger with carboxyl It can be used in mixed way individually or by two or more with monomer.
The aforementioned unsaturated monomer containing hydroxyl that the raw material as adhesive resin can be used, it can be mentioned, for example: (first Base) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 3- hydroxy propyl ester, (methyl) propylene Sour 4- hydroxybutyl, (methyl) acrylic acid 3- hydroxybutyl, (methyl) acrylic acid 5- hydroxyl pentyl ester, (methyl) acrylic acid 4- hydroxyl Pentyl ester, (methyl) acrylic acid 3- hydroxyl pentyl ester, the own ester of (methyl) acrylic acid 6- hydroxyl, the own ester of (methyl) acrylic acid 5- hydroxyl, (first Base) the own ester of acrylic acid 4- hydroxyl, (methyl) acrylic acid 5- hydroxy-3-methyl-pentyl ester, hexamethylene -1,4- dimethanol-mono- (methyl) Acrylate, (methyl) acrylic acid 2- (2- hydroxyethyl oxygroup) ethyl ester, glycerol monomethacrylate, polyethyleneglycol (first Base) hydroxyls such as acrylate, (methyl) acrylic acid 2- hydroxy methacrylates and poly- (ethylene glycol and 1,2-propylene glycol) monomethacrylates end Hold poly- alkylene glycols list (methyl) acrylate etc..The equal ethylene unsaturated monomer with hydroxyl can individually or by 2 kinds with On be used in mixed way.
Moreover, can be used the raw material as adhesive resin it is aforementioned other than unsaturated monomer it can be mentioned, for example benzene second Alkene, α-methylstyrene, o- vinyltoluene, m- vinyltoluene, p- vinyltoluene, o- chlorostyrene, m- chlorobenzene The aromatic ethenyl compounds such as ethylene, p- chlorostyrene, p-methoxystyrene；(methyl) methyl acrylate, (methyl) Ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) third Olefin(e) acid isobutyl ester, the second butyl ester of (methyl) acrylic acid, (methyl) tert-butyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylate, (first Base) benzyl acrylate, p-isopropyl phenoxy group ethylene glycol (methyl) acrylate, (methyl) acrylic acid 2- hydroxyl -3- benzene oxygen third Ester, o- phenyl phenol glycidol ether (methyl) acrylate, o- phenyl phenol (methyl) acrylate hydroxyethyl compound and (first Base) unsaturated carboxylate types such as phenoxyethyl acrylate；(methyl) acrylic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (first Base) acrylic acid 3-methyl cyclohexanol ester, (methyl) acrylic acid norbornyl ester, (methyl) acrylic acid norborny methyl esters, (methyl) third Olefin(e) acid phenyl norbornyl ester, (methyl) acrylic acid cyano norbornyl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid ice Piece ester, (methyl) acrylic acid menthol ester, (methyl) acrylic acid turnip ester, (methyl) acrylic acid Buddha's warrior attendant alkyl ester, (methyl) acrylic acid Dimethyladamantane ester, (methyl) acrylic acid tricyclic [5.2.1.02,6] decyl- 8- base ester, (methyl) acrylic acid tricyclic [5.2.1.02 ,6] decyl- 4- methyl ester, (methyl) acrylic acid ring last of the ten Heavenly stems ester, 2- (methyl) acryloyl-oxyethyl hexahydro phthalandione and (methyl) acrylic acid The alicyclic rings skeleton class such as t-butyl cyclohexyl methacrylate；Polyethyleneglycol (methyl) acrylate, (methyl) acrylic acid 2- hydroxy methacrylates and Poly- alkylene glycols list (methyl) esters of acrylic acid of the C-terminals such as poly- (ethylene glycol and 1,2-propylene glycol) monomethacrylates；Methoxyl group Polyethylene glycol monomethacrylate, laurel oxygroup polyethyleneglycol (methyl) acrylate, octyloxy polyethylene glycol poly- the third two Alcohol list (methyl) acrylate, Nonylphenoxy polyethylene glycol monoacrylate, Nonylphenoxy polypropylene glycol mono acrylic ester And poly- alkylene glycols list (methyl) acrylic acid of the alkyl ends such as allyloxy polyethylene glycol propylene glycol list (methyl) acrylate Esters；Acrylic acid 2- aminoethyl, methacrylic acid 2- aminoethyl, acrylic acid 2- amido propyl ester, methacrylic acid 2- amido The unsaturated carboxylic acids aminoalkyl esters such as propyl ester, acrylic acid 3- amido propyl ester and methacrylic acid 3- amido propyl ester；Acrylic acid contracting Water glyceride, glycidyl methacrylate, (methyl) acrylic acid 3,4- epoxy butyl ester, (methyl) acrylic acid (3,4- epoxy Cyclohexyl) the unsaturated carboxylic acids glycidol esters such as methyl esters and (methyl) acrylic acid 4- hydroxybutyl glycidol ether；Acetic acid second The generating vinyl carboxylates esters such as enester, vinyl propionate, vinyl butyrate and vinyl benzoate；Vinyl methyl ether, ethylene ethyl ether, The unsaturated ethers such as allyl glycidyl ether and methacrylic glycidol ether；Acrylonitrile, methacrylonitrile, α-chloropropene The vinyl cyanides compound such as nitrile and cyaniding Asia ethylene；Acrylamide, Methacrylamide, α-chloroacrylamide, N- phenyl Malaysia Acid imide, N- N-cyclohexylmaleimide, N- (methyl) acryloyl phthalimide, N- (2- hydroxyethyl) acrylamide, N- (2- Hydroxyethyl) unsaturated amides such as Methacrylamide and maleimide or unsaturated acyl imines；It is 1,3- butadiene, different Pentadiene and chlorine equality aliphatic conjugated diene class；And it is polystyrene, polymethyl acrylate, polymethyl methacrylate, poly- N-butyl acrylate, Vinalac 5920 and polysiloxanes (polysilicone) are equal to the end of polymer molecular chain Macromonomer class etc. with single acryloyl group or monomethacrylate acyl group.The equal unsaturated monomers can be individually or by 2 kinds It is used in mixed way above.
