CN102807778B - Hardening resin composition - Google Patents

Hardening resin composition Download PDF

Info

Publication number
CN102807778B
CN102807778B CN201210170208.9A CN201210170208A CN102807778B CN 102807778 B CN102807778 B CN 102807778B CN 201210170208 A CN201210170208 A CN 201210170208A CN 102807778 B CN102807778 B CN 102807778B
Authority
CN
China
Prior art keywords
methyl
formula
copolymer
acid
acrylic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201210170208.9A
Other languages
Chinese (zh)
Other versions
CN102807778A (en
Inventor
白川政和
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Chemical Co Ltd
Original Assignee
Sumitomo Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Chemical Co Ltd filed Critical Sumitomo Chemical Co Ltd
Publication of CN102807778A publication Critical patent/CN102807778A/en
Application granted granted Critical
Publication of CN102807778B publication Critical patent/CN102807778B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G02F1/133519—Overcoatings

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Optical Filters (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Liquid Crystal (AREA)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

【Problem】Hardening resin composition is provided, it forms film on the colour filter for the impurity for there are several μm or so, the diameter of the conical papilla formed on impurity is diminished.【Solution】Hardening resin composition, it contains：（A）Addition polymers containing the construction unit come from selected from least one of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and the construction unit for coming from the unsaturated compound with Oxyranyle,（B）Epoxy resin selected from least one of diglycidyl ether type epoxy resin and glycidyl ester type epoxy resin,（C）Formula（1）Shown compound,

