CN107075083A - Composition - Google Patents

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Publication number
CN107075083A
CN107075083A CN201680003422.1A CN201680003422A CN107075083A CN 107075083 A CN107075083 A CN 107075083A CN 201680003422 A CN201680003422 A CN 201680003422A CN 107075083 A CN107075083 A CN 107075083A
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CN
China
Prior art keywords
compound
epoxy compound
aromatic
composition
acid
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CN201680003422.1A
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Chinese (zh)
Inventor
高日俊辅
大野泰延
长坂辉
长坂一辉
松土和彦
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Adeka Corp
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Asahi Denka Kogyo KK
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Publication of CN107075083A publication Critical patent/CN107075083A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Epoxy Resins (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

A kind of composition, it is characterised in that as cationically polymerizable organic substance mixture (1), include aromatic epoxy compound (1 1)；Cycloaliphatic epoxy (1 2A) or aliphatic epoxy compound (1 2B)；And multifunctional aliphatic oxetane compound (1 3), aromatic epoxy compound (1 1) is main component.As above-mentioned aromatic epoxy compound (1 1), at least one of group of epoxides of the glycidol ether selected from phenols, the glycidol ether compound of aromatic compound with more than 2 alcohol hydroxyl groups, the glycidol ether compound of Polyphenols, the ethylene oxidic ester of benzoic acids, the ethylene oxidic ester of polynary acids, Styryl oxide or divinylbenzene is preferably comprised.

Description

Composition
Technical field
Bonding agent the present invention relates to composition and comprising said composition.
Background technology
Cationically polymerizable composition is used in the fields such as ink, coating, various coating agents, bonding agent, optical component.
For example, in following patent documents 1~4, disclosing various Photocurable adhesive agents.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2011-236389 publications
Patent document 2：Japanese Unexamined Patent Publication 2012-149262 publications
Patent document 3：No. 2008/111584 publication of International Publication
Patent document 4：No. 2015/005211 publication of International Publication
The content of the invention
Invent problem to be solved
It is an object of the invention to provide the composition of curability, cementability and excellent heat resistance.
Method for solving problem
The present invention is carried out based on above-mentioned cognition, and above-mentioned purpose, described group are reached by providing a kind of composition Compound is characterised by, as (1) cationically polymerizable organic substance mixture, is included aromatic epoxy compound (1-1)；Fat Ring type epoxide (1-2A) or aliphatic epoxy compound (1-2B)；And multifunctional aliphatic oxetane compound (1-3), aromatic epoxy compound (1-1) is main component.
In addition, the present invention provides the bonding agent for including above-mentioned composition.
Invention effect
The composition of the present invention is due to curability and excellent in adhesion, so particularly useful as bonding agent.
Embodiment
Hereinafter, to the present invention composition and the bonding agent comprising said composition are described in detail.
In above-mentioned (1) the cationically polymerizable organic substance mixture used in the present invention, the sun of the mixture is constituted Photopolymerizable organic substance is to cause producing high-molecular or friendship using the cationic polymerization initiators activated by light irradiation Join the compound of reaction.In the composition of the present invention, as cationically polymerizable organic substance, aromatic epoxy compound is used (1-1)；Cycloaliphatic epoxy (1-2A) and/or aliphatic epoxy compound (1-2B)；And multifunctional aliphatic oxa- ring Butane compound (1-3).
Above-mentioned aromatic epoxy compound (1-1) refers to the epoxide for including aromatic rings, is used as the aromatic epoxies The specific example of compound, can include phenol, cresols, butylphenol etc. with least one aromatic ring monohydric phenol or its The glycidol ether compounds of alkylene oxide adducts, such as bisphenol-A, Bisphenol F or the further addition epoxyalkane on them Compound glycidol ether compound or Epoxy novolac resin；Resorcinol or hydroquinones, catechol etc. have 2 The glycidol ether of the aromatic compound of phenolic hydroxyl group above；Benzene dimethanol or benzene diethanol, the butanol of benzene two etc. have 2 The glycidol ether compound of the aromatic compound of alcohol hydroxyl group above；Phthalic acid, terephthalic acid (TPA), trimellitic acid etc. The benzene first such as ethylene oxidic ester, benzoic acid or the toluic acid of the polyacid aromatic compound with the carboxylic acids of more than 2, naphthoic acid Epoxides of the ethylene oxidic ester of acids, Styryl oxide or divinylbenzene etc..
Wherein, as above-mentioned aromatic epoxy compound (1-1), containing the glycidol ether selected from phenols, with 2 with On the glycidol ether compound of aromatic compound of alcohol hydroxyl group, the glycidol ether compound of Polyphenols, benzoic acids In ethylene oxidic ester, the ethylene oxidic ester of polynary acids, the group of the epoxides of Styryl oxide or divinylbenzene at least A kind of Tg due to composition is uprised, it is advantageous to.