When manufacturing adhesive resin (copolymer), polymerization initiator is used.Wherein, used polymerization when synthetic copolymer It can be mentioned, for example α, α '-azo bis- (isobutyronitriles), 2,2 '-azos bis- (2- methylbutyronitriles), excessively sad uncle for the concrete example of initiator Butyl ester, di-tertiarybutyl, benzoyl peroxide base, methyl-ethyl-ketone peroxide etc..The use ratio of polymerization initiator For relative to 100 mass parts of whole monomer used in synthetic copolymer, polymerization initiator is 0.01 to 25 mass parts.Moreover, , it is preferable to use organic solvent, is had sufficient using monofunctional monomer, the polymerization initiator etc. for using when synthetic copolymer Dissolving power person.It can be used in the organic solvent of manufacture adhesive resin, can enumerate and aftermentioned colored resin composition of the invention The identical person of contained organic solvent.
Preferably 50 to 120 DEG C, particularly preferred 80 to 100 DEG C of reaction temperature when synthetic copolymer.Moreover, the reaction time is excellent It selects 1 to 60 hour, more preferable 3 to 20 hours.The preferred acid value of copolymer is 10 to 300 (mgKOH/g), and preferably hydroxyl valence is 10 To 200 (mgKOH/g).Developability can reduce when acid value or hydroxyl valence are 10 or less.The weight average molecular weight (Mw) of copolymer is preferred 2000 to 400000, more preferable 3000 to 100000.When weight average molecular weight is 2000 or less or 400000 or more, sensitivity And developability etc. can reduce.Also, the acid value in the present invention refers to the value that the method according to JIS K-2501 measures, hydroxyl valence refers to foundation The value of the method measurement of JIS K-1557, moreover, weight average molecular weight refers to according to the measurement result of GPC (gel permeation chromatography) with polyphenyl The calculated value of ethylene conversion.
Moreover, the polymer that the side chain of copolymer is further imported with unsaturated double-bond is also used as adhesive tree Rouge.It can be mentioned, for example: styrene, the vinyl phenol, acrylic acid, acrylic acid that makes maleic anhydride and can be closed with maleic anhydride The maleic anhydride portion of the copolymer of ester, acrylamide etc. and Hydroxyethyl Acrylate etc. have the acrylate of alcohol hydroxyl group, first The acrylate reactions with epoxy group such as base glycidyl acrylate, and half-esterification compound；And make acrylic acid, propylene The chemical combination that the hydroxyl of the copolymer of the acrylate with alcohol hydroxyl group such as acid esters and Hydroxyethyl Acrylate is reacted with acrylic acid Object etc..Moreover, amine ester resin, polyamide, polyimide resin, the polyester resin, (village Xin Zhong commercially available PSY-C1 also can be used Learn industry system) ACA-200M (DAICEL corporation), ORGA-3060 (Osaka organise length of schooling), AX3-BNX02 (Japanese catalyst System), UXE-3024 (Japanese chemical drug system), UXE-3000 (Japanese chemical drug system), ZGA-287H (Japanese chemical drug system), TCR-1338H (Japanese chemical drug system), ZXR-1722H (Japanese chemical drug system), ZFR-1401H (Japanese chemical drug system), ZCR-1642H (Japanese chemical drug System) it is used as adhesive resin.
Adhesive resin (E) can be independent in colored resin composition of the invention or two or more is used in mixed way.
It can be used the adhesive resin (E) in invention resin composition, the preferably aforementioned unsaturated monomer containing carboxyl, The copolymer of aforementioned unsaturated carboxylate type.The copolymer, such as PSY-C1 (village Xin Zhong chemical industry system) can be in taking on the market ?.
For the content ratio of the adhesive resin (E) of colored resin composition of the invention, combined in pigmentary resin Whole solids of object are divided in 100 mass parts, usually 0.5 to 99 mass parts, preferably 5 to 50 mass parts.Adhesive resin (E) When content is not up to 0.5 mass parts, alkali-developable can be reduced, and have the region other than the part for forming pixel that dirty, residual film occurs The problems such as situation.
In colour filter colored resin composition of the invention, the viscosity of colored resin composition can also be reduced, changed For the purpose of workability when kind colored resin composition coating and and use organic solvent.As organic solvent person, it is preferable to use right There is sufficient dissolving power in adhesive resin, Photoepolymerizationinitiater initiater of the constituent of colored resin composition etc., for closing Monofunctional monomer used in composite adhesives resin, polymerization initiator etc. also have sufficient dissolving power person.Moreover, also preferably using Dispersion stability person can also be kept even if when being made pigment dispersion.
The concrete example of organic solvent containing colored resin composition of the invention can be enumerated: benzene, toluene and dimethylbenzene etc. Benzene class；The Sai Lusu classes such as methyl Sai Lusu, ethyl Sai Lusu and butyl Sai Lusu；Methyl Sai Lusu acetic acid esters, ethyl Sai Lusu The Sai Lusu acetate esters such as acetic acid esters and butyl Sai Lusu acetic acid esters；Propylene glycol monomethyl ether, propylene glycol monoethyl The propylene-glycol monoalky lethers acetate esters such as acetic acid esters and glycol monobutyl ether acetic acid esters；Methoxy methyl propionate, methoxy propyl The propionic acid esters such as acetoacetic ester, ethoxypropanoate, ethoxyl ethyl propionate；Methyl lactate, ethyl lactate and butyl lactate etc. Lactic acid ester；The diethylene glycols class such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether；Methyl acetate, ethyl acetate and second The acetate esters such as acid butyl ester；The ethers such as dimethyl ether, Anaesthetie Ether, tetrahydrofuran and dioxane；Acetone, methyl ethyl ketone, The ketones such as methyl butyl ketone and cyclohexanone；And alcohols such as methanol, ethyl alcohol, butanol, isopropyl alcohol, diacetone alcohol and benzylalcohol etc., But not limited to this.