Description

Hardening resin composition
Technical field
The present invention relates to hardening resin composition.
Background technology
In liquid crystal display device etc., the film of color filter protecting layer etc. can be used as component.Color filter protecting layer, be The concavo-convex planarization on the surface produced by for making on colour filter or black matrix as ground makes for protecting colour filter etc. Its film from the infringement of the decoction from the component for forming its upper strata.In order to form color filter protecting layer, it can make Use hardening resin composition.
It is used as this hardening resin composition, it is known that for example only containing unsaturated carboxylic acid and aliphatic polycycle epoxidation The copolymer of compound as resin component hardening resin composition（Patent document 1）.
【Patent document 1】Japanese Unexamined Patent Publication 2009-149854 publications.
The content of the invention
When there is several μm or so of impurity（Iso things）Colour filter on formed film when, on the film, on the impurity Form conical papilla.When the diameter of the conical papilla is small, projection can be removed by grinding, but when its diameter is big, The removing of projection is carried out even with grinding, film can not be made fully to planarize.Do not have when being used in liquid crystal display device When having the film of substantially flatization, the reason for display is bad is formed.When the above-mentioned such previously known curable resin of utilization Composition, come on it there is several μm or so of the colour filter of impurity formed film when, the conical papilla formed on the impurity Diameter may not be sufficiently small.
The invention provides following ［ 1 ］~［ 6 ］.
［ 1 ］ hardening resin composition, it contains following（A）、（B）With（C）,
（A）Containing come from selected from least one of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides construction unit and come from The addition polymers of the construction unit of unsaturated compound with Oxyranyle
（B）Asphalt mixtures modified by epoxy resin selected from least one of diglycidyl ether type epoxy resin and glycidyl ester type epoxy resin Fat
（C）Formula（1）Shown compound
【Change 1】
［ formula（1）In, R1Represent that alkyl, phenyl, benzyl or carbon number that hydrogen atom, carbon number are 1~20 are 2~5 Cyanoalkyl,
R2~R4Independently of each other represent hydrogen atom, halogen atom, carbon number for 1~20 alkyl, phenyl, nitro or Carbon number is 1~20 acyl group, and the alkyl can be optionally substituted by a hydroxyl group with the hydrogen atom contained in the phenyl ］.
［ 2 ］ hardening resin composition as described above described in ［ 1 ］, wherein,（C）Content relative to（A）100 mass parts are The mass parts of 1 mass parts~25.
［ 3 ］ hardening resin composition as described above described in ［ 1 ］ or ［ 2 ］, wherein,（A）Content relative to（A）Content With（B）Content add up to the mass % of 50 mass %~99.
［ 4 ］ hardening resin composition as described above any one of ［ 1 ］~［ 3 ］, wherein, further containing with choosing From the compound of at least one of acryloyl group and methylacryloyl group.
［ 5 ］ film, it is formed using the hardening resin composition any one of above-mentioned ［ 1 ］~［ 4 ］.
［ 6 ］ display device, it contains film as described above described in ［ 5 ］.
According to the hardening resin composition of the present invention, formed and applied on the colour filter for the impurity for there are several μm or so Film, the diameter of the conical papilla formed on impurity is also small.Therefore, the painting formed by the hardening resin composition of the present invention Film can be planarized by grinding, therefore can manufacture the bad few liquid crystal display device of display.
Embodiment
The hardening resin composition of the present invention contains addition polymers（Hereinafter sometimes referred to " polymer（A）”）, the addition polymers Containing come from selected from least one of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides construction unit and come from oxirane The construction unit of the unsaturated compound of base.
It is used as polymer（A）, can enumerate for example
Polymer ［ A1 ］：At least one of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides will be selected from（a）（Hereinafter sometimes referred to “（a）”）And the unsaturated compound with Oxyranyle（b）（Hereinafter sometimes referred to "（b）”）The copolymerization being polymerized Thing,
Polymer ［ A2 ］：Will（a）With（b）And can be with（a）With（b）The monomer of copolymerization（c）（Wherein, be with（a）With（b）No Same monomer）（Hereinafter sometimes referred to "（c）”）Copolymer being polymerized etc..
（a）Acrylic acid, methacrylic acid, crotonic acid, adjacent vinyl benzoic acid, a vinyl benzene can specifically be enumerated Formic acid, the unsaturated monocarboxylic class to vinyl benzoic acid etc.；
The adjacent benzene of maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3- vinylphthalic acids, 4- vinyl Dioctyl phthalate, 3,4,5,6- tetrahydrophthalic acids, 1,2,3,6- tetrahydrophthalic acids, dimethyl tetrahydro phthalic acid, The unsaturated dicarboxylic class of Isosorbide-5-Nitrae-cyclohexene dioctyl phthalate etc.；
Bicyclic ［ 2.2.1 ］ hept-2-ene" of methyl -5- ENBs -2,3- dioctyl phthalate, 5- carboxyls, 5,6- dicarboxyls Bicyclic ［ 2.2.1 ］ hept-2-ene" of base, 5- carboxyl -5- methyl bicycles ［ 2.2.1 ］ hept-2-ene", 5- carboxyl -5- ethyls Bicyclic ［ 2.2.1 ］ hept-2-ene", 5- carboxyl -6- methyl bicycles ［ 2.2.1 ］ hept-2-ene", 5- carboxyl -6- ethyls are double The bicyclic unsaturated compound class containing carboxyl such as ring ［ 2.2.1 ］ hept-2-ene"；
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3- vinylphthalic acids acid anhydride, 4- vinylphthalic acids Acid anhydride, 3,4,5,6- tetrabydrophthalic anhydrides, 1,2,3,6- tetrabydrophthalic anhydrides, dimethyl tetrahydro phthalic acid The unsaturated dicarboxylic anhydride of acid anhydride, bicyclic ［ 2.2.1 ］ hept-2-ene" -5,6- dicarboxylic anhydride etc.；
Mono succinate (2-（Methyl）Acryloyl-oxyethyl) ester, phthalic acid list (2-（Methyl）Acryloxy Ethyl) more than 2 yuan of the polybasic carboxylic acid such as ester unsaturation it is single (（Methyl）Acryloxyalkyl) esters；
α-（Hydroxymethyl）Acrylic acid is such, the unsaturated acrylate containing hydroxyl and carboxyl in same molecule Class etc..
Wherein, from the point of view of copolyreaction, alkali-solubility, acrylic acid, methacrylic acid, maleic acid are preferably used Acid anhydride etc..
In this specification, "（Methyl）Acrylic acid " represents to be selected from least one of acrylic acid and methacrylic acid.“（First Base）Acryloyl group " and "（Methyl）The statement of acrylate " etc. also has the same meaning.
In the present invention, the unsaturated compound with Oxyranyle（b）Refer to oxirane ring and unsaturated bond Monomer.（b）The structure being for example at least partially epoxidized with chain type unsaturated aliphatic hydrocarbon base can be enumerated and ethene is unsaturated The monomer of key（b1）（Hereinafter sometimes referred to "（b1）”）Or the structure and ethene being at least partially epoxidized with ester ring type unsaturated alkyl The monomer of property unsaturated bond（b2）（Hereinafter sometimes referred to "（b2）”）.
In the present invention,（b）Preferably there is the monomer of Oxyranyle and ethene unsaturated bond, more preferably with ring Oxirane group and（Methyl）The monomer of acryloxy.In addition,（b）Preferably（b2）.
As（b1）, specifically, can enumerate（Methyl）Glycidyl acrylate,（Methyl）Propenoic acid beta-first Base glycidyl esters,（Methyl）Propenoic acid beta-ethyl glycidyl base ester, glycidyl vinyl ether, adjacent vinyl benzyl Base glycidyl ether, a vinylbenzyl glycidyl base ether, to vinylbenzyl glycidyl base ether, Alpha-Methyl-neighbour Vinylbenzyl glycidyl base ether, Alpha-Methyl-a vinylbenzyl glycidyl base ether, Alpha-Methyl-to vinyl benzyl Base glycidyl ether, 2,3- are double（Glycidyl oxy methyl）Styrene, 2,4- are double（Glycidyl oxy methyl） Styrene, 2,5- are double（Glycidyl oxy methyl）Styrene, 2,6- are double（Glycidyl oxy methyl）Styrene, 2, 3,4- tri-（Glycidyl oxy methyl）Styrene, 2,3,5- tri-（Glycidyl oxy methyl）Styrene, 2,3,6- Three（Glycidyl oxy methyl）Styrene, 3,4,5- tri-（Glycidyl oxy methyl）Styrene, 2,4,6- tri-（Contracting Water glyceryl epoxide methyl）Compound described in styrene, Japanese Unexamined Patent Publication 7-248625 publications etc..
As（b2）, a vinylcyclohexene oxide, 1,2- epoxy -4- vinyl cyclohexanes can be enumerated（Such as セ ロキサイド2000；ダ イ セ Le chemical industry（Strain）System）, acrylic acid 3,4- epoxycyclohexyl-methyl esters（Such as サ イ Network ロマーA400；ダ イ セ Le chemical industry（Strain）System）, methacrylic acid 3,4- epoxycyclohexanecarboxylates（Such as サ イ Network ロ マーM100；ダ イ セ Le chemical industry（Strain）System）, formula（I）Shown compound, formula（II）Shown compound etc..
【Change 2】
In formula（I）And formula（II）In, R1And R2Hydrogen atom or the alkyl that carbon number is 1~4 are represented independently of each other, should The hydrogen atom contained in alkyl can be optionally substituted by a hydroxyl group.
X1And X2Singly-bound ,-R are represented independently of each other3-, *-R3- O-, *-R3- S-, *-R3- NH-.
R3Represent the alkane diyl that carbon number is 1~6.
* the associative key with O is represented（Knot closes hand）.
As the alkyl that carbon number is 1~4, specifically, methyl, ethyl, n-propyl, isopropyl, positive fourth can be enumerated Base, sec-butyl, tert-butyl group etc..
Hydroxy alkyl can enumerate hydroxymethyl, 1- hydroxyethyls, 2- hydroxyethyls, 1- hydroxypropyls, 2- hydroxyls Propyl group, 3- hydroxypropyls, 1- hydroxyl -1- Methylethyls, 2- hydroxyl -1- Methylethyls, 1- hydroxybutyls, 2- hydroxyls Base butyl, 3- hydroxybutyls, 4- hydroxybutyls etc..
R1And R2Hydrogen atom, methyl, hydroxymethyl, 1- hydroxyethyls, 2- hydroxyethyls can be preferably enumerated, more preferably Enumerate hydrogen atom, methyl.
Alkane diyl can enumerate methylene, ethylidene, propane -1,2- diyl, propane -1,3- diyl, butane - Isosorbide-5-Nitrae-diyl, pentane -1,5- diyl, hexane -1,6- diyl etc..
X1And X2Singly-bound, methylene, ethylidene, *-CH can preferably be enumerated2- O-（* the associative key with O is represented） Base, *-CH2CH2- O- bases, more preferably enumerate singly-bound, *-CH2CH2- O- bases.
It is used as formula（I）Shown compound, can be with enumeration（I-1）~formula（I-15）Shown compound etc..It is preferred that Enumeration（I-1）, formula（I-3）, formula（I-5）, formula（I-7）, formula（I-9）, formula（I-11）~formula（I-15）.More preferably Enumeration（I-1）, formula（I-7）, formula（I-9）, formula（I-15）.
【Change 3】
【Change 4】
It is used as formula（II）Shown compound, can be with enumeration（II-1）~formula（II-15）Shown compound etc..It is excellent Select enumeration（II-1）, formula（II-3）, formula（II-5）, formula（II-7）, formula（II-9）, formula（II-11）~formula（II- 15）.
More preferably enumeration（II-1）, formula（II-7）, formula（II-9）, formula（II-15）.
【Change 5】
【Change 6】
Formula（I）Shown compound and formula（II）Shown compound can be used individually, can also be by two or more It is used in combination.When by formula（I）Shown compound and formula（II）Shown compound and used time, its ratio (formula（I）：Formula（II）〕（Rub You compare）It is arbitrary, but preferably 5：95~95：5, more preferably 10：90~90：10, particularly preferred 20：80~80：20.
（c）It can enumerate for example（Methyl）Methyl acrylate,（Methyl）Ethyl acrylate,（Methyl）N-butyl acrylate, （Methyl）Sec-butyl acrylate,（Methyl）Acrylate tert-buthyl etc.（Methyl）Alkyl-acrylates；
（Methyl）Cyclohexyl acrylate,（Methyl）Acrylic acid 2- methyl cyclohexanes base ester, three ring ［ 5.2.1.02,6The last of the ten Heavenly stems Alkane -8- bases（Methyl）Acrylate（In the art, as trivial name, it is referred to as（Methyl）Acrylic acid bicyclopentyl ester）、 （Methyl）Acrylic acid bicyclopentyl epoxide ethyl ester,（Methyl）Isobornyl acrylate etc.（Methyl）Acrylate base ester Class；
（Methyl）Phenyl acrylate,（Methyl）Benzyl acrylate etc.（Methyl）Acrylic acid aryl or aralkyl ester Class；
The dicarboxylic diester of diethyl maleate, diethyl fumarate, diethyl itaconate etc.；
（Methyl）2-Hydroxy ethyl acrylate,（Methyl）Acrylic acid 2- hydroxy propyl esters etc.（Methyl）Dihydroxypropyl Alkyl esters；
Bicyclic ［ 2.2.1 ］ hept-2-ene", 5- methyl bicycles ［ 2.2.1 ］ hept-2-ene", 5- ethyls are bicyclic ［ 2.2.1 ］ Bicyclic ［ 2.2.1 ］ hept-2-ene" of hept-2-ene", 5- hydroxyls, bicyclic ［ 2.2.1 ］ hept-2-ene" of 5- hydroxymethyls, 5- （2 '-hydroxyethyl）Bicyclic ［ 2.2.1 ］ hept-2-ene" of bicyclic ［ 2.2.1 ］ hept-2-ene", 5- methoxyl groups, 5- ethyoxyls are double Bicyclic ［ 2.2.1 ］ hept-2-ene" of ring ［ 2.2.1 ］ hept-2-ene", 5,6- dihydroxy, 5,6- bis-（Hydroxymethyl）Bicyclic 2.2.1 ］ hept-2-ene", 5,6- bis-（2 '-hydroxyethyl）Bicyclic ［ 2.2.1 ］ hept-2-ene", 5,6- dimethoxys it is bicyclic 2.2.1 ］ bicyclic ［ 2.2.1 ］ hept-2-ene" of hept-2-ene", 5,6- diethoxies, 5- hydroxy-5-methyl bases are bicyclic ［ 2.2.1 ］ Bicyclic ［ 2.2.1 ］ hept-2-ene" of hept-2-ene", 5- hydroxyl -5- ethyls, 5- methylol -5- methyl bicycles ［ 2.2.1 ］ Bicyclic ［ 2.2.1 ］ hept-2-ene" of hept-2-ene", 5- tert-butoxycarbonyls, 5- cyclohexyl Epoxide carbonyls are bicyclic ［ 2.2.1 ］ Bicyclic ［ 2.2.1 ］ hept-2-ene" of hept-2-ene", 5- phenyloxycarbonyls, 5,6- are double（Tert-butoxycarbonyl）Bicyclic ［ 2.2.1 ］ Hept-2-ene", 5,6- are double（Cyclohexyl Epoxide carbonyl）The bicyclic unsaturated compound class of bicyclic ［ 2.2.1 ］ hept-2-ene" etc.；
N-phenylmaleimide, N- N-cyclohexylmaleimides, N- benzyl maleimides, N- succinimides Base -3- maleimidobenzoyls ester, N- succinimido -4- malimidobutanoates, N- succinimides Base -6- maleimidohexanoic acids ester, N- succinimido -3- maleimidopropionic acids ester, N-（9- acridinyls）Horse Carry out the dicarbonyl imides derivative species of acid imide etc.；
Styrene, α-methylstyrene, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxybenzene The phenylethylene of ethene etc.；
The vinyl cyanide of acrylonitrile, methacrylonitrile etc.；The ethene of vinyl chloride, vinylidene chloride, vinyl-acetic ester etc. Based compound class；The acrylic amide of acrylamide, Methacrylamide etc.；1,3-butadiene, isoprene, 2,3- diformazans The diolefin compound class of base -1,3-butadiene etc.；