As above-mentioned aromatic epoxy compound (1-1), the compound that epoxide equivalent is 80~500 is because curability is excellent It is different, it is advantageous to.
As above-mentioned aromatic epoxy compound (1-1), the aromatic epoxy compound of commercially available product can be used, for example may be used Include Denacol EX-121, Denacol EX-141, Denacol EX-142, Denacol EX-145, Denacol EX- 146、Denacol EX-147、Denacol EX-201、Denacol EX-203、Denacol EX-711、Denacol EX- 721、On Court EX-1020、On Court EX-1030、On Court EX-1040、On Court EX-1050、On Court EX-1051、On Court EX-1010、On Court EX-1011、On Court 1012(Nagase ChemteX Corporation systems)；OGSOL PG-100、OGSOL EG-200、OGSOL EG-210、OGSOL EG-250(Osaka Gas Chemicals Co., Ltd. system)；HP4032, HP4032D, HP4700 (DIC societies system)；(aurification is lived to ESN-475V by Nippon Steel Society's system)；EPIKOTE YX8800 (society of Mitsubishi Chemical system)；(day is oily by Mar proof G-0105SA, Mar proof G-0130SP Society's system)；Epiclon N-665, Epiclon HP-7200 (DIC societies system)；EOCN-1020、EOCN-102S、EOCN-103S、 EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L (Japanese chemical drug society System)；Adeka Glycirol ED-501、Adeka Glycirol ED-509、Adeka Glycirol ED-529、Adeka Resin EP-4000、Adeka Resin EP-4005、Adeka Resin EP-4100、Adeka Resin EP-4901 (ADEKA societies system)；TECHMOREVG-3101L (PRINTEC, INC. system) etc..
As above-mentioned aromatic epoxy compound (1-1), containing at least one multi-functional epoxy compound from curability and From the viewpoint of cementability preferably.The composition of the present invention is preferably in the mass of (1) cationically polymerizable organic substance mixture 100 In part, the polyfunctional aromatic epoxy compound (1-1) containing 30~70 mass parts, further preferably 35~60 mass parts.
As above-mentioned cycloaliphatic epoxy (1-2A) specific example, it can include with least one ester ring type ring Polyalcohol poly epihydric alcohol etherate or the compound containing cyclohexene ring or cyclopentene ring is obtained with oxidant epoxidation The compound containing 7-oxa-bicyclo[4.1.0 or cyclopentane epoxide arrived.Hydrogenated bisphenol A diglycidyl ether, 3,4- rings can for example be included Oxygen cyclohexyl methyl -3,4- epoxycyclohexane carboxylates, 3,4- epoxy radicals -1- methylcyclohexyl -3,4- epoxy radicals -1- methyl oneself Alkane carboxylate, 6- methyl -3,4- epoxycyclohexyl-methyl -6- methyl -3,4- epoxycyclohexane carboxylates, 3,4- epoxy radicals -3- Methylcyclohexylmethyl -3,4- epoxy radicals -3- methylcyclohexanecarboxylic acids ester, 3,4- epoxy radicals -5- methylcyclohexylmethyls -3,4- Epoxy radicals -5- methylcyclohexanecarboxylic acids ester, double (3,4- epoxycyclohexyl-methyls) adipate esters, 3,4- epoxy radicals -6- methyl rings Cyclohexane carboxylic-acid ester, di-2-ethylhexylphosphine oxide (3,4- 7-oxa-bicyclo[4.1.0s), propane -2,2- diyls-bis- (3,4- 7-oxa-bicyclo[4.1.0s), 2,2- are double (3,4- epoxycyclohexyls) propane, bicyclopentadiene diepoxide, ethylenebis (3,4- epoxycyclohexane carboxylates), epoxy Di-2-ethylhexyl hexahydrophthalate, epoxy di-2-ethylhexyl hexahydrophthalate, 1- epoxy ethyl -3,4- epoxy hexamethylenes Alkane, 1,2- epoxy radicals -2- epoxy ethyls hexamethylene, australene olefinic oxide, limonene dioxide etc..
As cycloaliphatic epoxy (1-2A), preferably epoxide equivalent is 80~500 cycloaliphatic epoxy.
As above-mentioned cycloaliphatic epoxy (1-2A), the cycloaliphatic epoxy of commercially available product can be used, for example Celloxide 2021P, Celloxide 2081, the Celloxide 2000, (Daicel of Celloxide 3000 can be included Corporation systems) etc..