Organic solvent can be used singly or two or more kinds in combination in colored resin composition of the invention.It is just of the invention For organic solvent usage amount in chromoresin composition, whole solids relative to colored resin composition divide 100 mass parts, Usually 10000 below the mass, preferably 100 to 1000 mass parts.
Colored resin composition of the invention can also contain Photoepolymerizationinitiater initiater and/or hardening accelerator.Pigmentary resin group The Photoepolymerizationinitiater initiater that contains of object is closed, preferably for from projecting generally as extra-high-pressure mercury vapour lamp used in exposure light source Ultraviolet light has sufficient sensitivity person, and the light of free-radical polymerised optical free radical initiator, ionic hardening property also can be used Any one of acid producing agent or photobase generator etc..Moreover, can be used in combination title in order to be hardened with less exposure energy Make the polymerization accelerant ingredient of sensitizer.The concrete example of Photoepolymerizationinitiater initiater can be enumerated: dibenzoyl (benzil), benzoin Ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3,3 '-dimethyl -4- methoxy benzophenones, Benzoylbenzene Formic acid, the carboxylate of benzoyl benzoic acid, 4- benzoyl -4 '-dimethyl diphenyl sulfide, benzyl dimethyl ketal, 2- fourth Oxygroup ethyl -4- methylamino benzoic ether, chlorothiaxanthenone, methyl thioxanthone, ethyl thioxanthone, isopropyl thioxanthone anthracene Ketone, dimethyl thioxanthone, diethyl thioxanthone, diisopropyl thioxanthone, dimethylaminomethyl benzoic ether, 1- (4- dodecyl phenyl) -2- hydroxy-2-methyl propane -1- ketone, 1- hydroxycyclohexylphenylketone, 2- hydroxy-2-methyl -1- phenyl Propane-1- ketone, 1- (4- isopropyl phenyl)-2- hydroxy-2-methyl propane-1- ketone, methyl benzoylformate, 2- methyl-1- (4- methyl thio phenyl) -2- morpholinopropane -1- ketone, 2- benzyl -2- dimethyl amido -1- (4- morpholino phenyl)-butanone - 1, bis- (trichloromethyl) -6- (4- the methoxyphenyl) -1,3,5- s-triazine of 2,4-, 2,4,6- three (trichloromethyl) -1,3,5- are equal Bis- (trisbromomethyl) -6- (4 '-the methoxyphenyl) -1,3,5- s-triazine of triazine, 2,4-, 2,4,6- three (trisbromomethyl) -1,3, Bis- (the trichloromethyl) -6- of 5- s-triazine, 2,4- (1,3- benzo dioxolane -5- base) -1,3,5- s-triazine, hexichol first Ketone, benzoyl benzoic acid, 1- (4- phenylsulfartyl phenyl) butane -1,2- diketone -2- oxime-O- benzoic ether, 1- (4- methyl sulphur Base phenyl) butane -1,2- diketone -2- oxime-O- acetic acid esters, 1- (4- methylsulfanylphenyl) butane -1- ketoxime-O- acetic acid esters, 4, 4 '-bis- (diethyl amido) benzophenone, P- dimethyl amido isoamyl benzoate, P- dimethyl amine yl benzoic acid ethyl ester, 2,2 '-bis- (O- chlorphenyl) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxalines, diazo naphthoquinone series initiators；With it is commercially available Kayacure DMBI、Kayacure BDMK、Kayacure BP-100、Kayacure BMBI、Kayacure DETX-S、 Kayacure EPA (being all Japanese chemical drug system), Darocur 1173, Darocur 1116 (being all Merck Japan system), Irgacure 907 (BASF Japan system), Irgacure 369 (BASF Japan system), Irgacure 379EG (BASF Japan system), Irgacure OXE-01 (BASF Japan system), Irgacure OXE-02 (BASF Japan system), Irgacure PAG103 (BASF Japan system), TME- tri- (three and CHEMICAL system), bisglyoxaline (dark fund chemical conversion system), STR-110, STR-1 (being all RESPE CHEMICAL system) etc., but not limited to this.
In colored resin composition of the invention, Photoepolymerizationinitiater initiater can be used singly or two or more kinds in combination.Relative to 100 mass parts of whole solids of colored resin composition point, the content of Photoepolymerizationinitiater initiater is usually 0.5 to 50 mass parts, excellent Select 1 to 25 mass parts.
Colour filter of the invention promotes ionic hardening reaction to urge with the hardening accelerator that colored resin composition contains Agent, it can be mentioned, for example: the heterocyclic compound containing N such as 1 grade to 3 grades of amine or imidazoles, acid anhydrides etc..
The concrete example of amine can be enumerated: triethylamine, triethanolamine, Japanese chemical drug product Kayahard A-A, Kayabond C-100, Kayabond C-200S, Kayabond C-300S etc..
The concrete example of imidazoles can be enumerated: the Curezol 2MZ-H of four countries' chemical conversion industry product, Curezol C11Z, Curezol C17Z、Curezol 1,2DMZ、Curezol 2E4MZ、Curezol 2PZ、Curezol2P4MZ、Curezol 1B2MZ、Curezol 1B2PZ、Curezol 2MZ-CN、Curezol C11Z-CN、Curezol 2E4MZ-CN、Curezol 2PZ-CN、Curezol C11Z-CNS、Curezol2PZCNS-PW、Curezol 2MZ-A、Curezol C11Z-A、Curezol 2E4MZ-A、Curezol 2MA-OK、Curezol 2PZ-OK、Curezol 2PHZ-PW、Curezol 2P4MHZ-PW、 Curezol TBZ, Curezol 2PZL-T, Curezol VT, Curezol SFZ etc..
The concrete example of acid anhydrides can be enumerated: maleic anhydride, succinic anhydride, anhydride phthalic acid, tetrahydro anhydride phthalic acid, benzenetetrahydride, connection Benzene tertacarbonic acid's dianhydride, Kayahard MCD of Japanese chemical drug product etc..In the equal acid anhydrides, the preferred imidazoles of hardening accelerator, just For reactivity, more preferable Curezol 1B2PZ, Curezol2PZ, Curezol 1B2MZ and Curezol 2E4MZ.