3- methyl -3- methacryloxymethyls oxetanes, 3- methyl -3- acryloyloxymethyl oxygen Azetidine, 3- ethyl -3- methacryloxymethyls oxetanes, 3- ethyl -3- acryloyloxymethyls Oxetanes, 3- methyl -3- methacryloxyethyls oxetanes, 3- methyl -3- acryloxy second Base oxetanes, 3- ethyl -3- methacryloxyethyls oxetanes, 3- ethyl -3- acryloxies Ethyloxetane etc. contains oxetanyl（Methyl）Esters of acrylic acid；
Acrylic acid tetrahydro furfuryl ester（Such as Shuan コ ー ト V#150, Osaka Organic Chemical Industry（Strain）System）, methacrylic acid Tetrahydro furfuryl ester etc. contains tetrahydrofuran base（Methyl）Esters of acrylic acid etc..
Wherein, from the point of view of copolyreaction and alkali-solubility, preferably styrene, N-phenylmaleimide, N- N-cyclohexylmaleimides, N- benzyl maleimides, bicyclic ［ 2.2.1 ］ hept-2-ene" etc..
In polymer ［ A1 ］, the ratio of construction unit of each monomer is come from relative to the construction unit for constituting polymer ［ A1 ］ Total molal quantity, preferably following scope.
Come from（a）Construction unit；5~60 moles of %（More preferably 10~50 moles %）
Come from（b）Construction unit；40~95 moles of %（More preferably 50~90 moles %）
If the ratio of the construction unit of polymer ［ A1 ］ is in above-mentioned scope, with storage stability, gained film Chemical proofing, the trend of heat resistance and mechanical strength.
Polymer ［ A1 ］ may be referred to such as document " Gao Fen He Cheng experiment method "（The big grand row in Tianjin writes sale room（Strain） Chemistry is with the distribution on March 1st, 1972 of the 1st edition the 1st brush of people）Described in method and citation described in the document enter Row manufacture.
Specifically, following methods have been enumerated, i.e. by ormal weight（a）With（b）, polymerization initiator and solvent etc. load Into reaction vessel, oxygen, the method be thus stirred in deoxidizing atmosphere, heat, being incubated are replaced using nitrogen.Also, wherein Polymerization initiator used and solvent etc. are not particularly limited, and can use any material usually used in this field.For example, Polymerization initiator can enumerate azo-compound（2,2 '-azobis isobutyronitrile, 2,2 '-azo are double（2,4- methyl pentane nitriles） Deng）Or organic peroxide（Benzoyl peroxide etc.）, as long as solvent can dissolve the solvent of each monomer, can use down Solvent stated etc. as the present invention hardening resin composition solvent（E）.
Also, the copolymer of gained can directly use reacted solution, or can use what is concentrated or dilute Solution, or can also use by the use of the method for reprecipitation etc. and be used as solid（Powder）The material of taking-up.Especially, in the polymerization When, by using with following solvents（E）It is used as solvent for identical solvent, directly can be used for reacted solution solid The preparation of the property changed resin combination, can simplify the manufacturing process of hardening resin composition.
In polymer ［ A2 ］, relative to the total molal quantity for the entire infrastructure unit for constituting polymer ［ A2 ］, come from each The ratio of the construction unit of monomer is preferably following scope.
Come from（a）Construction unit；2~40 moles of %（More preferably 5~35 moles %）
Come from（b）Construction unit；2~95 moles of %（More preferably 5~80 moles %）
Come from（c）Construction unit；1~65 mole of %（More preferably 1~60 mole %）
In addition, coming from（a）Construction unit with coming from（b）Construction unit total relative to constituting polymer ［ A2 ］ The total molal quantity of entire infrastructure unit, preferably 70~99 moles %, more preferably 90~99 moles %.
If the ratio of the construction unit of polymer ［ A2 ］ has the film of storage stability, gained in above-mentioned scope Chemical proofing, the tendency of heat resistance and mechanical strength.
Polymer ［ A2 ］ can utilize the method same with polymer ［ A1 ］ to manufacture.
As polymer ［ A1 ］ specific example, it can enumerate（Methyl）Acrylic acid/formula（I-1）Copolymer,（Methyl） Acrylic acid/formula（I-2）Copolymer,（Methyl）Acrylic acid/formula（I-3）Copolymer,（Methyl）Acrylic acid/formula（I-4）'s Copolymer,（Methyl）Acrylic acid/formula（I-5）Copolymer,（Methyl）Acrylic acid/formula（I-6）Copolymer,（Methyl）Propylene Acid/formula（I-7）Copolymer,（Methyl）Acrylic acid/formula（I-8）Copolymer,（Methyl）Acrylic acid/formula（I-9）Copolymerization Thing,（Methyl）Acrylic acid/formula（I-10）Copolymer,（Methyl）Acrylic acid/formula（I-11）Copolymer,（Methyl）Propylene Acid/formula（I-12）Copolymer,（Methyl）Acrylic acid/formula（I-13）Copolymer,（Methyl）Acrylic acid/formula（I-14）'s Copolymer,（Methyl）Acrylic acid/formula（I-15）Copolymer,（Methyl）Acrylic acid/formula（II-1）Copolymer,（Methyl）Third Olefin(e) acid/formula（II-2）Copolymer,（Methyl）Acrylic acid/formula（II-3）Copolymer,（Methyl）Acrylic acid/formula（II-4） Copolymer,（Methyl）Acrylic acid/formula（II-5）Copolymer,（Methyl）Acrylic acid/formula（II-6）Copolymer,（Methyl） Acrylic acid/formula（II-7）Copolymer,（Methyl）Acrylic acid/formula（II-8）Copolymer,（Methyl）Acrylic acid/formula（II- 9）Copolymer,（Methyl）Acrylic acid/formula（II-10）Copolymer,（Methyl）Acrylic acid/formula（II-11）Copolymer, （Methyl）Acrylic acid/formula（II-12）Copolymer,（Methyl）Acrylic acid/formula（II-13）Copolymer,（Methyl）Acrylic acid/ Formula（II-14）Copolymer,（Methyl）Acrylic acid/formula（II-15）Copolymer,（Methyl）Acrylic acid/formula（I-1）/ formula （II-1）Copolymer,（Methyl）Acrylic acid/formula（I-2）/ formula（II-2）Copolymer,（Methyl）Acrylic acid/formula（I- 3）/ formula（II-3）Copolymer,（Methyl）Acrylic acid/formula（I-4）/ formula（II-4）Copolymer,（Methyl）Acrylic acid/formula （I-5）/ formula（II-5）Copolymer,（Methyl）Acrylic acid/formula（I-6）/ formula（II-6）Copolymer,（Methyl）Propylene Acid/formula（I-7）/ formula（II-7）Copolymer,（Methyl）Acrylic acid/formula（I-8）/ formula（II-8）Copolymer,（Methyl） Acrylic acid/formula（I-9）/ formula（II-9）Copolymer,（Methyl）Acrylic acid/formula（I-10）/ formula（II-10）Copolymer, （Methyl）Acrylic acid/formula（I-11）/ formula（II-11）Copolymer,（Methyl）Acrylic acid/formula（I-12）/ formula（II-12）'s Copolymer,（Methyl）Acrylic acid/formula（I-13）/ formula（II-13）Copolymer,（Methyl）Acrylic acid/formula（I-14）/ formula （II-14）Copolymer,（Methyl）Acrylic acid/formula（I-15）/ formula（II-15）Copolymer,（Methyl）Acrylic acid/formula （I-1）/ formula（I-7）Copolymer,（Methyl）Acrylic acid/formula（I-1）/ formula（II-7）Copolymer, crotonic acid/formula（I- 1）Copolymer, crotonic acid/formula（I-2）Copolymer, crotonic acid/formula（I-3）Copolymer, crotonic acid/formula（I-4）'s Copolymer, crotonic acid/formula（I-5）Copolymer, crotonic acid/formula（I-6）Copolymer, crotonic acid/formula（I-7）Copolymerization Thing, crotonic acid/formula（I-8）Copolymer, crotonic acid/formula（I-9）Copolymer, crotonic acid/formula（I-10）Copolymer, Crotonic acid/formula（I-11）Copolymer, crotonic acid/formula（I-12）Copolymer, crotonic acid/formula（I-13）Copolymer, bar Beans acid/formula（I-14）Copolymer, crotonic acid/formula（I-15）Copolymer, crotonic acid/formula（II-1）Copolymer, crotons Acid/formula（II-2）Copolymer, crotonic acid/formula（II-3）Copolymer, crotonic acid/formula（II-4）Copolymer, crotons Acid/formula（II-5）Copolymer, crotonic acid/formula（II-6）Copolymer, crotonic acid/formula（II-7）Copolymer, crotons Acid/formula（II-8）Copolymer, crotonic acid/formula（II-9）Copolymer, crotonic acid/formula（II-10）Copolymer, crotons Acid/formula（II-11）Copolymer, crotonic acid/formula（II-12）Copolymer, crotonic acid/formula（II-13）Copolymer, bar Beans acid/formula（II-14）Copolymer, crotonic acid/formula（II-15）Copolymer, maleic acid/formula（I-1）Copolymer, horse Carry out sour/formula（I-2）Copolymer, maleic acid/formula（I-3）Copolymer, maleic acid/formula（I-4）Copolymer, maleic acid/ Formula（I-5）Copolymer, maleic acid/formula（I-6）Copolymer, maleic acid/formula（I-7）Copolymer, maleic acid/formula （I-8）Copolymer, maleic acid/formula（I-9）Copolymer, maleic acid/formula（I-10）Copolymer, maleic acid/formula（I- 11）Copolymer, maleic acid/formula（I-12）Copolymer, maleic acid/formula（I-13）Copolymer, maleic acid/formula（I- 14）Copolymer, maleic acid/formula（I-15）Copolymer, maleic acid/formula（II-1）Copolymer, maleic acid/formula（II- 2）Copolymer, maleic acid/formula（II-3）Copolymer, maleic acid/formula（II-4）Copolymer, maleic acid/formula（II-5） Copolymer, maleic acid/formula（II-6）Copolymer, maleic acid/formula（II-7）Copolymer, maleic acid/formula（II-8）'s Copolymer, maleic acid/formula（II-9）Copolymer, maleic acid/formula（II-10）Copolymer, maleic acid/formula（II-11）'s Copolymer, maleic acid/formula（II-12）Copolymer, maleic acid/formula（II-13）Copolymer, maleic acid/formula（II-14） Copolymer, maleic acid/formula（II-15）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（I-1）Copolymer,（First Base）Acrylic acid/maleic anhydride/formula（I-2）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（I-3）Copolymer, （Methyl）Acrylic acid/maleic anhydride/formula（I-4）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（I-5）Copolymerization Thing,（Methyl）Acrylic acid/maleic anhydride/formula（I-6）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（I-7）Be total to Polymers,（Methyl）Acrylic acid/maleic anhydride/formula（I-8）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（I-9）'s Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（I-10）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（I- 11）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（I-12）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula （I-13）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（I-14）Copolymer,（Methyl）Acrylic acid/maleic acid Acid anhydride/formula（I-15）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（II-1）Copolymer,（Methyl）Acrylic acid/horse Carry out acid anhydrides/formula（II-2）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（II-3）Copolymer,（Methyl）Propylene Acid/maleic anhydride/formula（II-4）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（II-5）Copolymer,（Methyl） Acrylic acid/maleic anhydride/formula（II-6）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（II-7）Copolymer,（First Base）Acrylic acid/maleic anhydride/formula（II-8）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（II-9）Copolymer, （Methyl）Acrylic acid/maleic anhydride/formula（II-10）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（II-11）Be total to Polymers,（Methyl）Acrylic acid/maleic anhydride/formula（II-12）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（II- 13）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula（II-14）Copolymer,（Methyl）Acrylic acid/maleic anhydride/formula （II-15）Copolymer etc..
As polymer ［ A2 ］ specific example, it can enumerate（Methyl）Acrylic acid/formula（I-1）/（Methyl）Acrylic acid first The copolymer of ester,（Methyl）Acrylic acid/formula（I-2）/（Methyl）The copolymer of methyl acrylate,（Methyl）Acrylic acid/formula（I- 3）/（Methyl）The copolymer of methyl acrylate,（Methyl）Acrylic acid/formula（I-4）/（Methyl）The copolymer of methyl acrylate, （Methyl）Acrylic acid/formula（I-5）/（Methyl）The copolymer of methyl acrylate,（Methyl）Acrylic acid/formula（I-6）/（Methyl）Third The copolymer of e pioic acid methyl ester,（Methyl）Acrylic acid/formula（I-7）/（Methyl）The copolymer of methyl acrylate,（Methyl）Acrylic acid/ Formula（I-8）/（Methyl）The copolymer of methyl acrylate,（Methyl）Acrylic acid/formula（I-9）/（Methyl）Methyl acrylate is total to Polymers,（Methyl）Acrylic acid/formula（I-10）/（Methyl）The copolymer of methyl acrylate,（Methyl）Acrylic acid/formula（I-11）/ （Methyl）The copolymer of methyl acrylate,（Methyl）Acrylic acid/formula（I-12）/（Methyl）The copolymer of methyl acrylate,（First Base）Acrylic acid/formula（I-13）/（Methyl）The copolymer of methyl acrylate,（Methyl）Acrylic acid/formula（I-14）/（Methyl）Third The copolymer of e pioic acid methyl ester,（Methyl）Acrylic acid/formula（I-15）/（Methyl）The copolymer of methyl acrylate,（Methyl）Propylene Acid/formula（II-1）/（Methyl）The copolymer of methyl acrylate,（Methyl）Acrylic acid/formula（II-2）/（Methyl）Methyl acrylate Copolymer,（Methyl）Acrylic acid/formula（II-3）/（Methyl）The copolymer of methyl acrylate,（Methyl）Acrylic acid/formula（II- 4）/（Methyl）The copolymer of methyl acrylate,（Methyl）Acrylic acid/formula（II-5）/（Methyl）The copolymer of methyl acrylate, （Methyl）Acrylic acid/formula（II-6）/（Methyl）The copolymer of methyl acrylate,（Methyl）Acrylic acid/formula（II-7）/（Methyl） The copolymer of methyl acrylate,（Methyl）Acrylic acid/formula（II-8）/（Methyl）The copolymer of methyl acrylate,（Methyl）Propylene Acid/formula（II-9）/（Methyl）The copolymer of methyl acrylate,（Methyl）Acrylic acid/formula（II-10）/（Methyl）Acrylic acid first The copolymer of ester,（Methyl）Acrylic acid/formula（II-11）/（Methyl）The copolymer of methyl acrylate,（Methyl）Acrylic acid/formula （II-12）/（Methyl）The copolymer of methyl acrylate,（Methyl）Acrylic acid/formula（II-13）/（Methyl）Methyl acrylate Copolymer,（Methyl）Acrylic acid/formula（II-14）/（Methyl）The copolymer of methyl acrylate,（Methyl）Acrylic acid/formula（II- 15）/（Methyl）The copolymer of methyl acrylate,（Methyl）Acrylic acid/formula（I-1）/（Methyl）Acrylic acid bicyclopentyl ester is total to Polymers,（Methyl）Acrylic acid/formula（II-1）/（Methyl）The copolymer of acrylic acid bicyclopentyl ester,（Methyl）Acrylic acid/formula （I-1）/ formula（II-1）/（Methyl）Copolymer, the crotonic acid/formula of acrylic acid bicyclopentyl ester（I-1）/（Methyl）Acrylic acid Copolymer, the maleic acid/formula of bicyclopentyl ester（I-1）/（Methyl）The copolymer of acrylic acid bicyclopentyl ester,（Methyl）Propylene Acid/maleic anhydride/formula（I-1）/（Methyl）The copolymer of acrylic acid bicyclopentyl ester,（Methyl）Acrylic acid/formula（I-1）/（First Base）Methyl acrylate/（Methyl）Copolymer, the crotonic acid/formula of acrylic acid bicyclopentyl ester（II-1）/（Methyl）Acrylic acid two Copolymer, the maleic acid/formula of cyclopentyl ester（II-1）/（Methyl）The copolymer of acrylic acid bicyclopentyl ester,（Methyl）Propylene Acid/maleic anhydride/formula（II-1）/（Methyl）The copolymer of acrylic acid bicyclopentyl ester,（Methyl）Acrylic acid/formula（II-1）/ （Methyl）Methyl acrylate/（Methyl）The copolymer of acrylic acid bicyclopentyl ester,（Methyl）Acrylic acid/formula（I-1）/（Methyl） The copolymer of phenyl acrylate,（Methyl）Acrylic acid/formula（II-1）/（Methyl）The copolymer of phenyl acrylate,（Methyl） Acrylic acid/formula（I-1）/ formula（II-1）/（Methyl）Copolymer, the