Above-mentioned aliphatic epoxy compound (1-2B) refer to be not classified as above-mentioned aromatic epoxy compound (1-1) or The epoxide of cycloaliphatic epoxy (1-2A), as the specific example of the aliphatic epoxy compound, can be included Monofunctional epoxy compound, the aliphatic polyols such as glycidol ether compound, the ethylene oxidic ester of alkyl carboxylic acid of aliphatic alcohol Or the multifunctional ring such as poly epihydric alcohol etherate, the poly glycidyl ester of aliphatic long-chain polyacid of its alkylene oxide adducts Oxygen compound.As representational compound, allyl glycidyl ether, butyl glycidyl ether, 2- ethyl hexyls can be included The mixed alkyl glycidol ether of base glycidol ether, C12~13,1,4- butanediol diglycidyl ethers, 1,6-HD two contract Water glycerin ether, the triglycidyl ether of glycerine, the triglycidyl ether of trimethylolpropane, four glycidols of D-sorbite Ether, six glycidol ethers of dipentaerythritol, neopentylglycol diglycidyl ether, the diglycidyl ether of polyethylene glycol, poly- third The glycidol ether of the polyalcohols such as the diglycidyl ether of glycol, in addition by fat such as propane diols, trimethylolpropane, glycerine Poly epihydric alcohol etherate, the fat of PPG obtained from the one kind or two or more epoxyalkane of addition on fat race polyalcohol The 2-glycidyl ester of fat race long-chain biatomic acid.And then, the monoglycidyl ether or senior fat of aliphatic higher alcohol can be included Ethylene oxidic ester, epoxidised soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidised soybean oil, the epoxy of fat acid Change polybutadiene etc..
As aliphatic epoxy compound (1-2B), preferably epoxide equivalent is 80~500 aliphatic epoxy compound.
As above-mentioned aliphatic epoxy compound (1-2B), the aliphatic epoxy compound of commercially available product can be used, for example Denacol EX-121, Denacol EX-171, Denacol EX-192, Denacol EX-211, Denacol can be included EX-212、Denacol EX-313、Denacol EX-314、Denacol EX-321、Denacol EX-411、Denacol EX-421、Denacol EX-512、Denacol EX-521、Denacol EX-611、Denacol EX-612、Denacol EX-614、Denacol EX-622、Denacol EX-810、Denacol EX-811、Denacol EX-850、Denacol EX-851、Denacol EX-821、Denacol EX-830、Denacol EX-832、Denacol EX-841、Denacol EX-861、Denacol EX-911、Denacol EX-941、Denacol EX-920、Denacol EX-931(Nagase ChemteX Corporation systems)；Epolite M-1230、Epolite 40E、Epolite 100E、Epolite 200E、 Epolite 400E、Epolite 70P、Epolite 200P、Epolite 400P、Epolite 1500NP、Epolite 1600th, Epolite 80MF, Epolite 100MF (chemistry society of common prosperity society system), Adeka Glycirol ED-503, Adeka Glycirol ED-503G, Adeka Glycirol ED-506, Adeka Glycirol ED-523T (ADEKA societies system) etc..
In addition, the composition of the present invention preferably comprises at least one multi-functional epoxy compound as above-mentioned ester ring type ring Oxygen compound (1-2A) or aliphatic epoxy compound (1-2B).In the composition of the present invention, cationically polymerizable organic substance Polyfunctional cycloaliphatic epoxy (1-2A) and/or multifunctional aliphatic epoxide in the mass of mixture (1) 100 The total amount of (1-2B) is preferably 10~65 mass parts, particularly preferably 20~50 mass parts.In addition, cationically polymerizable is organic The content of polyfunctional cycloaliphatic epoxy (1-2A) in the mass parts of mixture of substances (1) 100 is preferably 0~10 mass Part, the content of polyfunctional aliphatic epoxy compound (1-2B) is preferably 10~45 mass parts.
Above-mentioned multifunctional aliphatic oxetane compound (1-3) is suitably used to obtain high Tg, it is many as this Functional aliphatic's oxetane compound (1-3), can include double (3- the oxetanyls) -5- oxa-s-nonanes of 3,7-, 1, Double [(3- ethyl -3- oxetanylmethoxies) methyl] benzene of 4-, the double [(3- ethyl -3- oxetanyl methoxies of 1,2- Base) methyl] ethane, double [(3- ethyl -3- oxetanylmethoxies) methyl] propane of 1,3-, the double (3- ethyls -3- of ethylene glycol Oxetanylmethyl) ether, double (3- ethyl -3- oxetanylmethyls) ethers of triethylene glycol, double (the 3- second of tetraethylene glycol Base -3- oxetanylmethyls) oxetane compound such as ether etc..
As above-mentioned multifunctional aliphatic oxetane compound (1-3), it can use with cationically polymerizable monomer As the multifunctional aliphatic oxetane compound of the commercially available product of main component, for example, it can include ARONOXETANE OXT-221, ARONOXETANE OXT-121 (East Asia synthesis society system)；Ethanacol OXBP、Ethanacol OXTP、 Ethanacol OXIPA (Yu Buxingchan societies system) etc..