Relative to 100 mass parts of whole solids point of colored resin composition, the content of hardening accelerator is usually 0.01 To 50 mass parts, preferably 0.05 to 20 mass parts.When the content of hardening accelerator is few compared with 0.01 mass parts, there is hardenability to reduce it Anxiety when more than 50 mass parts, there is the anxiety for saving stability variation.
When low for the dissolubility of the resin component of colorant (D), can and it be divided with dispersing agent, dispersing aid etc. It dissipates, this waits dispersing agents etc. that the pigment system dispersing agent and resin system dispersing agent, surface for having good adsorptivity to pigment can be used Activating agent etc..As pigment system dispersing agent, the commonly known method for mixing the sulfonated bodies of pigment or its metal salt with pigment is mixed Method etc. of the conjunction for aminomethyl derivative.Resin system dispersing agent also has non-polar nonionic system, and is typically attached The macromolecule resin of acid value, amine value with good pigment adsorption etc. can be enumerated: acrylic resin, polyurethane resin, polynary Carboxylic acid, polyamide, polyester resin etc..The commercially available product of pitch dispersant it can be mentioned, for example: ED211 (this chemical conversion of nanmu system), Ajisper PB821 (Ajinomoto Fine-Techno system), Solsperse71000 (Avecia system), Disperbyk- 2001 (BYK Japan systems) etc..
Moreover, when using acid dyes, basic dye, it is known to by make the dye class and organic amine compound (such as N-propyl amine, ethylhexyl propionic acid amine etc.) it reacts and is modified as amine salt dyestuff or makes its sulfonic group and same organic amine chemical combination Object reacts and is modified as having dyestuff of sulfoamido etc. and becoming soluble in organic solvent, and the side with organic solvent Method.The grade can be also used in combination through the modified dyestuff of amine with colored resin composition of the invention.Can the modified dyestuff of amine, in colorant rope In drawing, it can be mentioned, for example, solvent blue 2,3,4,5,6,23,35,36,37,38,43,48,58,59,67,70,78,98,102, 104；Blue 7；Acid blue 80,83,90；The solvent purple 8 of cudbear, 9；Purple 4,5,14；Alkaline purple 10 etc..
Colored resin composition of the invention, can be by compound (A), colorant (D), adhesive resin (E), other Additive of anticipating is mixed by dissolvers, homogeneous mixer etc. to be manufactured.The dyestuff that colorant (D) is pigment, dissolubility is low When, after becoming dispersion by dispersion machines such as coating oscillators (Paint Shaker) using dispersing agent appropriate, hybridization Close object (A), dispersion, adhesive resin (E) and obtain colored resin composition.
In colored resin composition of the invention, various additives can be further added depending on needed for, such as: filler, table Face activating agent, close adhesion promotor, antioxidant, ultraviolet absorbing agent, goes to coagulate agent etc. thermal polymerization inhibitor.Moreover, this hair Bright colored resin composition can also remove foreign matter etc. after its modulation and carry out secondary filter with filter etc..
It uses the colour filter of colored resin composition of the invention coloring cured film (following also known as " coloring cured film ") Manufacturing method, can mainly enumerate photo-engraving process, ink-jet method, the former uses the excellent sense of the developability containing Photoepolymerizationinitiater initiater Photosensitiveness colored resin composition, the latter are not necessarily required to Photoepolymerizationinitiater initiater, use the thermosetting containing hardening accelerator Chromoresin composition.
Moreover, also can and use Photoepolymerizationinitiater initiater such as when with ink-jet method using colored resin composition of the invention With thermal polymerization.Thermal polymerization is to have azo compound, organic peroxide system, it can be mentioned, for example: 2,2 '-is even Nitrogen double isobutyronitrile, 2,2 '-azos bis- (2,4- methyl pentane nitriles), 2,2 '-azos bis- (2- methylbutyronitriles), peroxidating two-tertiary fourth Base, dibenzoyl peroxide, peroxide neodecanoic acid isopropyl phenyl ester etc..
Also, and when with thermal polymerization, Photoepolymerizationinitiater initiater and thermal polymerization it is total, as long as being used in above-mentioned Amount in the content range of Photoepolymerizationinitiater initiater.
Secondly the method that explanation colours cured film by colored resin composition modulation of the invention.Firstly, by of the invention Colored resin composition is using the methods of spin-coating method, rolling method, slit and method of spin coating, die coating method, stick coating method so that film thickness It is coated on the substrates such as glass substrate, silicon substrate as 0.1 to 20 μm, the mode preferably as 0.5 to 5 μm.Then, depending on needed for In in relief groove, with usually in 23 to 150 DEG C, 1 to 60 minute, be preferable over the drying conditions of 60 to 120 DEG C, 1 to 10 minute into Row is dried under reduced pressure, then with heating plate or dustless baking oven etc. carry out prebake processing and are film-made.Secondly, general pre- by photo-engraving process warp Fixed mask pattern irradiation radioactive ray (it can be mentioned, for example: electron beam and ultraviolet light, preferably ultraviolet light), and with surfactant water The mixed aqueous solution of solution, alkaline aqueous solution or surfactant and alkaline agent develops.Visualization way can be enumerated: infusion process, Spray-on process, spray (shower) method, covering liquid (puddle) method, ultrasonic development method etc., the methods of being somebody's turn to do also can any combination.Pass through Development remove non-irradiation unit, after being eluted with water, usually with 130 to 300 DEG C, 1 to 120 minute, preferably with 150 to 250 DEG C, 1 to Roasting is handled after 30 minutes conditions carry out, and obtains coloring cured film of the invention.
Among the above, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether etc. can be used to be used as surfactant.Moreover, Sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, diethanol amine, tetramethyl ammonium hydroxide etc. can be used in alkaline agent.In the present invention In, it is preferable to use the aqueous solution comprising both alkaline agent and surfactant.Development is usually with 10 to 50 DEG C, 30 to 600 seconds, preferably 20 to 40 DEG C, 30 to 120 seconds treatment conditions carry out.