crotonic acid/formula of phenyl acrylate（I-1）/（Methyl）Third Copolymer, the maleic acid/formula of olefin(e) acid phenylester（I-1）/（Methyl）The copolymer of phenyl acrylate,（Methyl）Acrylic acid/horse Carry out acid anhydrides/formula（I-1）/（Methyl）The copolymer of phenyl acrylate,（Methyl）Acrylic acid/formula（I-1）/（Methyl）Acrylic acid Methyl esters/（Methyl）Copolymer, the crotonic acid/formula of phenyl acrylate（II-1）/（Methyl）The copolymer of phenyl acrylate, Maleic acid/formula（II-1）/（Methyl）The copolymer of phenyl acrylate,（Methyl）Acrylic acid/maleic anhydride/formula（II-1）/ （Methyl）The copolymer of phenyl acrylate,（Methyl）Acrylic acid/formula（II-1）/（Methyl）Methyl acrylate/（Methyl）Propylene The copolymer of sour phenylester,（Methyl）Acrylic acid/formula（I-1）The copolymer of/diethyl maleate,（Methyl）Acrylic acid/formula （II-1）The copolymer of/diethyl maleate,（Methyl）Acrylic acid/formula（I-1）/ formula（II-1）/ diethyl maleate is total to Polymers, crotonic acid/formula（I-1）Copolymer, the maleic acid/formula of/diethyl maleate（I-1）The copolymerization of/diethyl maleate Thing,（Methyl）Acrylic acid/maleic anhydride/formula（I-1）The copolymer of/diethyl maleate,（Methyl）Acrylic acid/formula（I-1）/ （Methyl）Copolymer, the crotonic acid/formula of methyl acrylate/diethyl maleate（II-1）The copolymer of/diethyl maleate, Maleic acid/formula（II-1）The copolymer of/diethyl maleate,（Methyl）Acrylic acid/maleic anhydride/formula（II-1）/ maleic acid The copolymer of diethylester,（Methyl）Acrylic acid/formula（II-1）/（Methyl）The copolymer of methyl acrylate/diethyl maleate, （Methyl）Acrylic acid/formula（I-1）/（Methyl）The copolymer of 2-Hydroxy ethyl acrylate,（Methyl）Acrylic acid/formula（II- 1）/（Methyl）The copolymer of 2-Hydroxy ethyl acrylate,（Methyl）Acrylic acid/formula（I-1）/ formula（II-1）/（Methyl）Third Copolymer, the crotonic acid/formula of olefin(e) acid -2- hydroxy methacrylates（I-1）/（Methyl）The copolymer of 2-Hydroxy ethyl acrylate, Maleic acid/formula（I-1）/（Methyl）The copolymer of 2-Hydroxy ethyl acrylate,（Methyl）Acrylic acid/maleic anhydride/formula （I-1）/（Methyl）The copolymer of 2-Hydroxy ethyl acrylate,（Methyl）Acrylic acid/formula（I-1）/（Methyl）Acrylic acid first Ester/（Methyl）Copolymer, the crotonic acid/formula of 2-Hydroxy ethyl acrylate（II-1）/（Methyl）Acrylic acid -2- hydroxyl second Copolymer, the maleic acid/formula of ester（II-1）/（Methyl）The copolymer of 2-Hydroxy ethyl acrylate,（Methyl）Acrylic acid/horse Carry out acid anhydrides/formula（II-1）/（Methyl）The copolymer of 2-Hydroxy ethyl acrylate,（Methyl）Acrylic acid/formula（II-1）/（First Base）Methyl acrylate/（Methyl）The copolymer of 2-Hydroxy ethyl acrylate,（Methyl）Acrylic acid/formula（I-1）/ bicyclic 2.2.1 ］ copolymer of hept-2-ene",（Methyl）Acrylic acid/formula（II-1）The copolymer of/bicyclic ［ 2.2.1 ］ hept-2-ene", （Methyl）Acrylic acid/formula（I-1）/ formula（II-1）Copolymer, the crotonic acid/formula of/bicyclic ［ 2.2.1 ］ hept-2-ene"（I-1）/ Copolymer, the maleic acid/formula of bicyclic ［ 2.2.1 ］ hept-2-ene"（I-1）The copolymer of/bicyclic ［ 2.2.1 ］ hept-2-ene",（First Base）Acrylic acid/maleic anhydride/formula（I-1）The copolymer of/bicyclic ［ 2.2.1 ］ hept-2-ene",（Methyl）Acrylic acid/formula（I- 1）/（Methyl）The copolymer, crotonic acid/formula of methyl acrylate/bicyclic ［ 2.2.1 ］ hept-2-ene"（II-1）/ bicyclic ［ 2.2.1 ］ Copolymer, the maleic acid/formula of hept-2-ene"（II-1）The copolymer of/bicyclic ［ 2.2.1 ］ hept-2-ene",（Methyl）Acrylic acid/ Maleic anhydride/formula（II-1）The copolymer of/bicyclic ［ 2.2.1 ］ hept-2-ene",（Methyl）Acrylic acid/formula（II-1）/（Methyl） The copolymer of methyl acrylate/bicyclic ［ 2.2.1 ］ hept-2-ene",（Methyl）Acrylic acid/formula（I-1）/ N- cyclohexyl Malaysia acyl The copolymer of imines,（Methyl）Acrylic acid/formula（II-1）The copolymer of/N- N-cyclohexylmaleimides,（Methyl）Acrylic acid/ Formula（I-1）/ formula（II-1）Copolymer, the crotonic acid/formula of/N- N-cyclohexylmaleimides（I-1）/ N- cyclohexyl Malaysia Imido copolymer, maleic acid/formula（I-1）The copolymer of/N- N-cyclohexylmaleimides,（Methyl）Acrylic acid/Malaysia Acid anhydrides/formula（I-1）The copolymer of/N- N-cyclohexylmaleimides,（Methyl）Acrylic acid/formula（I-1）/（Methyl）Acrylic acid Copolymer, the crotonic acid/formula of methyl esters/N- N-cyclohexylmaleimides（II-1）The copolymerization of/N- N-cyclohexylmaleimides Thing, maleic acid/formula（II-1）The copolymer of/N- N-cyclohexylmaleimides,（Methyl）Acrylic acid/maleic anhydride/formula（II- 1）The copolymer of/N- N-cyclohexylmaleimides,（Methyl）Acrylic acid/formula（II-1）/（Methyl）Methyl acrylate/N- rings The copolymer of hexyl maleimide,（Methyl）Acrylic acid/formula（I-1）The copolymer of/styrene,（Methyl）Acrylic acid/formula （II-1）The copolymer of/styrene,（Methyl）Acrylic acid/formula（I-1）/ formula（II-1）The copolymer of/styrene, crotonic acid/ Formula（I-1）Copolymer, the maleic acid/formula of/styrene（I-1）The copolymer of/styrene,（Methyl）Acrylic acid/maleic anhydride/ Formula（I-1）The copolymer of/styrene,（Methyl）Acrylic acid/formula（I-1）/（Methyl）The copolymerization of methyl acrylate/styrene Thing, crotonic acid/formula（II-1）Copolymer, the maleic acid/formula of/styrene（II-1）The copolymer of/styrene,（Methyl）Propylene Acid/maleic anhydride/formula（II-1）The copolymer of/styrene,（Methyl）Acrylic acid/formula（II-1）/（Methyl）Methyl acrylate/ The copolymer of styrene,（Methyl）Acrylic acid/formula（I-1）The copolymer of/N- N-cyclohexylmaleimides/styrene,（First Base）Acrylic acid/formula（II-1）The copolymer of/N- N-cyclohexylmaleimides/styrene,（Methyl）Acrylic acid/formula（I-1）/ Formula（II-1）Copolymer, the crotonic acid/formula of/N- N-cyclohexylmaleimides/styrene（I-1）/ N- cyclohexyl Malaysia acyl Copolymer, the maleic acid/formula of imines/styrene（I-1）The copolymer of/N- N-cyclohexylmaleimides/styrene,（Methyl） Acrylic acid/maleic anhydride/formula（I-1）The copolymer of/N- N-cyclohexylmaleimides/styrene,（Methyl）Acrylic acid/formula （I-1）/（Methyl）Copolymer, the crotonic acid/formula of methyl acrylate/N- N-cyclohexylmaleimides/styrene（II-1）/ Copolymer, the maleic acid/formula of N- N-cyclohexylmaleimides/styrene（II-1）/ N- N-cyclohexylmaleimides/benzene second The copolymer of alkene,（Methyl）Acrylic acid/maleic anhydride/formula（II-1）The copolymerization of/N- N-cyclohexylmaleimides/styrene Thing,（Methyl）Acrylic acid/formula（II-1）/（Methyl）The copolymer of methyl acrylate/N- N-cyclohexylmaleimides/styrene Deng.
Polymer（A）Polystyrene conversion weight average molecular weight be preferably 3,000~100,000, more preferably 5,000~ 50,000, further preferred 5,000~25,000, particularly preferred 5,000~15,000.Polymer（A）Weight average molecular weight exist During above range, coating has the tendency of to become good.
Polymer（A）Molecular weight distribution ［ weight average molecular weight（Mw）/ number-average molecular weight（Mn）It is preferably 1.1~6.0, more It is preferred that 1.2~4.0.Molecular weight distribution is in above range, and it is excellent that the film of gained has the tendency of chemical proofing.
Polymer（A）Acid number be preferably 30mg-KOH/g~180mg-KOH/g, more preferably 40mg-KOH/g~ 150mg-KOH/g, particularly preferred 50mg-KOH/g~135mg-KOH/g.Wherein, acid number is as neutralizing polymer The amount of potassium hydroxide required for 1g（mg）Come the value determined, it can be titrated to ask by using potassium hydroxide aqueous solution .Polymer（A）Acid number in above range, the excellent tendency of the tack of rewarding film and substrate.
Polymer（A）Content relative to polymer（A）Content and epoxy resin（B）Content total amount, preferably For 50~99 mass %, more preferably 60~95 mass %.Polymer（A）Content in above range, rewarding film with The tack and chemical proofing of substrate become good tendency.
The hardening resin composition of the present invention contains selected from diglycidyl ether type epoxy resin and glycidyl ester type ring The epoxy resin of at least one of oxygen tree fat（B）（Hereinafter sometimes referred to " epoxy resin（B）”）.
Diglycidyl ether type epoxy resin is the epoxy resin with glycidol ether structure, can be by making phenols or many First alcohol etc. is synthesized with epichlorohydrin reaction.
Diglycidyl ether type epoxy resin specifically, can enumerate such as bisphenol A type epoxy resin, bisphenol F type epoxy Resin, bisphenol-type epoxy resin, novolac type epoxy resins, orthoresol-novolac type epoxy resin, trihydroxy Phenylmethane type epoxy resin etc..
Glycidyl ester type epoxy resin is the epoxy resin with glycidol ester structure, can be by making phthalic acid The carboxyl of derivative or aliphatic acid etc. reacts to synthesize with epichlorohydrin.
Glycidyl ester type epoxy resin can be enumerated for example by P-hydroxybenzoic acid, m-hydroxybenzoic acid, terephthaldehyde Glycidyl ester type epoxy resin etc. derived from the aromatic carboxylic acid of acid etc..
The epoxy resin used in the hardening resin composition of the present invention（B）Preferably aromatic epoxy resin, preferably It is bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac type epoxy resins, orthoresol-novolac type ring The diglycidyl ether type epoxy resin of oxygen tree fat, many phenol-type epoxy resins etc..Wherein, particularly preferably bisphenol A type epoxy resin.
Above-mentioned diglycidyl ether type epoxy resin can make corresponding phenols and table by using existing known method Chloropharin is condensed to synthesize in the presence of a strong base.The reaction can utilize known to those skilled in the art Method is carried out.
Alternatively, it is also possible to use commercially available product.For example, as the commercially available product of bisphenol A type epoxy resin, can use JER157S70、エピコート1001、エピコート1002、エピコート1003、エピコート1004、エピコート 1007、エピコート1009、エピコート1010、エピコート828（Mitsubishi Chemical（Strain）System）Deng.It is used as bisphenol-f type The commercially available product of epoxy resin, can use エ ピ コ ー ト 807（Mitsubishi Chemical（Strain）System）, YDF-170（Dongdu is melted into（Strain） System）Deng.As the commercially available product of novolac type epoxy resins, エ ピ コ ー ト 152, エ ピ コ ー ト 154 can be used（Three Water chestnut chemistry（Strain）System）, EPPN-201, PPN-202（Japanese chemical drug（Strain）System）, DEN-438（ダ ウ ケ ミ カ Le society system）Deng. As the commercially available product of orthoresol-novolac type epoxy resin, EOCN-125S, EOCN-103S, EOCN- can be used 104S, EOCN-1020, EOCN-1025, EOCN-1027（Japanese chemical drug（Strain）System）Deng.It is used as many phenol-type epoxy resins Commercially available product, can use エ ピ コ ー ト 1032H60, エ ピ コ ー ト YX-4000（Mitsubishi Chemical（Strain）System）Deng.
Epoxy resin（B）Epoxide equivalent be preferably 100~500g/eq, more preferably 150~400g/eq.Wherein, ring Oxygen equivalent is defined by the molecular weight of the epoxy resin of every 1 epoxy radicals.Epoxide equivalent can be utilized in such as JIS K7236 Defined method is determined.
Epoxy resin（B）Acid number be typically smaller than 30mg-KOH/g, more preferably below 10mg-KOH/g.
In addition, epoxy resin（B）Weight average molecular weight be preferably 300~10,000, more preferably 400~6,000, further It is preferred that 500~4,800.
Epoxy resin（B）Content relative to polymer（A）100 mass parts, preferably 1~100 mass parts, more preferably 5~67 mass parts.Work as epoxy resin（B）Content in above range, the flatness for having the tendency of film is excellent.
The hardening resin composition of the present invention contains following formula（1）Shown imidazolium compounds（Hereinafter sometimes referred to " imidazoles Compound（C）”）.
【Change 7】
(formula（1）In, R1Represent that alkyl, phenyl, benzyl or carbon number that hydrogen atom, carbon number are 1~20 are 2~5 Cyanoalkyl.
R2~R4Independently of each other represent hydrogen atom, halogen atom, carbon number for 1~20 alkyl, phenyl, nitro or Carbon number is 1~20 acyl group, and the alkyl can be optionally substituted by a hydroxyl group with the hydrogen atom contained in the phenyl.〕
Carbon number for 1~20 alkyl can enumerate for example methyl, ethyl, propyl group, isobutyl group, butyl, the tert-butyl group, oneself Base, heptyl, octyl group, nonyl, decyl, heptadecyl, undecyl etc., preferably carbon number are 1~10, more preferably carbon number For 1~6, further preferred carbon number is 1~4.
As the cyanoalkyl that carbon number is 2~5, cyano methyl, cyano ethyl, cyanopropyl, cyano group can be enumerated Butyl, cyanopentyl etc..
Halogen atom can be enumerated such as fluorine atom, chlorine atom, bromine atoms.
Carbon number can enumerate such as formoxyl, acetyl group, propiono, isobutyryl, valeryl for 1~20 acyl group Base, isovaleryl, pivaloyl group, lauroyl, tetradecane acyl group and octadecanoyl etc..
R1Preferably hydrogen atom, benzyl or carbon number are 2~5 cyanoalkyl, more preferably benzyl.
R2It is preferred that being independently of one another in the alkyl or phenyl that hydrogen atom, carbon number are 1~20, the alkyl and the phenyl The hydrogen atom contained can be optionally substituted by a hydroxyl group, and more preferably hydrogen atom, carbon number are 1~20 alkyl or phenyl, further excellent Choosing is the alkyl or phenyl that carbon number is 1~20.
R3And R4It is preferred that being independently of one another the alkyl or phenyl that hydrogen atom, carbon number are 1~20, the alkyl and the benzene The hydrogen atom contained in base can be optionally substituted by a hydroxyl group, and more preferably hydrogen atom, carbon number are 1~20 alkyl or phenyl, enter one The alkyl that step is preferably hydrogen atom or carbon number is 1~20.
If R1~R4For these groups, then there are following tendencies：The shape on the colour filter for the impurity for having several μm or so Into film, the diameter of the conical papilla formed on impurity also diminishes, and the excellent heat resistance of gained film.