In above-mentioned (1) cationically polymerizable organic substance mixture, above-mentioned aromatic epoxy compound (1-1), alicyclic ring Formula epoxide (1-2A), aliphatic epoxy compound (1-2B) and multifunctional aliphatic oxetane compound (1-3) Use ratio use in such a way：In the mass parts of (1) cationically polymerizable organic substance mixture 100, aromatic series Epoxide (1-1) is 35~80 mass parts, and cycloaliphatic epoxy (1-2A) is 0~45 mass parts, aliphatic epoxy Compound (1-2B) is 0~45 mass parts, and multifunctional aliphatic oxetane compound (1-3) is 5~40 mass parts, alicyclic ring Formula epoxide (1-2A) and aliphatic epoxy compound (1-2B) and be not 0, aromatic epoxy compound (1-1) turns into Main component.
Wherein, so-called main component refers to a variety of mixing of cationically polymerizable organic substance, the compound of identical type The most composition of total quality.For example, the composition of embodiment 4 described later contains aromatic epoxy compound (1-1-1) 45 Mass parts, the mass parts of cycloaliphatic epoxy (1-2A-1) 5, the mass parts of aliphatic epoxy compound (1-2B-2) 30, many officials Energy aliphatic oxetane compound (1-3-1) 20 mass parts are used as cationically polymerizable organic substance.In this case, group The most aromatic epoxy compound of content in compound turns into the main component of said composition.Even in addition, embodiment 4 contains There are the mass parts of aromatic epoxy compound (1-1-1) 25 and the mass parts of aromatic epoxy compound (1-1-2) 20 this 2 kinds of aromatic series Epoxide replaces the situation of the mass parts of aromatic epoxy compound (1-1-1) 45, also due to the aromatic series of identical type Epoxide is that 1-1-1 and 1-1-2 total content is most in the composition, so aromatic epoxy compound turns into the group The main component of compound.
In above-mentioned (1) cationically polymerizable organic substance mixture, the cationically polymerizable for constituting the mixture is used as Organic substance, can also further use vinyl ether compound, HMW body with cationically polymerizable base etc..
The composition of the present invention can also further contain cationic polymerization initiators (2).
The above-mentioned cationic polymerization initiators (2) that are used in the present invention as long as can be produced by irradiation energy ray The compound of acid, then can be arbitrary compound, preferably release lewis acidic salt i.e. by the irradiation of energy-ray Double salt, or derivatives thereof.As the representational example of the compound, can include cation represented by following formulas with The salt of anion.
p[A]q+·s[B]t-
(A represents cation kind, and B represents anion kind, q and t separately represent 1 or 2, p and s represent to protect electric charge Hold as neutral coefficient.)
Wherein, cation [A]q+Preferably salt, its structure can for example be represented with following formulas.
[(R10)aQ]q+
And then, wherein, R10It is 1~60 for carbon number, the organic of atom beyond several carbon atoms can also be included Group.A is 1~5 integer.The R of a10Independently, it can be the same or different.In addition, at least one is preferably to have The organic group as described above of aromatic rings.Q is selected from being made up of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N=N Group in atom or atomic group.In addition, by cation [A]q+In Q valence when being set to t, it is necessary to set up q=a-t pass It is (wherein, N=N is handled as valence 0).
In addition, anion [B]t-Preferably halide complex, its structure can for example be represented with following formulas.
[LXb]t-
And then, wherein, L be as halide complex central atom metal or semimetal (Metalloid), be B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co etc..X is halogen atom.B is 3~7 integer.This Outside, by anion [B]t-In L valence when being set to p, it is necessary to set up r=b-p relation.
It is used as the anion [LX of above-mentioned formulab]t-Specific example, can include four (pentafluorophenyl group) borates, four (3, The fluoro- 4- methoxyphenyls of 5- bis-) borate, tetrafluoroborate (BF4)-, hexafluorophosphate (PF6)-, hexafluoro antimonate (SbF6)-、 Hexafluoro arsenate (AsF6)-, hexa chloro-antimonate (SbCl6)-Deng.
In addition, anion [B]t-The anion of the structure represented by following formulas can also be preferably used.
[LXb-1(OH)]t-
L, X, b are same as described above.In addition, as other anion that can be used, perchlorate can be included (ClO4)-, trifluoromethyl sulfite ion (CF3SO3)-, fluosulfonic acid radical ion (FSO3)-, toluenesulfonate anion, three nitre Base benzenesulfonate anion, camsilate, nine fluorine butane sulfonate, ten hexafluoro Perfluorooctane sulfonates, four aromatic yl acid salts, four (pentafluorophenyl group) borate etc..
It is especially effective using following (a)~(c) aromatic series salt in such salt in the present invention.In them, It can be used alone, or two or more is used in mixed way.