Coloring cured film of the invention can be used as being suitble to liquid crystal display device, organic el display or digital camera The colour filter of solid state photo element etc. Deng used in.Colour filter of the invention, it is of the invention comprising being modulated according to foregoing manner Colour the pixel of cured film.
The hardening thing of colored resin composition of the invention, can be used in suitable liquid crystal display device, organic el display, Or the colour filter of the patterned blue pixel of solid state photo element etc. used in digital camera etc., the present invention also include Equipped with colour filter person etc..
Liquid crystal display device of the invention, such as it is made as sequentially layered product: backlight, polarizing film, show electrode, liquid The construction of crystalline substance, oriented film, common electrode, colour filter of the invention, polarizing film etc..Moreover, organic el display is in multilayer Organic illuminating element up or down either side formed colour filter and make.Solid state photo element, such as by being provided with Transmission electrode, near-infrafed photodiodes Silicon Wafer (wafer) on, color-filter layer of the invention is set, and lamination lenticule and make.
Display element of the invention has colour filter person of the invention.Display element can be enumerated: color liquid crystal display device, Organic EL display element, Electronic Paper etc..The color liquid crystal display device for having colour filter of the invention can be that transmission-type also can be It is reflective, it can be construction appropriate.For example, can in from the driving different substrate of substrate configured with thin film transistor (TFT) (TFT) Upper formation colour filter, and make driving substrate be formed with the substrate of colour filter across liquid crystal layer be in it is opposite to construction, also may be used Make further in being formed with the substrate of colour filter on the surface of the driving substrate configured with thin film transistor (TFT) (TFT) and be formed with The substrate of ITO (mixing indium tin oxide target) electrode across liquid crystal layer be in it is opposite to construction.The construction of the latter can be improved particularly aperture opening ratio, Have the advantages that so-called become clear and the liquid crystal display element of high-fineness.
(embodiment)
Hereinafter, present invention will be further described in detail through examples, but the present invention is not limited to the embodiments such as this.Moreover, If being not particularly limited in embodiment, part indicates mass parts.Also, each physics value in embodiment is measured with following methods.
(1) it epoxide equivalent: is measured according to method described in JIS K7236:2001.
(2) it hardness: is measured according to method described in JIS K5600-5-4:1999.
(3) it refractive index: is measured according to method described in JIS K7142:1996.
Then, the calculating of following liquid phase refractive index is dilute with solvent in such a way that resulting compound concentration is changed at 3 points Sample is released and be made, its liquid phase refractive index is measured at 3 points, calculates the liquid phase refractive index of compound itself.Moreover, D line is 589nm.Also, the present invention is not limited in any way with following embodiment.
The synthesis of 1 epoxy resin (a) of synthesis example
Nitrogen flushing (nitrogen gas purge) is implemented in the flask with thermometer, cooling tube, blender, simultaneously N- phenyl phenolphthalein (SABIC PPPBP, 99% or more purity) 256g, epoxychloropropane 842g, methanol of phenolic compounds is added 180g, by warming-in-water to 75 DEG C.After time-consuming 90 minutes when temperature is more than 65 DEG C inside add flaky sodium hydrate 21g by several times, Then at 70 DEG C carry out 1 hour after react.After the reaction was completed, clean with water 300g it is secondary, by salt generated etc. removal after, It (is stirred to 70 DEG C, -0.08MPa to -0.09MPa), while with the epoxy chloropropionate of 3 hours distillation surpluses under heating decompression Alkane etc..Dissolution methyl iso-butyl ketone (MIBK) 600g is added in residue, is warming up to 70 DEG C.The hydroxide of 30 mass % is added under stiring Sodium water solution 26g is washed after carrying out reaction 1 hour until washing water is in neutrality.Solution after washing is steamed by rotation Device is sent out in depressurizing lower distillation methyl iso-butyl ketone (MIBK) etc., obtains target epoxy resin 305g.The epoxide equivalent of gained epoxy resin is 266g/eq., softening point are 89 DEG C, ICI melt viscosity be 0.42Pas (150 DEG C), in room temperature be solid.
The synthesis of embodiment 1-1 epoxy carboxylic acids ester compounds (A-1)
The addition toluene 76.8g as retarder thinner, 1 institute of synthesis example in the 1L flask with agitating device, return pipe Epoxy resin 135.6g (0.6eq.), as the 2,6- di-t-butyl-p-Cresol 0.53g of thermal polymerization inhibitor, conduct There is the acrylic acid 43.3g (0.6eq.) of the monocarboxylic acid compound of ethylene unsaturated group in molecule, as catalysts Triphenylphosphine 0.53g, in 98 DEG C react 24 hours, measure acid value be 1.7mgKOH/g, then completion react.By above-mentioned Step obtains the resin solution of 70 mass %.
Then, toluene 250g is added in the solution, is cleaned 3 times with water 100g, organic layer is concentrated under reduced pressure, obtains following light Compound (A-1) 161.0g of yellow coloured resin shape.
The physical property of the compound of the present invention (A-1) is as shown below.
Liquid phase refractive index (D line, 25 DEG C) 1.60
1H-NMR
3.58ppm=2H, 3.96-4.42ppm=10H, 5.58-5.60ppm=2H, 6.04-6.6.05ppm=2H, 6.26-6.27ppm=2H, 6.86-6.88ppm=4H, 7.12ppm=1H, 7.15-7.19ppm=6H, 7.42-7.43ppm= 2H, 7.57-7.58ppm=1H, 7.80-7.81ppm=2H, 7.91ppm=1H
The synthesis of embodiment 1-2 epoxy carboxylic acids ester compounds (A-2)
In the 1L flask with agitating device, return pipe, toluene 80.2g as retarder thinner, 1 institute of synthesis example are added Epoxy resin 135.6g (0.6eq.), as the 2,6- di-t-butyl-p-Cresol 0.56g of thermal polymerization inhibitor, conduct The methacrylic acid 51.6g (0.6eq.) of monocarboxylic acid compound in molecule with ethylene unsaturated group, it is urged as reaction The triphenylphosphine 0.56g of agent reacts 24 hours in 98 DEG C, and measured acid value is 2.1mgKOH/g, completes reaction then.Pass through Above-mentioned steps obtain the resin solution of 70 mass %.
Then, toluene 250g is added in the solution, is cleaned 3 times with water 100g, organic layer is concentrated under reduced pressure, obtains faint yellow Compound (A-2) 168.5g of resin-like.With1The construction of H-NMR measurement confirmation compound.
The physical property of the compound of the present invention (A-2) is as shown below.
Liquid phase refractive index (D line, 25 DEG C) 1.59
1H-NMR
2.01ppm=6H, 3.58ppm=2H, 3.96-4.42ppm=10H, 6.39-6.40ppm=2H, 6.47- 6.48ppm=2H, 6.86-6.88ppm=4H, 7.12ppm=1H, 7.15-7.19ppm=6H, 7.42-7.43ppm=2H, 7.57-7.58ppm=1H, 7.80-7.81ppm=2H, 7.91ppm=1H
The synthesis of polycarboxylic compounds (B)
The amount described in resulting epoxy carboxylic acids' ester compounds (A-1) addition table 1 of embodiment 1-1 is used as multi-anhydride (c) tetrahydro anhydride phthalic acid, and the toluene as solvent is added in a manner of being divided into 65 mass % using the solid of reaction solution.Later, It is reacted 10 hours in 100 DEG C, obtains polycarboxylic compounds' (B-1) solution and polycarboxylic compounds (B-2) solution.Then, The solution is cleaned 3 times with water 100g, organic layer is concentrated under reduced pressure, obtains the polycarboxylic compounds (B) of light yellow resin shape.Table 1 setting acid value, it is intended that the ideal solid of last resulting polycarboxylic compounds divides acid value.Using multi-anhydride (c) to reach At the calculation amount of the setting acid value.
[table 1]
Compare synthesis example 1 (synthesis of compound (H-1)) compared with Japanese Unexamined Patent Publication 9-272707 bulletin
It implements nitrogen in the flask with thermometer, cooling tube, blender and rinses, while by o- phenyl phenol (tri- light of O-PP Limited liability company's system) 170g, epoxychloropropane 370g, methanol 74g addition dissolution.It is further heated to 70 DEG C, time-consuming 90 points Clock after addition flaky sodium hydrate 41g, reacts 60 minutes by several times then at 70 DEG C.After the reaction was completed, it carries out cleaning two with water 200g It is secondary, after removing salt generated etc., (it is stirred to 70 DEG C, -0.08MPa to -0.09MPa), while with 3 under heating decompression The epoxychloropropane etc. of hour distillation surplus.Dissolution methyl iso-butyl ketone (MIBK) 450g is added in residue, is warming up to 70 DEG C.It is stirring The lower sodium hydrate aqueous solution 10g that 10 mass % are added is washed after carrying out reaction 1 hour until washing water is in neutrality.It will Solution after washing, in depressurizing lower distillation methyl iso-butyl ketone (MIBK) etc., obtains target epoxy resin 217g by rotary evaporator.Institute Epoxy resin epoxide equivalent be 233g/eq., in room temperature be liquid.
In the 1L flask with agitating device, return pipe, resulting epoxy resin 139.8g (0.6eq.), conduct are added The 2,6- di-t-butyl-p-Cresol 0.55g of thermal polymerization inhibitor, as in molecule with ethylene unsaturated group single carboxylic Acrylic acid 43.3g (0.6eq.), the triphenylphosphine 0.55g as catalysts of acid compound (b) are small in 98 DEG C of reactions 30 When, measured acid value is 2.4mgKOH/g, completes reaction then.The chemical combination of clear pale yellow chromoresin shape is obtained through the above steps Object (H-1) 180g.
The liquid phase refractive index of embodiment, the compound of comparative example and compound (H-1), (I-1) and (I-2) is shown in table 2. Also, the calculating of liquid phase refractive index, is that sample is diluted and be made with solvent in such a way that resulting compound concentration is changed at 3 points, Its liquid phase refractive index is measured at 3 points, calculates the liquid phase refractive index of compound itself.As a result it is shown in table 2.
[table 2]
A-1 A-2 B-1 B-2 H-1 I-1 I-2
Liquid phase refractive index 1.60 1.59 1.56 1.58 1.58 1.58 1.61
Note)
Measurement device: multi-wavelength Abbe refractometer DR-M2Atago limited liability company system
Measure wavelength: 589nm (D line)
(I-1) OPP-1: NIPPON PHARMACEUTICAL CO., LTD's system (terminal acrylic of the ethylene oxide adduct of 2- phenyl phenol Acid esters compound
(I-2) the OGSOL EA-200:Osaka Gas Chemicals limited liability company system (ethylene oxide of bisphenol fluorene The terminal acrylate compound of addition product)
Embodiment 2, the allotment of 2 resin combination of comparative example and test film are made
By compound synthesized by embodiment 1 (A-1, A-2, B-1, B-2) and 1 resulting compound (H-1) of comparative example with And (embodiment 2-1 to 2-4 and comparative example 2-1 are extremely to form the resin combination deployed shown in table 3 by (I-1), (I-2) 2-3；Blending amount (g)) using bar coater (No.20) be coated on easily then handle polyester film (Japan spin limited liability company's system: A-4300,188 μm of film thickness).Be coated with resin combination polyester film placed 1 minute in 80 DEG C of drying oven after, in The high-pressure mercury-vapor lamp that 120W/cm is used under air gas environment is shone by the distance of lamp height 10cm with 5m/ minutes transporting velocitys Ultraviolet light is penetrated, the film with hardening epithelium (10 to 15 μm) is obtained.
[table 3]
Note)
* 1:PET-30: NIPPON PHARMACEUTICAL CO., LTD's system, KAYARAD PET-30 (new penta tetrol triacrylate/ The mixture of new penta tetra-acrylate): (B-5)
* 2:Irg.184 (IRGACURE 184): Ciba Specialty Chemicals system (1- hydroxycyclohexylphenyl Ketone)
* 3:MEK: methyl ethyl ketone
Test example
For embodiment 2 or the resulting film of comparative example 2, following project evaluation results are shown in table 4.
(pencil hardness)
According to JIS K 5400, with the pencil hardness of pencil scratch measurement coating film.Also that is, there is hardening in measurement With 45 degree of angle on the polyester film of epithelium, by pencil, the weight bearing of 1kg is bestowed from above and scratches 5mm or so, and confirm damage Situation.5 measurements are carried out, undamaged number is calculated.
Assessment 5/5:5 times in 5 times it is all not damaged
0/5:5 all generation damage
(marresistance)
In bestowing 200g/cm on steel wool #00002Weight bearing, make steel wool round-trip 10 times, with visual judgement damage shape Condition.
Assessment 5: it does not observe damage completely
Assessment 4: 1 to 5 damage of generation is observed
Assessment 3: 6 to 50 damages of generation are observed
Assessment 2: 51 to 100 damages of generation are observed
Assessment 1: painting film stripping is observed
(close adhesion)
According to JIS K 5400, vertical/horizontal each 11 cut marks are cut out with the interval of 1mm in film surface, are made 100 chesses Disk lattice.Record by adhesive tape close adhesion behind its surface, it is unstripped and remain when at a dass stripping adhesive tape Grid number.
(warpage)
The polyester film with hardening epithelium that will be measured is cut into 5cm × 5cm, and it is small to place 1 in 80 DEG C of drying ovens When after, return to room temperature.The height for measuring 4 sides floated respectively on horizontal platform, using average value as measured value (unit: mm).At this point, the warpage of substrate itself is 0mm.
(appearance)
With the state of the crack, albefaction, the atomization that visually judge surface etc..
Assessment zero: good
△: a little crack is generated
×: generate significant crack
[table 4]
Test sample Pencil hardness 2H It is scratch resistance Close adhesion Warpage Appearance
Embodiment 2-1 5/5 5 100 6 ○
Embodiment 2-2 5/5 5 100 5 ○
Embodiment 2-3 3/5 3 100 3 ○
Embodiment 2-4 5/5 5 100 5 ○
Comparative example 2-1 1/5 3 85 5 ○
Comparative example 2-2 0/5 1 100 5 ○
Comparative example 2-3 5/5 3 60 10 ○
The hardening thing of resin combination of the invention and comparative example 2 are compared, with regard to hardness, marresistance, close viscous It is more excellent for conjunction property, and depth of camber is degree identical with comparative example 2 or low compared with comparative example 2.It is of the invention known to accordingly The curing shrinkage of resin combination is few compared with the curing shrinkage of comparative example 2.
The modulation and assessment of 3 active energy beam constrictive type optics resist of embodiment
Using the resulting polycarboxylic compounds of 20g embodiment 1-3 (B-1), 5g as the free radical of reactive compounds (C) New penta tetrol, six acrylate of the two of the monomer of response type, IRGACURE of the 1.5g as ultraviolet light response type Photoepolymerizationinitiater initiater 184, which are mixed and heated dissolution, obtains optics composition.
The optics is coated in such a way that film thickness when making dry becomes 20 microns by manual applicator with composition On quartz plate, make solvent seasoning with electric dry oven with 80 DEG C, 30 minutes.After drying, mask pattern is covered from the top of painting object, is led to The ultraviolet light vertical exposure device (ORC production is made) for having high-pressure mercury-vapor lamp is crossed, irradiation exposure dose is 1000mJ/cm2's Ultraviolet light is hardened, and optics material is obtained.Then, spraying 1 mass % aqueous sodium carbonate, makes unexposed portion dissolve and show Shadow.Its result can form pattern, indicate that polycarboxylic compounds (B) of the invention have resist adaptive.
Compare synthesis example 2 (synthesis of compound (H-2))
In the 1L flask with agitating device, return pipe, the bis- [4- of toluene 89.6g, 9,9- as retarder thinner are added (glycidoxypropyl) phenyl] -9H- fluorenes (Osaka Gas Chemicals limited liability company system: PG-100) 162.5g (0.6eq.), as thermal polymerization inhibitor 2,6- di-t-butyl-p-Cresol 0.63g, as in molecule have ethylene Acrylic acid 46.5g (0.6eq.), the triphenylphosphine 0.63g as catalysts of the monocarboxylic acid compound of unsaturated group, in 98 DEG C are reacted 24 hours, and measured acid value is 0.3mgKOH/g, complete reaction then.Obtain 70 mass %'s through the above steps Resin solution.
Then, toluene 250g is added in the solution, is cleaned 3 times with water 100g, organic layer is concentrated under reduced pressure, obtains faint yellow Bis- [4- [2- hydroxyl -3- (acryloyl-oxy) propoxyl group] phenyl] -9H- fluorenes (H-1) 189.0g of the 9,9- of resin-like.(H-1) liquid Phase refractive index with1H-NMR is as follows.
Liquid phase refractive index (D line, 25 DEG C): 1.61
1H-NMR
3.95ppm=2H, 4.16ppm=2H, 4.20ppm=2H, 4.41ppm=2H, 4.69ppm=2H, 5.77ppm= 2H, 5.83ppm=2H, 6.12ppm=2H, 6.41ppm=2H, 6.85ppm=4H, 7.18ppm=4H, 7.28ppm=2H, 7.38ppm=2H, 7.55ppm=2H, 7.90ppm=2H.
The synthesis of colorant (D1)
According to the synthesis example 1 of Japanese Unexamined Patent Publication 2014-153441, cyanine based dye (D1) shown in following formula (2) is synthesized.
The synthesis of colorant (D2)
According to the synthesis example 2 of Japanese Unexamined Patent Publication 2013-050707, synthesizes dibenzo piperazine shown in following formula (3) and mutter based dye (D2)。
Embodiment 4,5, comparative example 3, the allotment of 4 resin combinations and hardening thing are made
By the compound (A-1) of embodiment 1-1 and compare 2 resulting compound (H-2) of synthesis example and (I-2) according to table 5 The deployed resin combination of shown composition (embodiment 4,5 and comparative example 3-1 to 3-3,4-1 to 4-3；Blending amount (g)) respectively It is coated on glass substrate, prebake was carried out with 80 DEG C × 10 minutes conditions.Then, across having figuratum light shield for resulting painting Film exposure, is exposed the hardening of part.Thereafter, developed with the alkaline aqueous solution containing surfactant, eluted with water Afterwards, with 230 DEG C, progress heat hardening in 30 minutes.Its result obtains the assessment substrate with colored pattern.
[table 5]
Note)
DPHA: NIPPON PHARMACEUTICAL CO., LTD KAYARAD DPHA (two new penta tetrol, five acrylate and two new penta Six acrylate mixture of tetrol)
Colorant (D1): cyanine based dye
Colorant (D2): dibenzo piperazine is muttered based dye
Adhesive resin (E-1): PSY-C1 (village Xin Zhong chemical industry system)
NMP:N- methylpyrrole pyridine ketone
Irg.369 (IRGACURE 369): Ciba Specialty Chemicals system (1- hydroxycyclohexylphenylketone)
Using the assessment substrate, the assessment of developability, resolution ratio and the close adhesion to substrate, resulting figure are carried out It is 5 μm that case, which has line & spacing,2Analyticity, and do not confirm residue, the peeling of pixel etc..Therefore, pigmentary resin of the invention Composition is suitable for requiring the high-resolution colour filter of solid state photo element.
Test example
For embodiment 4,5, comparative example 3,4 resulting hardening things, the assessment result of following projects is shown in table 6.
(heat resistance: the color difference after rear roasting)
The light splitting penetrance of the front and back measurement aforementioned evaluations substrate of the roasting processing after being carried out with 230 DEG C, 30 minutes, calculates color Poor (△ Eab) is simultaneously assessed.Smaller color difference is more excellent.
(solvent resistance: the color difference of NMP dipping front and back)
The N- methylpyrrole pyridine ketone 15 that the aforementioned evaluations substrate that processing is roasted after 230 DEG C, 30 minutes is impregnated in 25 DEG C is divided Clock, the light splitting penetrance of measurement dipping front and back, calculates color difference (△ Eab) and is assessed.
[table 6]
By the hardening thing for using cyanine based dye, (embodiment 4, comparative example 3-1 to 3-3) are compared, and this case is invented hard Compound compared with comparative example, heat resistance is especially excellent, solvent resistance be also comparative example it is same more than.Moreover, hexichol will be used And the mutter hardening thing (embodiment 5, comparative example 4-1) of based dye of piperazine is compared, the hardening thing of this case invention is for heat resistance It is same therewith.It is muttered in the hardening thing of based dye using dibenzo piperazine, it is same with regard to used epoxy carboxylic acids' ester compounds and (A-1) For comparative example 4-2 to 4-3 with aromatic ring, heat resistance/solvent resistance is worse compared with embodiment 2.
(industrial availability)
The compound of the present invention (A) can be used in hardened with active energy beam, for high heat resistance and high refractive index and Heat resistance/excellent solvent resistance simultaneously has the photosensitive material of the transparency and the various fields of color filter materials.

Claims (12)

1. a kind of epoxy carboxylic acids' ester compounds have for epoxy resin shown in the following general formula (1) and simultaneously ethylene in molecule Property unsaturated group and carboxyl compound reaction obtained by epoxy carboxylic acids' ester compounds；
In general formula (1), R1For any one of the alkoxy of alkyl, carbon number 1 to 6 selected from hydrogen atom, carbon number 1 to 6, a indicates to replace Base R1Number, be 1 or 2；
Having the compound of ethylene unsaturated group and carboxyl in be set forth in molecule simultaneously is selected from (methyl) acrylic compounds, crotons Acid, alpha-cyano cinnamic acid, cinnamic acid and make the compound simultaneously with unsaturated group and hydroxyl and saturation or unsaturated dibasic acid Compound obtained by reaction compound one or more of in groups.
2. epoxy carboxylic acids' ester compounds as described in claim 1, which is characterized in that the R in general formula (1)1For hydrogen atom.
3. a kind of polycarboxylic compounds react with multi-anhydride and are obtained for epoxy carboxylic acids' ester compounds described in claim 1.
4. a kind of resin combination includes epoxy carboxylic acids' ester compounds of any of claims 1 or 2.
5. a kind of resin combination includes polycarboxylic compounds as claimed in claim 3.
6. resin combination as described in claim 4 or 5 includes epoxy carboxylic acids' ester compounds and the polycarboxylic acid Close the reactive compounds other than object.
7. resin combination as claimed in claim 6, which is characterized in that the reactive compounds are selected from polyester (methyl) third Olefin(e) acid ester, amine ester (methyl) acrylate, epoxy (methyl) acrylate, polyethers (methyl) acrylate, (methyl) acrylic acid Alkyl ester or (methyl) acrylic acid alkylene carbonate, (methyl) acrylate with aromatic rings, (methyl) propylene with alicyclic ring construction Acid esters, the compound containing dimaleoyl imino, (methyl) acrylamide compound and unsaturated polyester (UP) in groups in a kind Above compound.
8. resin combination as claimed in claim 6, which is characterized in that the reactive compounds are selected from amine ester (methyl) Acrylate, (methyl) alkyl acrylate or (methyl) acrylic acid alkylene carbonate and with aromatic rings (methyl) acrylate institute at The compound of one or more of group.
9. a kind of resin combination contains epoxy carboxylic acids' ester compounds, colorant and adhesive resin described in claim 1.
10. a kind of hardening thing is the hardening thing of the described in any item resin combinations of claim 4 to 9.
11. a kind of colour filter has hardening thing described in any one of claim 10.
12. a kind of display element has colour filter described in claim 11.
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