Imidazolium compounds（C）Such as 1- methylimidazoles, 2-methylimidazole, 2- hydroxymethylimidazoles, 2- can be enumerated Methyl -4- hydroxymethylimidazoles, 5- hydroxymethyls -4-methylimidazole, 2- ethyl imidazol(e)s, 2- undecyl imidazoles, 2- heptadecyl imidazoles, 1,2- methylimidazoles, 2-ethyl-4-methylimidazole, 4- hydroxymethyl -2- phenyl miaows Azoles, 2- phenylimidazoles, 2- phenyl -2- hydroxymethylimidazoles, 1- benzyls -4-methylimidazole, 1- benzyl -4- methyl Imidazoles, 1- benzyl -4- phenylimidazoles, 1- benzyl -5- hydroxymethylimidazoles, 2-（P-hydroxybenzene）Imidazoles, 1- cyanogen Ylmethyl -2-methylimidazole, 1-（2- cyano ethyls）- 2- hydroxymethylimidazoles, 2,4- diphenyl-imidazoles, 1- cyano group Methyl -2- undecyl imidazoles, 1- cyano methyls -2-ethyl-4-methylimidazole, 1- cyano methyl -2- phenyl Imidazoles, 1-（2- cyano ethyls）- 2-ethyl-4-methylimidazole etc..Wherein be preferably 1- benzyl -4- phenylimidazoles, 2-ethyl-4-methylimidazole, 1-（2- cyano ethyls）- 2-ethyl-4-methylimidazole.They can be used alone, Or two or more is applied in combination.
Imidazolium compounds（C）Content relative to polymer（A）The mass parts of 100 mass parts, preferably 1 mass parts~25, The mass parts of more preferably 3 mass parts~20.Imidazolium compounds（C）Content in above range, have even in there is several μm or so Impurity colour filter on form film, the tendency that the diameter of the conical papilla formed on impurity also diminishes.
Imidazolium compounds（C）Content be more preferably the mass parts of 3 mass parts~15.Imidazolium compounds（C）Content In above range, there is the excellent heat resistance of gained film.
The hardening resin composition of the present invention, which is preferably comprised, to be had in acryloyl group and methylacryloyl extremely Few a kind of group（Hereinafter sometimes referred to "（Methyl）Acryloyl group "）Compound（D）（Hereinafter sometimes referred to "（Methyl）Acrylic acid Compound（D）”）.By containing（Methyl）Acyclic compound（D）, have the tendency of gained film chemical proofing it is excellent.
As with 1（Methyl）Acryloyl group（Methyl）Acyclic compound（D）, can enumerate with as above-mentioned （a）、（b）With（c）Cited compound is identical compound, wherein, preferably（Methyl）Esters of acrylic acid.
As with 2（Methyl）Acryloyl group（Methyl）Acyclic compound（D）, 1,3-butanediol can be enumerated Two（Methyl）Acrylate, 1,3-BDO（Methyl）Acrylate, 1,6- hexylene glycols two（Methyl）Acrylate, ethylene glycol Two（Methyl）Acrylate, diethylene glycol (DEG) two（Methyl）Acrylate, neopentyl glycol two（Methyl）Acrylate, triethylene glycol two（First Base）Acrylate, tetraethylene glycol two（Methyl）Acrylate, polyethyleneglycol diacrylate, pair of bisphenol-A（Acryloxy second Base）Ether, Ethoxylated bisphenol A bis-（Methyl）Acrylate, ethoxylated neopentylglycol two（Methyl）Acrylate, ethoxylation Neopentyl glycol two（Methyl）Acrylate, 3- methyl pentanediols two（Methyl）Acrylate etc..
As with more than 3（Methyl）Acryloyl group（Methyl）Acyclic compound（D）, trihydroxy methyl can be enumerated Propane three（Methyl）Acrylate, pentaerythrite three（Methyl）Acrylate, three（2- hydroxyethyls）Isocyanuric acid three（Methyl） Acrylate, ethoxylated trimethylolpropane three（Methyl）Acrylate, propoxylation trimethylolpropane tris（Methyl）Third Olefin(e) acid ester, pentaerythrite four（Methyl）Acrylate, dipentaerythritol five（Methyl）Acrylate, dipentaerythritol six（Methyl） Acrylate, tripentaerythritol four（Methyl）Acrylate, tripentaerythritol five（Methyl）Acrylate, tripentaerythritol six （Methyl）Acrylate, tripentaerythritol seven（Methyl）Acrylate, tripentaerythritol eight（Methyl）Acrylate, pentaerythrite Three（Methyl）Reactant, the dipentaerythritol five of acrylate and acid anhydrides（Methyl）The reactant of acrylate and acid anhydrides, three seasons Penta tetrol seven（Methyl）Reactant, the caprolactone modification trimethylolpropane tris of acrylate and acid anhydrides（Methyl）Acrylate, Caprolactone modification pentaerythrite three（Methyl）Acrylate, caprolactone modification three（2- hydroxyethyls）Isocyanuric acid three（Methyl） Acrylate, caprolactone modification pentaerythrite four（Methyl）Acrylate, caprolactone modification dipentaerythritol five（Methyl）Propylene Acid esters, caprolactone modification dipentaerythritol six（Methyl）Acrylate, caprolactone modification tripentaerythritol four（Methyl）Acrylic acid Ester, caprolactone modification tripentaerythritol five（Methyl）Acrylate, caprolactone modification tripentaerythritol six（Methyl）Acrylate, Caprolactone modification tripentaerythritol seven（Methyl）Acrylate, caprolactone modification tripentaerythritol eight（Methyl）Acrylate, oneself Lactone-modified pentaerythrite three（Methyl）Reactant, the caprolactone modification dipentaerythritol five of acrylate and acid anhydrides（Methyl）Third Reactant, the caprolactone modification tripentaerythritol seven of olefin(e) acid ester and acid anhydrides（Methyl）Reactant of acrylate and acid anhydrides etc..
As（Methyl）Acyclic compound（D）, preferably with more than 3（Methyl）Acryloyl group（Methyl）Propylene Acid compound（D）, more preferably dipentaerythritol six（Methyl）Acrylate.
（Methyl）Acyclic compound（D）Content relative to polymer（A）100 mass parts, preferably 20~100 mass Part, more preferably 25~70 mass parts.（Methyl）Acyclic compound（D）Content in above range, rewarding film Flatness, reliability and mechanical strength become good tendency.
The hardening resin composition of the present invention preferably comprises solvent（E）.
Solvent（E）It is not particularly limited, solvent usually used in the field can be used.Can be for example from ester solvent （Intramolecular contains-COO-, the solvent without-O-）, ether solvents（Intramolecular contains-O-, molten without-COO- Agent）, ether-ether solvent（Intramolecular contains-COO- and-O- solvent）, ketone solvent（Intramolecular contain-CO-, do not contain- COO- solvent）, alcoholic solvent（Intramolecular contains OH, the solvent without-O- ,-CO- and-COO-）, aromatic hydrocarbon it is molten Selection is used in agent, amide solvent, dimethyl sulfoxide (DMSO) etc..
Ester solvent can enumerate methyl lactate, ethyl lactate, butyl lactate, 2- hydroxy-methyl isobutyl acids, ethyl acetate, N-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl isobutyrate, ethyl butyrate, butyric acid fourth Ester, methyl pyruvate, ethyl pyruvate, Propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, adnoral acetate, Gamma-butyrolacton etc..
Ether solvents can enumerate ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether, ethylene glycol only son Base ether, diethylene glycol monomethyl ether, carbiphene, diethylene glycol monobutyl ehter, propylene glycol monomethyl ether, propane diols list ethyl Ether, propylene glycol monopropyl ether, glycol monobutyl ether, 3- methoxyl groups-n-butyl alcohol, 3- methoxyl group -3- methyl butanols, four Hydrogen furans, oxinane, the dioxane of Isosorbide-5-Nitrae-, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol (DEG) methyl ethyl ether, two Glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole etc..
Ether-ether solvent can enumerate methoxy menthyl acetate, ethyl methoxyacetate, methoxyacetic acid butyl ester, ethyoxyl second Sour methyl esters, ethoxy ethyl acetate, 3- methoxy methyl propionates, 3- methoxypropionates, 3- ethoxypropanoates, 3- ethoxyl ethyl propionates, 2- methoxy methyl propionates, 2- methoxypropionates, 2- methoxy propyls propyl propionate, 2- second Epoxide methyl propionate, 2- ethoxyl ethyl propionates, 2- methoxyl groups -2 Methylpropionic acid methyl esters, 2- ethyoxyl -2- methyl Ethyl propionate, 3- methoxybutyls acetic acid esters, 3- methyl -3- methoxybutyls acetic acid esters, propylene glycol monomethyl ether Ester, propylene glycol monoethyl acetic acid esters, propylene glycol monopropyl ether acetic acid esters, ethylene glycol single methyl ether acetic acid esters, ethylene glycol list second Base ether acetic acid ester, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ehter acetic acid esters etc..
Ketone solvent can enumerate 4- hydroxy-4-methyl-2-pentanones, acetone, 2- butanone, 2-HEPTANONE, 3- heptanone, 4- heptanone, 4-methyl-2 pentanone, cyclopentanone, cyclohexanone, isophorone etc..
Alcoholic solvent can enumerate methanol, ethanol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, propane diols, glycerine etc..
Aromatic hydrocarbon solvents can enumerate benzene,toluene,xylene, mesitylene etc..
Amide solvent can enumerate DMF, DMA, 1-METHYLPYRROLIDONE Deng.
These solvents may be used alone, or two or more kinds may be used in combination.
In above-mentioned solvent, from the point of view of coating, drying property, the boiling point under preferably 1atm is 120 DEG C~180 DEG C Organic solvent.Wherein, preferably propylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol (DEG) methyl ethyl ether, 3- methoxybutyls acetic acid esters, 3- methoxyl groups-n-butyl alcohol and the mixed solvent containing them.
Solvent in hardening resin composition（E）Content relative to hardening resin composition, preferably 60~95 Quality %, more preferably 70~95 mass %.In other words, the solid composition of hardening resin composition is preferably 5~40 matter Measure %, more preferably 5~30 mass %.Wherein, solid composition refers to eliminate solvent from hardening resin composition（E）'s Amount.Solvent（E）Content in above range, be coated with the flatness of the film of hardening resin composition have the tendency of it is high.
The hardening resin composition of the present invention preferably comprises antioxidant（F）.Antioxidant（F）It can enumerate for example The 2- tert-butyl groups -6-（The 3- tert-butyl group -2- hydroxy-5-methyl base benzyls）- 4- aminomethyl phenyls acrylate, 2- ［ 1- （2- hydroxyl -3,5- di-tert-pentyl-phenyls）Ethyl ］ -4,6- di-tert-pentyl-phenyls acrylate, 6- ［ 3-（The tertiary fourths of 3- Base -4- hydroxy-5-methyl base phenyl）Propoxyl group ］ -2,4,8,10- tetra-tert dibenzo ［ d, f ］ ［ 1,3,2 ］ dioxas Double ［ 2- { the 3- of phospha cycloheptene, 3,9-（3- tertiary butyl-4-hydroxy -5- aminomethyl phenyls）Propionyloxy } -1,1- bis- Methylethyl ］ -2,4,8,10- tetra- oxaspiro ［ 5.5 ］ hendecanes, 2,2 '-di-2-ethylhexylphosphine oxide（The 6- tert-butyl group -4- methyl Phenol）, 4,4 '-butylidene is double（The 6- tert-butyl group -3- methylphenols）, 4,4 '-thiobis（The 2- tert-butyl group -5- methyl Phenol）, 2,2 '-thiobis（6- tert-butyl-4-methyl-Phenols）, 3,3 '-thio-2 acid two（Dodecyl）Ester, 3, 3 '-thio-2 acid two（Myristyl）Ester, 3,3 '-thio-2 acid two（Octadecyl）Ester, pentaerythrite four（3- ten Dialkyl propionic ester）, 1,3,5- tri-（3,5- di-tert-butyl-4-hydroxyl benzyls）- 1,3,5-triazines -2,4,6 （1H, 3H, 5H）- triketone, 3,3 ', 3 ", 5,5 ', 5 "-six tert-butyl group-a, a ', a "-（Mesitylene -2,4, the bases of 6- tri-） Three-paracresol, ［ 3- of pentaerythrite four（3,5- di-tert-butyl-hydroxy phenyls）Propionic ester ］, 2,6- di-t-butyls- 4- methylphenols etc..IRGANOX can be used（Registration mark）3114（BASF ジ ャ パ Application society system）Deng commercially available product.
Antioxidant（F）Content relative to polymer（A）100 mass parts, are the mass parts of 0.1 mass parts~5, are preferably The mass parts of 0.5 mass parts~3.Antioxidant（F）Content within the above range when, the film of gained has heat resistance and pencil hard The excellent tendency of degree.Antioxidant（F）Content more than 5 mass parts when, pencil hardness is likely to decrease.
The hardening resin composition of the present invention can contain surfactant（G）.Surfactant can be enumerated for example Silicone type surface active agent, fluorine system surfactant, silicone type surface active agent with fluorine atom etc..
Silicone type surface active agent can enumerate the surfactant with siloxanes key.Specifically, ト ー can be enumerated レ シ リ コ ー Application DC3PA, ibid SH7PA, ibid DC11PA, ibid SH21PA, ibid SH28PA, ibid SH29PA, ibid SH30PA, polyether modified silicon oil SH8400（Trade name：Eastern レ ダ ウ コ ー ニ Application グ（Strain）System）、KP321、KP322、 KP323、KP324、KP326、KP340、KP341（SHIN-ETSU HANTOTAI's chemical industry（Strain）System）、TSF400、TSF401、TSF410、 TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460（モメンティブ・パフォーマンス・ マ テ リ ア Le ズ ジ ャ パ Application contracts commercial firm system）Deng.
Fluorine system surfactant can be enumerated with fluorocarbon chain（Off Le オ ロ カ ー ボ ン Lock）Surfactant.
Specifically, Off ロ リ ナ ー ト can be enumerated（Registration mark）FC430, ibid FC431（Sumitomo ス リ ー エ system（Strain） System）；メガファック（Registration mark）F142D, ibid F171, ibid F172, ibid F173, ibid F177, ibid F183, Ibid F552, ibid F553, ibid F554, ibid F555, ibid F556, ibid F558, ibid F559, ibid R30（DIC （Strain）System）；エフトップ（Registration mark）EF301, ibid EF303, ibid EF351, ibid EF352（Mitsubishi's マ テ リ ア Le electricity Son chemical conversion（Strain）System）；サーフロン（Registration mark）S381, ibid S382, ibid SC101, ibid SC105（Asahi Glass （Strain）System）；E5844（（Strain）The research of ダ イ キ Application Off ァ イ Application ケ ミ カ Le is made）Deng.
As the silicone type surface active agent with fluorine atom, the surface with siloxanes key and fluorocarbon chain can be enumerated Activating agent.Specifically, メ ガ Off ァ ッ Network can be enumerated（Registration mark）It is R08, ibid BL20, ibid F475, ibid F477, same Upper F443（DIC（Strain）System）Deng.It is preferred that enumerating メ ガ Off ァ ッ Network（Registration mark）F475.
Surfactant（G）Relative to hardening resin composition, it is the mass % of 0.001 mass %~0.2, is preferably The mass % of 0.002 mass %~0.1 mass %, more preferably 0.01 mass %~0.05.Lived by containing surface with the scope Property agent, can make the flatness of film good.
As needed, can in the hardening resin composition of the present invention containing filler, other high-molecular compound, The additive of hot radical producing agent, ultra-violet absorber, chain-transferring agent, adhesion promoter etc..
Filler can enumerate glass, silica, aluminum oxide etc..
As other high-molecular compounds, the heat-curing resin or poly- second of maleimide resin etc. can be enumerated Thermoplastic resin of enol, polyacrylic acid, polyalkylene glycol monoalkyl ether, poly- fluoroalkyl, polyester, polyurethane etc. etc..
Hot radical producing agent can specifically enumerate 2, and 2 '-azo is double（2- methyl valeronitriles）, 2,2 '-azo is double（2, 4- methyl pentane nitriles）Deng.
Ultra-violet absorber specifically, can enumerate 2-（The 3- tert-butyl group -2- hydroxy-5-methyl base phenyl）- 5- chlorobenzotriazoles, alkoxy benzophenone etc..
Chain-transferring agent can enumerate lauryl mercaptan, 2,4- diphenyl -4-methyl-1-pentene etc..