(a) phenyldiazonium hexafluorophosphate, 4- methoxyphenyl diazonium hexafluoro antimonate, 4- aminomethyl phenyl diazonium The aryl diazonium salts such as hexafluorophosphate
(b) diphenyl iodine hexafluoro antimonate, two (4- aminomethyl phenyls) iodine hexafluorophosphates, two (4- tert-butyl-phenyls) The diaryl group iodized salts such as iodine hexafluorophosphate, tolylcumyl iodine four (pentafluorophenyl group) borate
(c) sulfonium cation and hexafluoro antimony ion, four (pentafluorophenyl group) borate ions represented by following groups of I or group II etc. Sulfonium salt
[chemical formula 1]
<Group I>
[chemical formula 2]
<Group II>
In addition, as other preferred materials, can also include (η5- 2,4- cyclopentadiene -1- bases) ((1,2,3,4,5, 6- η)-(1- Methylethyls) benzene) iron-arene complex, aluminium tris(acetylacetonate), the three (ethyl acetones such as-iron-hexafluorophosphate Acetic acid) mixture of the silane alcohols such as aluminium complex and tri-phenyl-silane alcohol such as aluminium, three (salicylide) aluminium etc..
In them, from the viewpoint of practical face and photo sensitivity, preferably use aromatic iodonium salts, aromatic series sulfonium salt, iron- Arene Complex.
(2) use ratio of the cationic polymerization initiators relative to above-mentioned (1) cationically polymerizable organic substance mixture It is not particularly limited, as long as with general common use ratio use in the range of the purpose of the present invention is not hindered, For example, relative to the mass parts of (1) cationically polymerizable organic substance mixture 100, (2) cationic polymerization initiators can be set It is set to 0.5~20 mass parts, is preferably set to 1.0~10 mass parts.If very few, solidifying easily becomes insufficient, if excessively, Each physical property such as water absorption rate, solidfied material intensity then sometimes to solidfied material have undesirable effect.
In the composition of the present invention, silane coupler can be used as needed.
As silane coupler, for example, it can use dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl Ethyldimethoxysilane, Methylethyl diethoxy silane, MTMS, MTES, ethyl The alkyl functional such as trimethoxy silane, ethyl trimethoxy silane alkoxy silane, vinyl trichlorosilane, vinyl front three The alkenyl functionality such as TMOS, VTES, allyltrimethoxysilanis alkoxy silane, 3- methyl Acryloxypropyl triethoxysilane, 3- methacryloxypropyl trimethoxy silanes, 3- methacryloxies Hydroxypropyl methyl diethoxy silane, 3- methacryloyloxypropyl methyls dimethoxysilane, 2- methacryloxies third Base trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxypropyl diethoxy silicon The epoxy functional alkoxy silanes such as alkane, β-(3,4- epoxycyclohexyls) ethyl trimethoxy silane, N- β (amino-ethyl)-γ- TSL 8330, γ aminopropyltriethoxy silane, N- phenyl-gamma-amino propyl trimethoxy silicane etc. The Mercaptofunctional such as amino functional alkoxy silane, γ mercaptopropyitrimethoxy silane alkoxy silane, four isopropanols The titaniums such as double (ethohexadiol) titaniums of the titanium alkoxide classes such as titanium, four n-butyl titaniums, two octyloxies, double (ethyl acetoacetate) titaniums of diisopropoxy The acyls such as zirconium chelate class, the three butoxy monostearate zirconiums such as chelates, four acetylacetone,2,4-pentanedione zirconiums, three butoxy single acetyl acetone zirconiums Change isocynate silane classes such as zirconium class, methyl triisocyanate silane etc..
The usage amount of above-mentioned silane coupler is not particularly limited, generally, relative to the total amount of the solid content in composition 100 mass parts are the scope of 1~20 mass parts.
In the composition of the present invention, thermal polymerization can be used as needed.
So-called thermal polymerization, as cation kind or lewis acidic compound is produced by heating, can be enumerated Go out the salt such as sulfonium salt, thiophene salt, thiophane salt, hexadecyldimethyl benzyl ammonium, pyridiniujm, hydrazonium salt；Diethylenetriamines, triethylene The poly- alkyl polyamine class such as triamine, tetren；1,2- diaminocyclohexanes, 1,4- diaminourea -3,6- diethyl cyclohexanes, The many amines of the ester ring types such as IPD；The fragrance such as the methanediamine of isophthalic two, diaminodiphenyl-methane, diamino diphenyl sulfone The many amines of race；Make above-mentioned many amines and phenyl glycidyl ether, butyl glycidyl ether, bisphenol-A-diglycidyl ether, bis-phenol The various epoxy resin such as the glycidol esters of the glycidol such as F- diglycidyl ethers ethers or carboxylic acid are anti-by conventional method The polycyclic oxygen addition modification thing answered and manufactured；Make above-mentioned organic polyamine class and phthalic acid, M-phthalic acid, dimer acid etc. Carboxylic acids by conventional method react and manufacture amidatioon modifier；Make the aldehydes such as above-mentioned many amines and formaldehyde and phenol, The phenols with least one aldehyde reaction position passes through normal on the cores such as cresols, xylenols, tert-butyl phenol, resorcinol The Mannich modifier that rule method is reacted and manufactured；Polybasic carboxylic acid (oxalic acid, malonic acid, butanedioic acid, glutaric acid, adipic acid, heptan Diacid, suberic acid, azelaic acid, decanedioic acid, 12 diacid, 2- methylsuccinic acids, 2- methyl adipic acid, 3- methyl adipic acid, 3- Methylglutaric acid, 2- methyl suberic acid, 3,8- dimethyl decanedioic acid, 3,7- dimethyl decanedioic acid, hydrogenation dimer acid, dimer The aliphatic dicarboxylic acid class such as acid；The aromatic dicarboxylic acid class such as phthalic acid, terephthalic acid (TPA), M-phthalic acid, naphthalene dicarboxylic acids； The ester ring type omega-dicarboxylic acids such as cyclohexane dicarboxylic acid；The tricarboxylic acids such as trimellitic acid, trimesic acid, the trimer of Castor Oil Fatty Acid Class；Tetracarboxylic acid acids such as Pyromellitic Acid etc.) acid anhydrides；Dicyandiamide, imidazoles, carboxylate, sulphonic acid ester, amine acid imide etc..
As above-mentioned thermal polymerization, commercially available product can also be used, can for example include Adeka Opton CP77, Adeka Opton CP66 (ADEKA societies system), CI-2639, CI-2624 (Japanese Cao Da societies system), San-Aid SI-60L, San- AidSI-80L, San-AidSI-100L (three new chemical industry society systems) etc..
The usage amount of above-mentioned thermal polymerization is not particularly limited, generally, total relative to the solid content in composition The scope that 100 mass parts are 0.001~10 mass parts is measured, in the case of using the thermal polymerization, preferably sends out this Bright composition is heated 20 minutes~1 hour when solidifying at 130~180 DEG C.
In the composition of the present invention, solidfied material can also be improved as desired by using thermoplastic organic polymer Characteristic.As the thermoplastic organic polymer, for example, it can include polystyrene, polymethyl methacrylate, methacrylic acid Methyl esters-ethyl acrylate copolymer, poly- (methyl) acrylic acid, styrene-(methyl) acrylic copolymer, (methyl) acrylic acid- Methylmethacrylate copolymer, (methyl) glycidyl acrylate-poly- (methyl) methyl acrylate copolymer, polyvinyl alcohol Butyral, cellulose esters, polyacrylamide, saturated polyester etc..
In the composition of the present invention, can use without particular limitation can dissolve each composition of above-mentioned (1) and (2) Or scattered solvent, it can for example include methyl ethyl ketone, methyl amyl ketone, metacetone, acetone, methyl isopropyl Ketone, first The ketones such as base isobutyl ketone, cyclohexanone, 2-HEPTANONE；Ethylether, dioxanes, tetrahydrofuran, 1,2- dimethoxy-ethanes, 1,2- bis- The ether series solvents such as Ethoxyethane, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether；Methyl acetate, ethyl acetate, acetic acid are just The ester such as propyl ester, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, Texanol system is molten Agent；The cellosolve series solvent such as ethylene glycol single methyl ether, ethylene glycol monomethyl ether；Methanol, ethanol, exclusive OR normal propyl alcohol, exclusive OR are just The alcohol series solvents such as butanol, amyl group alcohol；Ethylene glycol monomethyl acetic acid esters, ethylene glycol list ethylhexoate, propane diols -1- monomethyls Ether -2- acetic acid esters (PGMEA), DPGME acetic acid esters, 3- methoxybutyls acetic acid esters, ethoxy ethyl propionate Deng ether-ether series solvent；The BTX series solvents such as benzene,toluene,xylene；The aliphatic hydrocarbon series solvent such as hexane, heptane, octane, hexamethylene； The terpenic series hydrocarbon ils such as turpentine oil, D- limonenes, firpene；Mineral spirits, Swasol#310 (Cosmo Matsuyama oil Ltd.), The paraffin series solvents such as Solvesso#100 (Exon Chemical Co., Ltd.)；Carbon tetrachloride, chloroform, trichloro ethylene, dichloro The halogenated aliphatic hydrocarbon system solvents such as methane, 1,2- dichloroethanes；The halogenated aromatic hydrocarbon system solvent such as chlorobenzene；Propylene carbonate, card Must alcohol series solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, carbon disulfide, N,N-dimethylformamide, N, N- dimethyl Acetamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), water etc., these solvents can use a kind or as mixing of more than two kinds Solvent is used.