Adhesion promoter can enumerate such as vinyltrimethoxy silane, VTES, vinyl Three（2- methoxy ethoxies）Silane, 3- glycidyloxypropyls trimethoxy silane, 3- glycidoxypropyls Dimethoxysilane, 3- glycidoxypropyls dimethoxysilane, 3- glycidoxypropyls diethoxy silane, 2-（3,4- epoxycyclohexyls）Ethyl trimethoxy silane, 3- chloropropylmethyldimethoxysilanes, 3- chloropropyl front threes TMOS, 3- methacryloxypropyl trimethoxy silanes, 3-mercaptopropyi trimethoxy silane, 3- sulfanyls Propyl trimethoxy silicane, 3- NCOs propyl-triethoxysilicane, N-2-（Amino-ethyl）- 3- aminopropyls Methyl dimethoxysilane, N-2-（Amino-ethyl）- 3-amino propyl methyl diethoxy silane, N-2-（Amino second Base）- 3- TSL 8330s, N-2-（Amino-ethyl）- 3-amino propyl methyl diethoxy silane, 3- TSL 8330s, APTES, N- phenyl -3- aminopropyl trimethoxies Silane, N- phenyl-APTES etc..
The hardening resin composition of the present invention contains substantially no Photoepolymerizationinitiater initiater.That is, in the curability of the present invention In resin combination, Photoepolymerizationinitiater initiater is, for example, less than 1 mass %, preferably smaller than 0.5 matter relative to the content of all compositions Measure %.As Photoepolymerizationinitiater initiater, alkyl phenones compound, triaizine compounds, acylphosphine oxide compound and oxime can be enumerated Compound etc..
In addition, the hardening resin composition of the present invention contains substantially no the colouring agent of pigment and dyestuff etc..That is, at this In the hardening resin composition of invention, colouring agent is, for example, to be less than 1 mass % relative to the content of all compositions, preferably small In 0.5 mass %.
In addition, the hardening resin composition of the present invention is filled into the quartz cell that light path is 1cm, spectrophotometric is used Meter is when determining measure transmission coefficient under conditions of wavelength is 400~700nm, and average transmission coefficient is preferably more than 70%, more Preferably more than 80%.
The hardening resin composition of the present invention when being formed as film, the average transmission coefficient of film be preferably 90% with On, more preferably more than 95%.The average transmission coefficient is for being heating and curing（Such as 100~250 DEG C, 5 minutes~3 hours）Afterwards Thickness be 3 μm of film, use spectrophotometer determining average value when being determined under conditions of wavelength is 400~700nm. Thus, it is possible to provide the transparent excellent film in visible region.
The hardening resin composition of the present invention can utilize existing known method by polymer（A）, epoxy resin（B） And imidazolium compounds（C）, it is as needed（Methyl）Acyclic compound（D）Or solvent, other additive etc. stir on one side, While mixing to be manufactured.After mixing, filtered preferably by aperture for 0.05~1.0 μm or so of filter.
Using the present invention hardening resin composition formation film, can by by the present invention curable resin group Compound is coated on substrate, and its solidification is made using heat.
Substrate can enumerate glass, metal, plastics etc., and colour filter, various dielectric films or conduction can be formed on substrate Film, drive circuit etc..
Spin coater, slit ＆ spin coaters, slit coater, ink discharge device can be used（インクジェット）, roller The various apparatus for coating of painting machine, dip coater etc., the hardening resin composition of the present invention is coated on substrate.
It is preferred that after coating, being dried in vacuo or preliminary drying, the volatile ingredient of solvent etc. is removed.
By the way that the film for eliminating volatile ingredient to be implemented to 150~240 DEG C, 10~120 minutes of rear baking, painting can be formed Film.
The film so obtained is for example as covering for being used in liquid crystal display device, organic EL display or Electronic Paper Cap rock is useful.Alternatively, it is also possible in the display device component for touch panel etc..Thereby, it is possible to high finished product The display device of film of the rate manufacture with high-quality.
Embodiment
Hereinafter, the present invention is illustrated by embodiment in more detail.Example in " % " and " part " unless otherwise specified, All it is quality % and mass parts.
（Synthesis example 1）
Nitrogen was flowed into 0.02L/ minutes in the flask with reflux condenser, dropping funel and mixer, nitrogen is formed Atmosphere, loads 140 parts of diethylene glycol (DEG) ethyl-methyl ether, stirs while being heated to 70 DEG C.Then modulation makes 40 parts of methacrylic acid； And monomer（I-1）And monomer（II-1）The mixture { monomer in mixture（I-1）：Monomer（II-1）Mol ratio =50：50 } 360 parts, the solution being dissolved in 190 parts of diethylene glycol (DEG) ethyl-methyl ether, should with 4 hours using dropping funel Solution is added drop-wise in the flask of 70 DEG C of insulations.
【Change 8】
On the other hand, polymerization initiator 2 is made, 2 '-azo is double（2,4- methyl pentane nitriles）30 parts are dissolved in diethylene glycol (DEG) second Solution is formed in 240 parts of ylmethyl ether, the solution is added drop-wise in flask with 5 hours using other dropping liquid pump.Polymerization is drawn After the completion of dropwise addition for sending out agent solution, kept for 4 hours at 70 DEG C, be subsequently cooled to room temperature, obtained solid composition and be total to for 42.3% Polymers（Resin A a）Solution.The Resin A a of gained weight average molecular weight（Mw）For 8000, molecular weight distribution（Mw/Mn）For 1.91, acid number is 60mg-KOH/g（The acid number of solid composition conversion）.
Resin A a has following construction unit.
【Change 9】
（Synthesis example 2）
Nitrogen was flowed into 0.02L/ minutes in the flask with reflux condenser, dropping funel and mixer, nitrogen is formed Atmosphere, adds 3- methoxyl groups-mass parts of n-butyl alcohol 200 and the mass parts of 3- methoxybutyls acetic acid esters 105, stir while It is heated to 70 DEG C.Then, by 60 parts of methacrylic acid and monomer（I-1）And monomer（II-1）Mixture { in mixture Monomer（I-1）：Monomer（II-1）Mol ratio=50：50 } 240 parts are dissolved in 140 parts of 3- methoxybutyls acetic acid esters In, solution is prepared, the solution is added drop-wise to insulation in 70 DEG C of flask with 4 hours using dropping liquid pump.
On the other hand, by polymerization initiator 2,2 '-azo is double（2,4- methyl pentane nitriles）30 parts are dissolved in 3- methoxyl groups Form solution in 225 parts of butylacetic acid ester, by the solution with other dropping funel, spend be added drop-wise in flask within 4 hours.Poly- After the completion of dropwise addition for the solution for closing initiator, kept for 4 hours at 70 DEG C, be subsequently cooled to room temperature, obtaining solid composition is 32.6% copolymer（Resin A b）Solution.The Resin A b of gained weight average molecular weight（Mw）For 13,400, molecular weight distribution （Mw/Mn）For 2.50, acid number is 113.9mg-KOH/g（The acid number of solid composition conversion）.Resin A b has following structure list Member.
【Change 10】
The Resin A a and Resin A b of gained weight average molecular weight（Mw）And number-average molecular weight（Mn）Measure using GPC method, Carry out under the following conditions.
Device；K2479（（Strain）Shimadzu Seisakusho Ltd.'s system）
Pillar；SHIMADZU Shim-pack GPC-80M
Column temperature；40℃
Solvent；THF（Tetrahydrofuran）
Flow velocity；1.0mL/min
Detector；RI
Correction standard substance；TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A- 500（Dong ソ ー（Strain）System）.
The weight average molecular weight and the ratio of number-average molecular weight that polystyrene obtained above is converted（Mw/Mn）It is used as molecule Amount distribution.
（Embodiment 1~8 and comparative example 1）
The composition of table 1 is mixed, hardening resin composition is obtained.
【Table 1】
In table 1, unless otherwise specified, unit is " part ".Polymer（A）Containing number represent solid composition convert Mass parts.
Polymer（A）；Aa；The Resin A a obtained in synthesis example
Polymer（A）；Ab；The Resin A b obtained in synthesis example
Epoxy resin（B）：Ba：Bisphenol A type epoxy resin（JER157S70；Mitsubishi Chemical（Strain）System）（Acid number： 0.1mgKOH/g, epoxide equivalent：210g/eq）
Imidazolium compounds（C）：Ca：1- benzyl -2- phenylimidazoles（キュアゾール1B2PZ；Four countries' chemical conversion industry （Strain）System）
【Change 11】
Imidazolium compounds（C）：Cb：1-（2- cyano ethyls）- 2-ethyl-4-methylimidazole（キュアゾール 2E4MZ-CN；Four countries' chemical conversion industry（Strain）System）
【Change 12】
Imidazolium compounds（C）：Cc：2-ethyl-4-methylimidazole（キュアゾール2E4MZ；Four countries' chemical conversion industry （Strain）System）
【Change 13】
（Methyl）Acyclic compound（D）：Da：Dipentaerythritol acrylate（KAYARAD（Registration mark） DPHA； Japanese chemical drug（Strain）System）
Antioxidant（F）；Fa；1,3,5- tri-（4- hydroxyl -3,5- di-t-butyl benzyls）- 1,3,5-triazines -2, 4,6（1H, 3H, 5H）- triketone（IRGANOX（Registration mark）3114；BASFジャパン（Strain）System）
Solvent（E）；Ea；Propylene glycol monomethyl ether
Solvent（E）；Eb；3- methoxyl groups-n-butyl alcohol
Solvent（E）；Ec；Diethylene glycol (DEG) ethyl-methyl ether
Solvent（E）；Ed；3- ethoxy ethyl propionates
Solvent（E）；Ee；3- methoxybutyl acetic acid esters
By solvent（E）Mixing, so that the solid component amount of hardening resin composition is " the solid component amount of table 1 （%）", solvent（E）In solvent composition（Ea）~（Ee）Value represent solvent（E）In mass ratio.
＜ viscosimetric analysis ＞
For the hardening resin composition of gained, respectively using viscosimeter（Type；TV-30；Eastern machine industry（Strain）System） To determine viscosity.As a result it is shown in table 2.
The transmission coefficient ＞ of ＜ hardening resin compositions
For the hardening resin composition of gained, respectively using UV, visible light near infrared spectrometer（V-650；Day This light splitting（Strain）System）（Quartz cell, light path；1cm）Determine 400~700nm average transmission coefficient（%）.As a result it is shown in table 2.
The transmission coefficient ＞ of ＜ films
By the square glass substrate that the length of side is 2 inches（#1737；コ ー ニ Application グ societies system）Successively with neutral lotion, After water and isopropanol washing, it is dried.On the glass substrate, spin coating hardening resin composition, so that the film after rear baking Thickness is 2.0 μm.Then, in cleaning oven, the preliminary drying of 10 minutes is carried out at 90 DEG C.Then, after 230 DEG C are carried out 40 minutes Dry, obtain film.For the film of gained, microspectrophotometer device is used（OSP-SP200；OLYMPUS societies system）Determine 400~700nm average transmission coefficient（%）.As a result it is shown in table 2.
The measure ＞ of conical papilla on ＜ impurity
By a diameter of 8 μm of acrylic beads（アクリルビーズ）（Trade name：エポスターYS77；（Strain）Japan touches Matchmaker's system）It is dispersed in toluene, makes 0.01% dispersion liquid.It is thin for the chromium formed on 15cm square glass substrate in the length of side On film, the dispersion liquid is coated with spin coater, the experiment substrate of acrylic beads has been spread.
On the experiment substrate, respectively using slit die coating machine（スリットダイコーター）（Tall and erect ダ イ -100 ITOCHU production machine (strain) system）Institute is coated with using the condition as 1.5 μm of the thickness after solidification and with the coating speed of 70mm/ seconds The hardening resin composition obtained.Then, pressure Reduction Dryer is utilized（VCDマイクロテック（Strain）System）It is dried, until Degree of decompression reaches 0.5torr.On hot plate, in 90 DEG C of preliminary dryings 2 minutes, further make after it dries, 40 points are carried out at 230 DEG C The rear baking of clock, forms film.
On the film of gained, centered on the acrylic beads on the experiment substrate for being dispersed in bottom, formed coniform Projection.Use petrographic microscope（× 100 times）The projection is observed, the newton of the concentric circles observation using center as acrylic beads is determined The diameter of the most peripheral of ring.Using the diameter of most peripheral as conical papilla diameter.As a result it is shown in table 2.
＜ Evaluation of Heat Tolerance ＞
Slit die coating machine is used respectively（Tall and erect ダ イ -100 ITOCHUs production machine (strain) system）Using the thickness after solidification as 2.0 Condition as μm and with the hardening resin composition obtained by the coating of the coating speed of 120mm/ seconds.Then, it is dry using decompression Dry machine（VCDマイクロテック（Strain）System）Dry it, until degree of decompression reaches 0.5torr.On hot plate, at 90 DEG C Preliminary drying 2 minutes, further makes after its drying, and the rear baking of 40 minutes is carried out at 230 DEG C, film is made.By the film at 240 DEG C Heated 4 hours in cleaning oven, determine the transmission coefficient before and after heating.By the measured value of gained, transmission system is tried to achieve according to the following formula Number change.When variations in transmissivity is more than 92%, it can be determined that heat resistance is good.As a result it is shown in table 2.
Variations in transmissivity（%）=Tb/Ta×100
In formula, TbRepresent the transmission coefficient before 400nm heating, TaRepresent the transmission coefficient after 400nm heating.
【Table 2】
From the above results, according to the hardening resin composition of the present invention, the shape on the substrate for exist impurity Into film, the diameter of the conical papilla formed on impurity is also small.It is possible to further confirm by the curability tree of the present invention The heat resistance for the film that oil/fat composition is obtained is high.Thus, it is known that the film pair obtained by the hardening resin composition of the present invention Show that bad few liquid crystal display device is useful in manufacture.
Industry utilizability
According to the hardening resin composition of the present invention, formed and applied on the colour filter for the impurity for there are several μm or so Film, the diameter of the conical papilla formed on impurity is also small.