In the composition of the present invention, from the viewpoint of curability, cementability, fluid preservation stability, amount of moisture is preferred For less than 5%, more preferably less than 3%.If excess moisture, it is likely that occur gonorrhoea or into analyzing, so unexcellent Choosing.
The composition of the present invention is applicable by means known to roll coater, curtain coater, various printings, impregnating In in support substrate.In addition, once implemented in the support substrates such as film, can also be transferred in other support substrates, it is right Its usability methods is not limited.
As the material of above-mentioned support substrate, it is not particularly limited, commonly used material can be used, for example, can enumerates Go out the inorganic material such as glass；Diacetyl cellulose, triacetyl cellulose (TAC), propionyl cellulose, butyryl cellulose, levulinic The cellulose esters such as acyl cellulose, NC Nitroncellulose；Polyamide；Polyimides；Polyurethane；Epoxy resin；Makrolon；Gather to benzene Naphthalate, PEN, polybutylene terephthalate (PBT), poly terephthalic acid -1,4- hexamethylenes The polyester such as alkane diformazan alcohol ester, polyethylene -1,2- biphenoxyl ethane -4,4'- dicarboxylic esters, polybutylene terephthalate (PBT)； Polystyrene；The polyolefin such as polyethylene, polypropylene, polymethylpentene；Polyvinyl acetate, polyvinyl alcohol (PVA), polychlorostyrene second The vinyl compounds such as alkene, polyvinyl fluoride；The acrylic resins such as polymethyl methacrylate, polyacrylate；Polysulfones；Polyethers Sulfone；Polyether-ketone；PEI；Polyoxyethylene, norbornene resin, cyclic olefin polymer (COP) Polymer material.
Alternatively, it is also possible to carry out Corona discharge Treatment, flame treatment, UV treatment, high frequency treatment to above-mentioned support substrate The processing of the surface activations such as reason, glow discharge process, reactive plasma treatment, laser treatment.
As long as in addition, not damaging the effect of the present invention, other monomers, other energy-rays can be added as needed on The colouring agents such as sensitivity polymerization initiator, inorganic filler, organic filler, pigment, dyestuff, light sensitizer, defoamer, tackifier, Surfactant, levelling agent, fire retardant, thixotropic agent, diluent, plasticizer, stabilizer, polymerization inhibitor, ultra-violet absorber, antioxygen Various resin additives such as agent, antistatic additive, flow modifier, adhesion promoters etc..
The composition of the present invention is solidified by the irradiation of active energy beam, as active energy beam, can be included Ultraviolet, electron ray, X-ray, radioactive ray, high frequency etc., ultraviolet is economically most preferably., can as the light source of ultraviolet Include ultraviolet laser, mercury lamp, xenon laser, metal halide lamp etc..
As the present invention composition specific purposes, can include using glasses, imaging lens as representative optics Material, coating, coating agent, lining agent, ink, resist, liquid resist, bonding agent, galley, insulating varnish, insulating trip Material, plywood, printed base plate, semiconductor device with LED encapsulation with liquid crystal injecting port with organic EL optical elements With sealant, moulding material, putty, glass fibre impregnant, joint fillings such as electric insulation electricity consumption subassembly seperation film use Agent, semiconductor are made with the passivating film such as used for solar batteries, interlayer dielectric, diaphragm, the backlight of liquid crystal display device The lens section of the lens such as the Fresnel lens, the bi-convex lens sheet that are used in the screen of prismatic lens, projection TV etc. or The optical lenses such as backlight of such eyeglass etc., lenticule, optical element, optical connector, light-guide wave path, optics has been used to make Type cast agent etc., such as, as the base material that can be applicable as coating agent, can include metal, timber, rubber, plastics, glass Glass, ceramic etc..
The composition of the present invention is due to curability and excellent in adhesion, so can be used as bonding agent is particularly suitable.
Embodiment
Hereinafter, embodiment etc. is included the present invention is further described in detail, but the present invention is not limited to these Embodiment.
Hereinafter, composition for the present invention and solidfied material obtained from said composition is solidified, pass through embodiment, evaluate Example and comparative example are specifically described.In addition, part refers to mass parts in embodiment and comparative example.
[embodiment 1~24, comparative example 1~3]
Each composition is sufficiently mixed with the formula shown in following [table 1]~[table 4], implementation composition 1 is respectively obtained ~24, comparative composition 1~3.
As (1) cationically polymerizable organic substance, following compound (1-1-1)~(1-1-2), (1-2A-1) are used ~(1-2A-2), (1-2B-1)~(1-2B-3) and (1-3-1).