Claims (5)

1. hardening resin composition, it contains following（A）、（B）With（C）,（C）Content relative to（A）100 mass parts are 3 The mass parts of mass parts~20,（B）Content relative to（A）100 mass parts are 1~100 mass parts,
（A）Have containing coming from the construction unit for being selected from least one of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and coming from The addition polymers of the construction unit of the unsaturated compound of Oxyranyle,
（B）Epoxy resin selected from least one of diglycidyl ether type epoxy resin and glycidyl ester type epoxy resin,
（C）Formula（1）Shown compound,
【Change 1】
Formula（1）In, R1Represent the cyano group that alkyl, phenyl, benzyl or carbon number that hydrogen atom, carbon number are 1~20 are 2~5 Alkyl,
R2~R4Represent that hydrogen atom, halogen atom, carbon number are former for 1~20 alkyl, phenyl, nitro or carbon independently of each other Subnumber is 1~20 acyl group, and the alkyl can be optionally substituted by a hydroxyl group with the hydrogen atom contained in the phenyl.
2. hardening resin composition as claimed in claim 1, wherein,（A）Content relative to（A）Content and（B）'s Content adds up to the mass % of 50 mass %~99.
3. hardening resin composition as claimed in claim 1, wherein, further containing with selected from acryloyl group and methyl The compound of at least one of acryloyl group group.
4. film, it is formed using the hardening resin composition described in claim 1.
5. display device, it contains the film described in claim 4.
CN201210170208.9A 2011-05-30 2012-05-29 Hardening resin composition Active CN102807778B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011119911 2011-05-30
JP2011-119911 2011-05-30