Compound 1-1-1：Adeka Resin EP-4100L (bisphenol-A epoxies：ADEKA societies system)
Compound 1-1-2：Adeka Resin EP-4901L (bisphenol-A epoxies：ADEKA societies system)
Compound 1-2A-1：Celloxide 2021P (ester ring type epoxies；Daicel Corporation systems)
Compound 1-2A-2：(4R) -1,2- epoxy radicals -4- (2- methyl oxiranes base) -1- hexahydrotoluenes methyl 3, 4- epoxycyclohexane carboxylates
Compound 1-2B-1：1,4- butanediol diglycidyl ethers
Compound 1-2B-2：Adeka Glycirol ED-523T (ADEKA societies system)
Compound 1-2B-3：1,6 hexanediol diglycidylether
Compound 1-3-1：ARONOXETANE OXT-221 (East Asia synthesis society system)
As (2) cationic polymerization initiators, following compounds (2-1) is used.
Compound 2-1：The mixture of the compound represented by compound and [chemical formula 4] represented by [chemical formula 3] The solution of propylene carbonate 50%
[chemical formula 3]
[chemical formula 4]
[evaluating example 1~24, comparative evaluation example 1~3]
To the comparative composition obtained in the implementation composition and comparative example 1~3 that are obtained in above-described embodiment 1~24, enter Row is following to be evaluated.Show the result in above-mentioned [table 1]~[table 4].
(viscosity)
1~24, the 1~3 of comparative composition to resulting implementation composition is measured at 25 DEG C with E types viscosity respectively Determine viscosity.Show the result in [table 1]~[table 4].
(Tg)
The resulting composition 1~24, comparative composition implemented 1~3 is applied with bar coater with 30 μm of thickness respectively Cloth uses metal halide light irradiation 3000mJ/cm on PET film2Energy.After 24 hours by bonding agent solidfied material from film Take out, determined using Hitachi High-Tech Science Corporation determination of viscoelasticity device (DMA7100) Tg.Show the result in [table 1]~[table 4].
(curability)
Curability is also confirmed in the lump when making Tg test film.Coated face after firm irradiation is become inviscid Test film is evaluated as ◎, the test film for becoming inviscid after 5 minutes is evaluated as into zero, by also residual tack over the course of 15 mins Test film is evaluated as ×.Show the result in [table 1]~[table 4].
(cementability)
Resulting implementation composition 1~24, comparative composition 1~3 are respectively coated and implement corona to one and put After on TAC (triacetyl cellulose) film of electric treatment, by the film is using laminating machine and implements another of Corona discharge Treatment COP (cyclic olefin polymer) film is fitted, and uses metal halide light irradiation 800mJ/cm2Energy and be bonded, tried Test piece.90 degree of disbonded tests of the test film obtained by carrying out.Show the result in [table 1]~[table 4].
It is clear by [table 1]~[table 4], curability, cementability and the excellent heat resistance of composition of the invention.

Claims (7)

1. a kind of composition, it is characterised in that as cationically polymerizable organic substance mixture (1), include aromatic epoxies Compound (1-1)；Cycloaliphatic epoxy (1-2A) or aliphatic epoxy compound (1-2B)；And multifunctional aliphatic oxa- Cyclobutane compound (1-3), aromatic epoxy compound (1-1) is main component.
2. composition according to claim 1, it is characterised in that the aromatic epoxy compound (1-1), which is contained, to be selected from The glycidol ether of monovalence phenols, the glycidol ether compound of aromatic compound with more than 2 alcohol hydroxyl groups, Polyphenols Glycidol ether compound, the ethylene oxidic ester of benzoic acids, the ethylene oxidic ester of polynary acids, Styryl oxide or divinyl At least one of group of epoxides of base benzene.
3. composition according to claim 1 or 2, it is characterised in that the aromatic epoxy compound (1-1) is containing extremely A kind of few multi-functional epoxy compound.
4. according to composition according to any one of claims 1 to 3, it is characterised in that the aromatic epoxy compound (1- 1) epoxide equivalent is 80~500.
5. according to composition according to any one of claims 1 to 4, it is characterised in that relative to the cationically polymerizable The mass parts of organic substance mixture (1) 100, the cationic polymerization initiators (2) comprising 0.5~20 mass parts.
6. according to composition according to any one of claims 1 to 5, wherein, the cationic polymerization initiators (2) are p [A ]q+·s[B]t-In represented cation and the salt of anion, formula, A represents cation kind, and B represents anion kind, and q and t divide Independently expression 1 or 2, p and s are the coefficient that electric charge is remained to neutrality.
7. a kind of bonding agent, it is characterised in that it includes composition according to any one of claims 1 to 6.
CN201680003422.1A 2015-03-30 2016-03-18 Composition Pending CN107075083A (en)

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Application publication date: 20170818