Publications (2)

Publication Number Publication Date
CN102807778A CN102807778A (en) 2012-12-05
CN102807778B true CN102807778B (en) 2017-11-07

Family

ID=47231654

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210170208.9A Active CN102807778B (en) 2011-05-30 2012-05-29 Hardening resin composition

Country Status (4)

Country Link
JP (1) JP6193542B2 (en)
KR (1) KR101928100B1 (en)
CN (1) CN102807778B (en)
TW (1) TWI538948B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110452601A (en) * 2019-08-24 2019-11-15 深圳市交通工程试验检测中心有限公司 A kind of road mark paint and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101445578A (en) * 2007-11-29 2009-06-03 住友化学株式会社 Heat curing resin combination
CN101738859A (en) * 2008-11-18 2010-06-16 住友化学株式会社 Photosensitive resin composition and display
CN102040795A (en) * 2009-10-15 2011-05-04 住友化学株式会社 Resin composition

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05163331A (en) * 1991-12-13 1993-06-29 Sumitomo Chem Co Ltd Epoxy resin composition
JP2715792B2 (en) * 1992-02-13 1998-02-18 信越化学工業株式会社 Light transmitting epoxy resin composition and optical semiconductor device
JP2007182539A (en) * 2005-12-06 2007-07-19 Jsr Corp Resin composition, method for forming preventive film of color filter and preventive film of the color filter
JP5224030B2 (en) * 2007-03-22 2013-07-03 Ｊｓｒ株式会社 Thermosetting resin composition, protective film and method for forming protective film
JP5279703B2 (en) * 2007-05-11 2013-09-04 株式会社ダイセル Light and / or thermosetting copolymer, curable resin composition, and cured product
KR101002736B1 (en) * 2008-08-13 2010-12-21 제일모직주식회사 Thermocurable composition for protective film of color filter, and color filter using same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101445578A (en) * 2007-11-29 2009-06-03 住友化学株式会社 Heat curing resin combination
CN101738859A (en) * 2008-11-18 2010-06-16 住友化学株式会社 Photosensitive resin composition and display
CN102040795A (en) * 2009-10-15 2011-05-04 住友化学株式会社 Resin composition

Also Published As

Publication number Publication date
KR20120134026A (en) 2012-12-11
KR101928100B1 (en) 2018-12-11
JP2013010939A (en) 2013-01-17
TWI538948B (en) 2016-06-21
JP6193542B2 (en) 2017-09-06
TW201313816A (en) 2013-04-01
CN102807778A (en) 2012-12-05

Similar Documents

Publication Publication Date Title
CN103048881A (en) Curable resin composition
CN102645844B (en) Colored curable resin composition
CN102445844B (en) Photosensitive composition
TWI770368B (en) Compound, colored resin composition, color filter, and display device
CN102445851B (en) Coloring photosensitive combination
CN103365080A (en) Colored photopolymer composition
CN102636957B (en) Photosensitive composition and compound
CN102809897B (en) Hardening resin composition
CN108241258A (en) Liquid crystal display device resin combination, liquid crystal display device film and copolymer
CN107272331A (en) Hardening resin composition and cured film
CN102807778B (en) Hardening resin composition
CN103116247B (en) Colored curable resin composition
CN107434941A (en) Resin combination and cured film
CN102866584B (en) Photosensitive polymer combination
CN103421403B (en) Hardening resin composition
CN103116244B (en) Hardening resin composition
CN106662809A (en) Photosensitive coloring resin composition
CN102372825B (en) Curable resin composition
CN106795376A (en) A kind of compound and the colored curable resin composition comprising the compound
CN102453298B (en) Hardening resin composition
CN108459468A (en) Resin combination and cured film
CN102372888B (en) Hardening resin composition
CN102850893A (en) Curable resin composition
CN103293854A (en) Photosensitive resin composition
CN101792568A (en) Cured film

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant