CN104955866B - cationically polymerizable composition - Google Patents
cationically polymerizable composition Download PDFInfo
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- CN104955866B CN104955866B CN201480005618.5A CN201480005618A CN104955866B CN 104955866 B CN104955866 B CN 104955866B CN 201480005618 A CN201480005618 A CN 201480005618A CN 104955866 B CN104955866 B CN 104955866B
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- polymerizable composition
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
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Abstract
The cationically polymerizable composition of the present invention contains (1) cationically polymerizable organic substance mixture and the sensitivity cationic polymerization initiators of (2) energy-ray, in (1) the cationically polymerizable organic substance mixture, it is used as cationically polymerizable organic substance, containing aromatic epoxy compound (1A) as main component, further containing at least one of aliphatic epoxy compound (1B) or cycloaliphatic epoxy (1C).As above-mentioned aliphatic epoxy compound (1B) or cycloaliphatic epoxy (1C), at least one multi-functional epoxy compound is preferably comprised.
Description
Technical field
The present invention relates to cationically polymerizable composition and by irradiating active-energy to the cationically polymerizable composition
Solidfied material obtained from ray.It is useful to bonding agent that the cationically polymerizable composition, which is particularly,.
Background technology
Cationically polymerizable composition is made in the fields such as ink, coating, various coating agents, bonding agent, optical component
With.
For example in following patent documents 1~3, various Photocurable adhesive agents are disclosed.
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
The content of the invention
Invent problem to be solved
It is an object of the invention to provide the cationically polymerizable composition of curability, cementability and excellent water resistance.
Means for solving the problems
The present invention is carried out based on above-mentioned cognition, above-mentioned to reach by providing a kind of cationically polymerizable composition
Purpose, the cationically polymerizable composition is characterised by, contains (1) cationically polymerizable organic substance mixture and (2) energy
Measure in the sensitivity cationic polymerization initiators of ray, (1) the cationically polymerizable organic substance mixture, it is poly- as cation
Conjunction property organic substance, containing aromatic epoxy compound (1A) as main component, and then contains aliphatic epoxy compound
At least one of (1B) or cycloaliphatic epoxy (1C).
In addition, the present invention provides the bonding agent being made up of above-mentioned cationically polymerizable composition.
Invention effect
The cationically polymerizable composition of the present invention is due to curability, cementability and excellent water resistance, so being used as bonding
Agent purposes is particularly useful.
Embodiment
Hereinafter, the bonding agent constituted to cationically polymerizable composition of the invention and by the cationically polymerizable composition
It is described in detail.
In above-mentioned (1) the cationically polymerizable organic substance mixture used in the present invention, constitute the mixture sun from
Sub- polymerism organic substance is caused using the sensitivity cationic polymerization initiators of energy-ray activated by light irradiation
The compound of producing high-molecular or cross-linking reaction, preferably epoxide.As the epoxide, aromatic epoxies can be used
Compound (1A), cycloaliphatic epoxy (1C), aliphatic epoxy compound (1B), the weight average molecular weight with epoxy radicals are
1000~1000000 HMW body (1D).In addition, as cationically polymerizable organic substance, vinyl can also be used
Ether compound or oxetane compound (1E).
Above-mentioned aromatic epoxy compound (1A) refers to the epoxide for including aromatic rings, is aoxidized as the aromatic ring
The specific example of compound, can include phenol, cresols, butylphenol etc. with least one aromatic ring monohydric phenol or its
Single multi- glycidol ether compound, such as bisphenol-A, Bisphenol F or the further addition epoxy on them of alkylene oxide adducts
The glycidol ether compound or epoxy radicals novolac resin of compound obtained from alkane；Resorcinol or hydroquinones, youngster
Tea phenol etc. has the glycidol ether of the aromatic compound of the phenolic hydroxyl group of more than 2；Benzene dimethanol or benzene diethanol, benzene two
Butanol etc. has the single multi- glycidol ether compound of the aromatic compound of the alcohol hydroxyl group of more than 2；It is phthalic acid, right
Phthalic acid, trimellitic acid etc. have the ethylene oxidic ester of polyacid aromatic compound of the carboxylic acid of more than 2, benzoic acid or
Epoxides of the ethylene oxidic esters of the benzoic acids such as methyl benzoic acid, naphthoic acid, Styryl oxide or divinylbenzene etc..
Wherein, the contracting of the aromatic compound containing the glycidol ether selected from phenols, with the alcohol hydroxyl groups of more than 2
Water glycerine etherate, the glycidol ether compound of Polyphenols, the ethylene oxidic ester of benzoic acids, the glycidol of polynary acids
At least one of group of epoxides of ester, Styryl oxide or divinylbenzene goes out from the viewpoint of the lowering viscousity of composition
Hair is preferred.
As above-mentioned aromatic epoxy compound, epoxide equivalent for 80~500 compound due to curability it is excellent, so
It is preferred that.
As above-mentioned aromatic epoxy compound (1A), commercially available product can be used, such as Denacol EX- can be included
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. make)；HP4032, HP4032D, HP4700 (DIC company systems)；ESN-475V (aurification company system is lived by Nippon Steel)；
Epikote YX8800 (Mitsubishi Chemical Ind's system)；Mar proof G-0105SA, Mar proof G-0130SP (You companies
System)；Epiclon N-665, Epiclon HP-7200 (DIC company systems)；EOCN-1020、EOCN-102S、EOCN-103S、
(Japanese chemical drug is public by EOCN-104S, XD-1000, NC-3000, EPPN-501H, EPPN-501HY, EPPN-502H, NC-7000L
Department's system)；Adeka Glycirol ED-501、Adeka Glycirol ED-502、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 company systems)；TECHMOREVG-3101L、EPOX-MKR710、EPOX-MKR151
(Printec Corporation systems) etc..
As above-mentioned aromatic epoxy compound (1A), containing at least one multi-functional epoxy compound is from curability and glues
It is preferred from the viewpoint of connecing property.In the cationically polymerizable composition of the present invention, preferably with respect to (1) cationically polymerizable
The mass parts of organic substance mixture 100, it is further excellent containing the polyfunctional aromatic epoxy compound of 25~70 mass parts (1A)
Choosing contains 30~60 mass parts.
Here, the amount of above-mentioned (1A) is the amount for including the compound for meeting (1D).
As above-mentioned cycloaliphatic epoxy (1C) specific example, the ester ring type ring with least one can be included
Polyalcohol polyglycidyl ether compound or by the way that the compound containing cyclohexene or cyclopentene ring is carried out into ring with oxidant
Compound containing 7-oxa-bicyclo[4.1.0 or cyclopentane epoxide obtained from oxidation.For example, hydrogenated bisphenol A 2-glycidyl can be included
Ether, 3,4- epoxycyclohexylmethyl -3,4- epoxycyclohexane carboxylates, 3,4- epoxy radicals -1- methylcyclohexyl -3,4- rings
Oxy-1-methyl hexane carboxylate, 6- methyl-3,4- epoxycyclohexylmethyl-6- methyl-3,4- epoxy-cyclohexane carboxylic acids
Ester, 3,4- epoxy radicals -3- methylcyclohexylmethyl -3,4- epoxy radicals -3- methylcyclohexanecarboxylic acids ester, 3,4- epoxy radicals -5- first
Butylcyclohexyl methyl -3,4- epoxy radicals -5- methylcyclohexanecarboxylic acids ester, double (3,4- epoxycyclohexylmethyls) adipate esters,
3,4- epoxy radicals -6- methylcyclohexanecarboxylic acids ester, di-2-ethylhexylphosphine oxide (3,4- epoxy-cyclohexanes), propane -2,2- diyls-bis- (3,
4- epoxy-cyclohexanes), double (3,4- expoxycyclohexyls) propane of 2,2-, bicyclopentadiene diepoxide, ethylenebis (3,
4- epoxycyclohexane carboxylates), epoxy radicals di-2-ethylhexyl hexahydrophthalate, -2- the second of epoxy radicals hexahydrophthalic acid two
The own ester of base, 1- epoxy radicals ethyl -3,4- epoxy-cyclohexanes, 1,2- epoxy radicals -2- epoxy radicals ethyl cyclohexane, oxidation australene
Alkene, limonene dioxide etc..
As cycloaliphatic epoxy (1C), preferably epoxide equivalent is 80~500 compound.
As above-mentioned cycloaliphatic epoxy (1C), commercially available product can be used, such as CELLOXIDE can be included
2021P, CELLOXIDE 2081, CELLOXIDE 2000, CELLOXIDE3000 (Daicel Corporation systems) etc..
Above-mentioned aliphatic epoxy compound (1B) refers to not be classified as above-mentioned aromatic epoxy compound (1A) or alicyclic ring
The epoxide of formula epoxide (1C), as the specific example of the aliphatic epoxy compound, can include aliphatic
Monofunctional epoxy compound or the aliphatic polyols such as glycidol ether compound, the ethylene oxidic ester of alkyl carboxylic acid of alcohol or its ring
Multi-functional epoxy's chemical combination such as the polyglycidyl ether compound of oxygen alkane addition product, many ethylene oxidic esters of aliphatic long-chain polyacid
Thing.As representative compound, allyl glycidyl ether, butyl glycidyl ether, 2- ethylhexylglycidylethers can be included sweet
The mixed alkyl glycidol ether of oily ether, C12~13,1,4- butanediol diglycidyl ethers, 1,6 hexanediol diglycidylether,
The triglycidyl ether of glycerine, the triglycidyl ether of trimethylolpropane, four glycidol ethers of D-sorbite, two seasons penta 4
The shrink of the polyalcohols such as six glycidol ethers, the diglycidyl ether of polyethylene glycol, the diglycidyl ether of polypropylene glycol of alcohol
Glycerin ether and pass through the one kind or two or more ring of the addition on the aliphatic polyols such as propane diols, trimethylolpropane, glycerine
The polyglycidyl ether compound of PPG obtained from oxygen alkane, the 2-glycidyl ester of aliphatic long-chain binary acid.Enter
And, the monoglycidyl ether of aliphatic higher alcohol or the ethylene oxidic ester of higher fatty acids, epoxidised soybean oil, ring can be included
Oxygen octyl stearate, butyl epoxy stearate, epoxidised soybean oil, epoxidized polybutadiene etc..
As aliphatic epoxy compound (1B), preferably epoxide equivalent is 80~500 compound.
As above-mentioned aliphatic epoxy compound (1B), commercially available product can be used, such as Denacol EX- can be included
121、Denacol EX-171、Denacol EX-192、Denacol EX-211、Denacol 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
System)；Epolight M-1230、Epolight 40E、Epolight 100E、Epolight 200E、Epolight 400E、
Epolight 70P、Epolight 200P、Epolight 400P、Epolight 1500NP、Epolight 1600、
Epolight80MF, Epolight 100MF (chemical company of common prosperity society system), Adeka Glycirol ED-503, Adeka
Glycirol ED-503G, Adeka Glycirol ED-506, Adeka Glycirol ED-523T (ADEKA company systems) etc..
In addition, the cationically polymerizable composition of the present invention preferably comprises at least one multi-functional epoxy compound as upper
The aliphatic epoxy compound (1B) or cycloaliphatic epoxy (1C) stated.In the cationically polymerizable composition of the present invention,
Relative to the mass parts of (1) cationically polymerizable organic substance mixture 100, polyfunctional aliphatic epoxy compound (1B) and many
The total amount of the cycloaliphatic epoxy (1C) of function is 10~65 mass parts, particularly preferably 20~50 mass parts.In addition,
Relative to the mass parts of (1) cationically polymerizable organic substance mixture 100, polyfunctional aliphatic epoxy compound (1B's) contains
Amount is preferably 10~45 mass parts, and the content of polyfunctional cycloaliphatic epoxy (1C) is preferably 0~10 mass parts.
Wherein, above-mentioned (1B) and (1C) amount are the amount for including the compound for meeting (1D).
As the HMW body (1D) that the above-mentioned weight average molecular weight with epoxy radicals is 1000~1000000, it can enumerate
Go out by polymer obtained from radical polymerization, preferably by the ethylenically unsaturated monomers with cationically polymerizable substituent
A kind of polymer of homopolymerization or with the ethylenically unsaturated monomers copolymerization without cationically polymerizable substituent
Polymer.
It is used as the alkene for constituting the HMW body (1D) that the above-mentioned weight average molecular weight with epoxy radicals is 1000~1000000
Keyed unsaturated monomer, can be without particular limitation using known monomer.For example, being taken as without cationically polymerizable
One of Dai Ji ethylenically unsaturated monomers, can include the group shown in following formula (1), as poly- with cation
One of the ethylenically unsaturated monomers of conjunction property substituent, can include alkyl, aryl or the ester ring type in following formula (1)
The group that 1 in alkyl or the hydrogen atom of more than 2 are replaced by epoxy radicals, oxetanyl or vinyl ether group.
[changing 1]
R11R12=R13R14 (1)
(in formula, R11、R12、R13And R14Be separately hydrogen atom, carbon number be 1~10 straight-chain, branched
Alkyl, the carbon number of ring-type be 6~12 aryl or carbon number be 6~10 alicyclic type hydrocarbon, in these groups
Methylene can also be replaced by-CO- ,-O- or-COO-)
In addition, in the case of above-mentioned copolymer, HMW body (1D) preferably comprises having for 10~80 mass %
The ethylenic of the structure replaced by the cationically polymerizable substituent such as epoxy radicals, oxetanyl, vinyl ether group is unsaturated
Monomer, containing 20~90 mass % not by cationically polymerizable substituent replace by methyl, ethyl or carbon number be 3~
The ethylenic insatiable hunger for the alicyclic type hydrocarbon substitution that aryl that 7 branched alkyl, carbon number are 6~12, carbon number are 6~10
And monomer, and 100 mass % are amounted in the lump with other ethylenically unsaturated monomers.
The HMW body (1D) that the above-mentioned weight average molecular weight with epoxy radicals is 1000~1000000 preferably Weight-average molecular
Measure as 5000~100000, more preferably 7000~70000.
As above-mentioned vinyl ether compound or oxetane compound (1E), ethylene glycol divinyl base can be included
Ether, triethyleneglycol divinylether, dodecyl vinyl ethers, cyclohexyl vinyl ether, 2- ethylhexyl vinyl ethers, 2-
Chloroethyl vinyl ether, ethyl vinyl ether, IVE, triethylene glycol vinyl ethers, 2- hydroxyethylvinyls
Ether, 4- hydroxybutyl vinyl ethers, 1,6- cyclohexane dimethanol monovinyl ethers, 1,4- butanediols mono vinyl ether, diethyl two
The vinyl ether compounds such as alcohol mono vinyl ether, 1,4- butanediols divinyl ether, 1,6- cyclohexanedimethanol divinyl base ethers；
Double (3- the oxetanyls) -5- oxa-s-nonanes of 3,7-, 1,4- are double [(3- ethyl -3- oxetanylmethoxies) methyl]
Double [(3- ethyl -3- oxetanylmethoxies) methyl] ethane of benzene, 1,2-, the double [(3- ethyl -3- oxetanes of 1,3-
Ylmethoxy) methyl] propane, double (3- ethyl -3- oxetanylmethyls) ethers of ethylene glycol, the double (3- ethyls -3- of triethylene glycol
Oxetanylmethyl) ether, double (3- ethyl -3- oxetanylmethyls) ethers of tetraethylene glycol, the double (3- ethyls -3- of 1,4-
Oxetanylmethoxy) butane, 1,6- double (3- ethyl -3- oxetanylmethoxies) hexane, 3- ethyl -3- [(benzene
Epoxide) methyl] oxetanes, 3- ethyls -3- (hexoxymethyl) oxetanes, 3- ethyls -3- (2- ethyl hexyl oxy first
Base) oxa- such as oxetanes, 3- ethyls -3- (hydroxymethyl) oxetanes, 3- ethyls -3- (chloromethyl) oxetanes
Cyclobutane compound etc..As vinyl ether compound, preferred molecular weight is 58~500 compound, preferably 70~300
Compound.As oxetane compound, preferred molecular weight is 100~1000 compound, preferably 110~500 change
Compound.In addition, as above-mentioned vinyl ether compound or oxetane compound (1E), simple function can be used and multifunctional
Any of compound, but preferably use vinyl ether compound with 1 or 2 vinyl ether group or with 1 or 2
The oxetane compound of individual oxetanyl.
As above-mentioned vinyl ether compound or oxetane compound (1E), it can use with cationically polymerizable list
Body can include such as 2- hydroxyethyl vinyl ethers, diethylene glycol monovinyl base ether, 4- hydroxyls as the commercially available product of main component
Base butyl vinyl ether (ball is apt to petrochemistry company system)；ARONOXETANE OXT-121、OXT-221、EXOH、POX、OXA、
OXT-101, OXT-211, OXT-212 (East Asia Synesis Company system), ETERNACOLL OXBP, OXTP (the emerging production company system in space portion)
Deng.
In above-mentioned (1) cationically polymerizable organic substance mixture, above-mentioned aromatic epoxy compound (1A), ester ring type
The height that epoxide (1C), aliphatic epoxy compound (1B), the weight average molecular weight with epoxy radicals are 1000~1000000
The use ratio of molecular weight body (1D), vinyl ether compound or oxetane compound (1E), preferably according to relative to (1)
The mass parts of cationically polymerizable organic substance mixture 100, aromatic epoxy compound (1A) is 25~70 mass parts, is particularly
For 30~60 mass parts, cycloaliphatic epoxy (1C) is 0~45 mass parts, especially for 0~30 mass parts, aliphatic ring
Oxygen compound (1B) be 0~45 mass parts, especially for 10~40 mass parts, the weight average molecular weight with epoxy radicals be 1000~
1000000 HMW body (1D) is 0~50 mass parts, especially for 0~15 mass parts, vinyl ether compound or oxa-
Cyclobutane compound (1E) is 0~30 mass parts, especially for 0~25 mass parts, cycloaliphatic epoxy (1C) and fat
Race's epoxide (1B) and be 0, aromatic epoxy compound (1A) turn into main component mode use.
But, here, (1B) and (1C) amount are the amount in addition to the compound for meeting above-mentioned (1D), and the amount of (1A) is bag
Amount containing the compound for meeting (1D).
Here, so-called main component refers to a variety of mixing of epoxide, the epoxide of identical type it is total
The most composition of amount, when cationically polymerizable organic substance mixture has comprising the cationically polymerizable in addition to epoxide
During machine material, in a variety of epoxides the total amount of the most species of total amount than in addition to epoxide sun from
The total amount of sub- polymerism organic substance is more.Here include and meet (1D) in the total amount of so-called various epoxide
The amount of compound.
Above-mentioned (2) that are used in the present invention as long as the sensitivity cationic polymerization initiators of energy-ray pass through energy-ray
Irradiation can discharge the compound for the material for triggering cationic polymerization, then any compound can be preferably to be penetrated by energy
The irradiation of line and discharge lewis acidic salt i.e. double salt, or derivatives thereof.As the representative example of the compound, it can arrange
The salt of the cation and anion shown in following formulas is enumerated,
[A]r+[B]r-(in formula, A represents cation kind, and B represents anion kind, and r represents valence mumber.).
Here, cation [A]r+Preferably, its structure can for example be represented with following formulas.
[(R1)aQ]r+
And then, here, R1It is 1~60 for carbon number, the organic group of the atom beyond several carbon atoms can be included.
A is 1~5 integer.The R of a1It is each independent, it can be the same or different.In addition, at least one is preferably to have aromatic rings
Organic group as described above.Q is in the group being made up of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, N=N
Atom or atomic group.In addition, setting cation [A]r+In Q valence be q when, (wherein, this relations of r=a-q must be set up
N=N is handled as valence 0).
In addition, anion [B]r-Preferably halide complex, its structure can for example be represented with following formulas.
[LXb]r-
And then, here, 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, if anion [B]r-In L valence be p when, this relations of r=b-p must be set up.
It is used as the anion [LX of above-mentioned formulab]r-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]r-The anion of the structure shown in following formulas can also be preferably used.
[LXb-1(OH)]r-
L, X, b are same as described above.In addition, the anion that can be used as other, can include perchlorate
(ClO4)-, trifluoromethyl sulfite ion (CF3SO3)-, fluosulfonic acid radical ion (FSO3)-, toluenesulfonate anion, trinitro-
Benzene sulfonate anion, camsilate, nine fluorine butane sulfonate, ten hexafluoro Perfluorooctane sulfonates, four aromatic yl acid salts, four (five fluorine
Phenyl) borate etc..
It is especially effective using following (a)~(c) aromatic series salt in such salt in the present invention.In them,
Its a kind is can be used alone, or two or more can be 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-antimonic acid radical ion, hexafluorophosphoricacid acid ions, four (five fluorine shown in following groups of I or group II
Phenyl) sulfonium salt such as borate ion
[changing 2]
<Group I>
[changing 3]
<Group II>
In addition, as other preferred examples, can also include (η5- 2,4- cyclopentadiene -1- bases) ((1,2,3,4,5,
6- η)-(1- Methylethyls) benzene) iron-arene complex or aluminium tris(acetylacetonate), the three (acetoacetates such as-iron-hexafluorophosphate
Ethyl ester) 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) the sensitivity cationic polymerization initiators of energy-ray are mixed relative to above-mentioned (1) cationically polymerizable organic substance
The use ratio of compound is not particularly limited, if in the range of the purpose of the present invention is not damaged with general common use than
Example use, for example, relative to the mass parts of (1) cationically polymerizable organic substance mixture 100, the sensitization of (2) energy-ray
Property cationic polymerization initiators can be set to 0.001~10 mass parts, be preferably set to 0.1~5 mass parts.If very few, solidify
Easily become insufficient, if excessively, all physical property such as water absorption rate sometimes to solidfied material or solidfied material intensity have undesirable effect.
In the cationically polymerizable composition of the present invention, silane coupler can be used as needed.
As silane coupler, such as dimethyldimethoxysil,ne, dimethyldiethoxysilane, methyl can be used
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
Epoxy functional's alkoxy silane, N- β (the amino second such as alkane, β-(3,4- expoxycyclohexyls) ethyl trimethoxy silane
Base)-gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, N- phenyl-gamma-amino propyl group trimethoxy
Mercaptofunctional alkoxy silane, four such as the amino functional such as base silane alkoxy silane, γ mercaptopropyitrimethoxy silane
Double (octamethylene ethyl glycolate) titaniums of the Titanium alkoxides classes such as isopropyl titanate, four n-butyl titaniums, two octyloxies, the double (acetyl of diisopropoxy
Ethyl acetate) zirconium chelate class, three fourths such as titanium chelate class, four acetylacetone,2,4-pentanedione zirconiums, the three butoxy monoacylphosphine acetone zirconiums such as titanium
The zirconiums such as epoxide monostearate zirconium are acylated isocyanato silanes classes such as species, methyl triisocyanate base silane etc..
The usage amount of above-mentioned silane coupler is not particularly limited, and is commonly angled relative to consolidating in cationically polymerizable composition
The mass parts of total amount 100 of shape thing are the scope of 1~20 mass parts.
In the cationically polymerizable composition of the present invention, thermal polymerization can be used as needed.
Thermal polymerization is that cation kind or lewis acidic compound are produced by heating, can include sulfonium salt,
The salt such as thiophene salt, thiophane salt, hexadecyldimethyl benzyl ammonium, pyridiniujm, hydrazonium salt；Diethylenetriamines, diethylenetriamine, four Asias
The poly- alkyl polyamine class such as the amine of ethyl five；1,2- diaminocyclohexanes, 1,4- diaminourea -3,6- diethyl cyclohexanes, isophorone
The many amines of the ester ring types such as diamines；The aromatic polyamines such as MXDP, diaminodiphenyl-methane, diamino diphenyl sulfone
Class；By by above-mentioned many amines and phenyl glycidyl ether, butyl glycidyl ether, bisphenol-A-diglycidyl ether, Bisphenol F-
The various epoxy resin such as the glycidol esters of the glycidol such as diglycidyl ether ethers or carboxylic acid are carried out using conventional method
The polycyclic epoxide addition modification thing for reacting and manufacturing；By by above-mentioned organic polyamine class and phthalic acid, M-phthalic acid, two
The amidatioon modifier that the carboxylic acids such as polyacids are reacted and manufactured using conventional method；By by above-mentioned many amines and formaldehyde etc.
Aldehydes and phenol, cresols, xylenols, tert-butyl phenol, resorcinol etc. have the aldehyde reaction of at least one on core
The Mannich modifier that the phenols at position is reacted and manufactured using conventional method；Polybasic carboxylic acid (oxalic acid, malonic acid, amber
Amber acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, dodecanedioic acid, 2- methylsuccinic acids, 2- methyl
Adipic acid, 3- methyl adipic acid, 3- methylpentanes diacid, 2- methyloctanes diacid, 3,8- dimethyl decanes diacid, 3,7- diformazans
The aliphatic dicarboxylic acid classes such as base decane diacid, hydrogenated dimer acids, dimeric dibasic acid；Phthalic acid, terephthalic acid (TPA), isophthalic diformazan
The aromatic dicarboxylic acid class such as acid, naphthalene dicarboxylic acids；The ester ring type omega-dicarboxylic acids such as cyclohexane dicarboxylic acid；Trimellitic acid, trimesic acid,
The tricarboxylic acids such as trimer of Castor Oil Fatty Acid；Tetracarboxylic acid acids such as Pyromellitic Acid etc.) acid anhydrides；Dicyandiamide, imidazoles, carboxylic
Acid esters, sulphonic acid ester, amine acid imide etc..
As above-mentioned thermal polymerization, commercially available product can also be used, can include such as Adeka Opton CP77,
Adeka Opton CP66 (ADEKA company systems), CI-2639, CI-2624 (Japanese Cao reach at company system), San-Aid SI-60L,
San-Aid SI-80L, San-Aid SI-100L (three new chemical industrial company's systems) etc..
The usage amount of above-mentioned thermal polymerization is not particularly limited, and is commonly angled relative in cationically polymerizable composition
The mass parts of total amount 100 of solid content are the scope of 0.001~10 mass parts, excellent in the case of using the thermal polymerization
Heated 20 minutes~1 hour at 130~180 DEG C when being selected in the cationically polymerizable composition solidification for making the present invention.
In the cationically polymerizable composition of the present invention, as desired by use thermoplastic organic polymer (wherein, no
Including the HMW body (1D) that the weight average molecular weight with epoxy radicals is 1000~1000000), additionally it is possible to improve solidfied material
Characteristic.As the thermoplastic organic polymer, such as polystyrene, polymethyl methacrylate, methacrylic acid can be included
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 cationically polymerizable composition of the present invention, can without particular limitation using it is usually used can will be upper
Each composition dissolving of (1) and (2) or scattered solvent are stated, such as methyl ethyl ketone, methyl amyl ketone, diethyl can be included
The ketones such as ketone, acetone, methyl isopropyl Ketone, methyl iso-butyl ketone (MIBK), cyclohexanone, 2-HEPTANONE；Ethylether, dioxanes, tetrahydrofuran,
The ether series solvents such as 1,2- dimethoxy-ethanes, 1,2- diethoxyethane, propylene glycol monomethyl ether, dipropylene glycol dimethyl ether；
Methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, butanedioic acid
The ester series solvents such as dimethyl ester, Texanol；The cellosolve series solvent such as ethylene glycol single methyl ether, ethylene glycol monomethyl ether；Methanol, second
The alcohol series solvent such as alcohol, isopropanol or normal propyl alcohol, isobutanol or n-butanol, amylalcohol；Ethylene glycol monomethyl acetic acid esters, ethylene glycol list second
Yl acetate, propane diols -1- monomethyl ether -2- acetic acid esters (PGMEA), DPGME acetic acid esters, 3- methoxyl group fourths
The ether-ether series solvent such as yl acetate, ethoxy ethyl propionate；The BTX series solvents such as benzene,toluene,xylene；It is hexane, heptane, pungent
The aliphatic hydrocarbon series solvent such as alkane, hexamethylene；The terpenic series hydrocarbon ils such as turpentine oil, orange limonene, firpene；Mineral spirits, Swasol#310
The paraffin series such as (COSMO MATSUYAMA OIL CO., LTD.), Solvesso#100 (Exon Chemical Co., Ltd.) are molten
Agent；The halogenated aliphatic hydrocarbon system solvents such as carbon tetrachloride, chloroform, trichloroethanes, dichloromethane, 1,2- dichloroethanes；The halogen such as chlorobenzene
For aromatic hydrocarbon series solvent；Propylene carbonate, carbitol series solvent, aniline, triethylamine, pyridine, acetic acid, acetonitrile, curing
Carbon, DMF, DMA, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), water etc., these solvents
1 kind can be used or used as mixed solvent of more than two kinds.
(1) cationically polymerizable organic substance mixture and (2) energy are removed in the cationically polymerizable composition of the present invention
The total amount of optional member beyond the amount sensitivity cationic polymerization initiators of ray is also different because of purposes of the present invention etc., but from
From the viewpoint of the effect for further improving the present invention, relative to the mass parts of (1) cationically polymerizable organic substance mixture 100
It is set to below 20 mass parts, is particularly preferably set to below 10 mass parts.
The cationically polymerizable composition of the present invention is from the viewpoint of curability, cementability, fluid preservation stability, water
Component is preferably more preferably below 3 mass % below 5 mass %.If excess moisture, it is likely that occur gonorrhoea or into
Analyze, so not preferred.Amount of moisture is determined by the method described in embodiment described later.
The cationically polymerizable composition of the present invention is from the viewpoint of coating, and viscosity is preferably below 200mPas,
More preferably 10~150mPas.The viscosity is the viscosity at 25 DEG C, is surveyed by the method described in embodiment described later
It is fixed.
The cationically polymerizable composition of the present invention passes through known in roll coater, episodic curtain coater, various printings, impregnating
Means and be applied in support substrate.In addition it is also possible to after temporarily imposing in the support substrates such as film, be transferred to other branch
On support group body, it is applied to method and does not limit.
As the material of above-mentioned support substrate, commonly used material can be used without particular limitation, can be included
The inorganic material such as glass；Diacetyl cellulose, tri acetyl cellulose (TAC), propionyl cellulose, bytyry fiber
The cellulose esters such as element, acetylpropionyl cellulose, NC Nitroncellulose；Polyamide；Polyimides；Polyurethane；Epoxy resin；It is poly-
Carbonic ester；It is polyethylene terephthalate, PEN, polybutylene terephthalate (PBT), poly- to benzene two
Formic acid -1,4 cyclohexane dimethanol ester, poly- ethylidene -1,2- biphenoxyl ethane -4,4'- dicarboxylic esters, poly terephthalic acid
The polyester such as butanediol ester；Polystyrene；The polyolefin such as polyethylene, polypropylene, polymethylpentene；Polyvinyl acetate, polychlorostyrene second
The vinyl compounds such as alkene, polyvinyl fluoride；The acrylic resins such as polymethyl methacrylate, polyacrylate；Makrolon；
Polysulfones；Polyether sulfone；Polyether-ketone；PEI；The macromolecules such as polyoxyethylene, norbornene resin, cyclic olefin polymer (COP)
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
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 cationically polymerizable composition of the present invention is solidified by the irradiation of active energy beam, is penetrated as active-energy
Line, can include ultraviolet, electron ray, X-ray, radioactive ray, high frequency waves etc., ultraviolet in economic aspect most preferably.As
The light source of ultraviolet, can include ultraviolet laser, mercury lamp, xenon laser, metal halide lamp etc..
As the specific purposes of the cationically polymerizable composition of the present invention, it can include with glasses, imaging lens
For the optical material of representative, coating, coating agent, liner agent, ink, resist, liquid resist, bonding agent, galley, insulation
Varnish, insulating trip, plywood, printed base plate, semiconductor device are used with LED encapsulation liquid crystal injecting port with organic EL
Sealant, moulding material, putty, the glass fibre of optical element use electric insulation electricity consumption subassembly seperation film use etc. infiltrate
Agent, caulking compound, semiconductor with passivating film used for solar batteries etc., interlayer dielectric, diaphragm, liquid crystal display device the back of the body
The lens such as the Fresnel lens, the bi-convex lens sheet that are used in the screens such as the prismatic lens, the projection TV that are used in light source it is saturating
Mirror portion has used the optical lenses such as backlight of such eyeglass etc., lenticule, optical element, optical connector, optical guided wave
Road, optics moulding casting agent etc., as the base material that can be for example applied as coating agent, can include metal, timber, rubber
Glue, plastics, glass, ceramic etc..
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, obtained on the cationically polymerizable composition and the cationically polymerizable composition of the present invention are solidified
Solidfied material, by embodiment, evaluate example and comparative example and be specifically described.In addition, in embodiment and comparative example, part refers to matter
Part is measured, % refers to quality %.
[embodiment 1~30, comparative example 1~2]
Each composition is sufficiently mixed with the formula shown in following [table 1]~[table 3], implementation composition 1 is respectively obtained
~30, comparative composition 1~2.
As (1) cationically polymerizable organic substance, using following compound (1A-1)~(1A-12), (1B-1)~
(1B-4), (1C-1)~(1C-3), (1D-1)~(1D-2) and (1E-1)~(1E-4).Their epoxide equivalent is shown in the lump
In [table 1]~[table 5].
Compound 1A-1：Resorcinolformaldehyde resin
Compound 1A-2：O-phthalic acid diglycidyl ester
Compound 1A-3：Aoxidize divinylbenzene
Compound 1A-4：Phenyl glycidyl ether
Compound 1A-5：Styryl oxide
Compound 1A-6：EP-4100L (bisphenol-A epoxy bases：ADEKA company systems)
Compound 1A-7：Adeka Resin EP-4901L
Compound 1A-8：Adeka Resin EP-4000L
Compound 1A-9：TECHMOREVG-3101L
Compound 1A-10：Adeka Glycirol ED-509S (ADEKA company systems)
Compound 1A-11：Adeka Glycirol ED-501 (ADEKA company systems)
Compound 1A-12：Adeka Glycirol ED-529 (ADEKA company systems)
Compound 1B-1：Neopentylglycol diglycidyl ether
Compound 1B-2：Triglycidyl group three (2- hydroxyethyls) isocyanuric acid ester
Compound 1B-3：2- hexyl glycidyl ethers
Compound 1B-4：1,4- butanediol diglycidyl ethers
Compound 1C-1：CELLOXIDE 2021P (ester ring type epoxy radicals；Daicel Corporation systems)
Compound 1C-2：3,4- epoxy-cyclohexane carboxylate methyl esters
Compound 1C-3：(the ester ring type epoxy radicals of CELLOXIDE 3000；Daicel Corporation systems)
Compound 1D-1：GMA/MMA=3/7 copolymer (Mw：8000)
Compound 1D-2：GMA/MMA=3/7 copolymer (Mw：15000)
Compound 1E-1：ARONOXETANE OXT-101 (East Asia Synesis Company system)
Compound 1E-2：ARONOXETANE OXT-211 (East Asia Synesis Company system)
Compound 1E-3：Hydroxybutyl vinyl ether
Compound 1E-4：1,4- butanediol divinyl ethers
As the sensitivity cationic polymerization initiators of (2) energy-ray, the following compound (2- of following compounds is used
1)。
Compound 2-1：CPI-100P (San-Apro Ltd. systems)
Table 1
Table 2
Table 3
Table 4
Table 5
[evaluating example 1~30, comparative evaluation example 1~2]
The comparative composition obtained in the implementation composition and comparative example 1~2 that are obtained in above-described embodiment 1~30 is carried out
It is following to evaluate.Show the result in above-mentioned [table 1]~[table 5].
(viscosity)
1~30, the 1~2 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 5].
(curability)
By it is resulting implement composition 1~30, comparative composition 1~2 respectively with bar coater with 3~6 μm of thickness
It is applied in PET film, 1000mJ/cm is irradiated using electrodeless ultraviolet lamp2Energy.Coated face becomes after irradiating 5 minutes
Obtain inviscid situation and be evaluated as ◎, becoming inviscid situation after irradiating 15 minutes is evaluated as zero, after irradiation 15 minutes
Also the situation of residual tack be evaluated as ×.Show the result in above-mentioned [table 1]~[table 5].
(heatproof water test)
Resulting implementation composition 1~30, comparative composition 1~2 are respectively coated TAC (TACs
Element) on film after, it is film adhered using laminating machine and COP (cyclic olefin polymer), use electrodeless ultraviolet light from COP film sides
Light irradiation 1000mJ/cm2Energy be bonded and obtain test film.After 48 hours, test film is cut out into 2cm × 4cm, soaked
Stain observes process into 60 DEG C of warm water.12nd, after 24 hours viewing test piece state, by with start before do not see change
Test film is evaluated as 〇, and the test film that peeling is seen in end face is evaluated as into △, and the laminating of film is peeled off and completely fallen off
Test film is evaluated as ×.Show the result in above-mentioned [table 1]~[table 5].
(cementability)
Resulting implementation composition 1~30, comparative composition 1~2 are respectively coated and implement corona to one and put
After on COP (cyclic olefin polymer) film of electric treatment, by the film using laminating machine with implementing the another of Corona discharge Treatment
One COP (cyclic olefin polymer) is film adhered, and 1000mJ/cm is irradiated using electrodeless ultraviolet lamp2Energy be bonded
And obtain test film.90 degree of disbonded tests of the test film obtained by carrying out, by the test film evaluation that intensity is more than 2.0N/cm
For ◎, intensity is evaluated as 〇 for 1.0~2.0N/cm test film, the test film for below 1.0N/cm is evaluated as ×.Will
As a result it is shown in [table 1]~[table 5].
(amount of moisture)
1~30, the 1~2 of comparative composition to resulting implementation composition, determined respectively according to karl-Fischer method
Amount of moisture.Show the result in above-mentioned [table 1]~[table 5].
Shown by [table 1]~[table 5], curability, the heatproof of cationically polymerizable composition of the invention be aqueous and bonding
Property is excellent.
Claims (9)
1. a kind of cationically polymerizable composition, it is characterised in that containing (1) cationically polymerizable organic substance mixture and
(2) the sensitivity cationic polymerization initiators of energy-ray,
In (1) the cationically polymerizable organic substance mixture, as cationically polymerizable organic substance, contain aromatic ring
Oxygen compound (1A) is as main component, further containing aliphatic epoxy compound (1B) or cycloaliphatic epoxy (1C)
At least one of,
Relative to the mass parts of cationically polymerizable organic substance mixture 100, the amount of aromatic epoxy compound (1A) for 25~
70 mass parts, the amount of aliphatic epoxy compound (1B) is 10~45 mass parts, the amount of cycloaliphatic epoxy (1C) for 0~
45 mass parts.
2. cationically polymerizable composition according to claim 1, it is characterised in that be used as above-mentioned aliphatic epoxy chemical combination
Thing (1B) or cycloaliphatic epoxy (1C), contain at least one multi-functional epoxy compound.
3. cationically polymerizable composition according to claim 1 or 2, it is characterised in that be used as above-mentioned aromatic epoxies
Compound (1A), the shrink of the aromatic compound containing the glycidol ether selected from phenols, with more than 2 alcohol hydroxyl groups is sweet
Oily etherate, the glycidol ether compound of Polyphenols, the ethylene oxidic ester of benzoic acids, the ethylene oxidic ester of polynary acids, ring
At least one of group of epoxides of oxygen vinylbenzene or divinylbenzene.
4. cationically polymerizable composition according to claim 1 or 2, it is characterised in that be used as above-mentioned aromatic epoxies
Compound (1A), contains at least one multi-functional epoxy compound.
5. cationically polymerizable composition according to claim 1 or 2, it is characterised in that above-mentioned aromatic epoxies chemical combination
The epoxide equivalent of thing (1A) is 80~500.
6. cationically polymerizable composition according to claim 1 or 2, wherein, it is used as (1) cationically polymerizable organic matter
Matter, HMW body (1D) further comprising the weight average molecular weight with epoxy radicals for 1000~1000000, vinyl etherificate
At least one of compound or oxetane compound (1E).
7. cationically polymerizable composition according to claim 1 or 2, wherein, the sensitivity cation of (2) energy-ray gathers
It is [A] to close initiatorr+[B]r-In shown cation and the salt of anion, formula, A represents cation kind, and B represents anion kind,
R represents valence mumber.
8. cationically polymerizable composition according to claim 1 or 2, it is characterised in that amount of moisture be 5 mass % with
Under.
9. a kind of bonding agent, it is characterised in that by cationically polymerizable composition structure according to any one of claims 1 to 8
Into.
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| JP2013-143866 | 2013-07-09 | ||
| JP2013143866 | 2013-07-09 | ||
| PCT/JP2014/067779 WO2015005211A1 (en) | 2013-07-09 | 2014-07-03 | Cation-polymerizable composition |
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| KR (1) | KR102219443B1 (en) |
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| TWI690577B (en) | 2015-03-12 | 2020-04-11 | 日商松下知識產權經營股份有限公司 | Photocationically polymerizable composition, bonding method, electronic device, and producing method thereof, as well as displaying device, and producing method thereof |
| KR20170133312A (en) * | 2015-03-30 | 2017-12-05 | 가부시키가이샤 아데카 | Composition |
| JP6688063B2 (en) * | 2015-10-07 | 2020-04-28 | アイカ工業株式会社 | Photocurable resin composition and laminate |
| CN105199643B (en) * | 2015-10-26 | 2017-07-14 | 黑龙江省科学院石油化学研究院 | A kind of cation type ultraviolet photo and hot dual deep cure adhesive and preparation method thereof |
| JP6817702B2 (en) * | 2015-12-25 | 2021-01-20 | 株式会社Adeka | Curable composition, its curing method, the resulting cured product and adhesive |
| WO2017110951A1 (en) * | 2015-12-25 | 2017-06-29 | 株式会社Adeka | Curable composition, method for curing same, and cured product obtained thereby |
| KR102265025B1 (en) * | 2016-03-31 | 2021-06-14 | 가부시키가이샤 아데카 | Curable composition, manufacturing method of cured product, and cured product thereof |
| JP7008398B2 (en) * | 2016-03-31 | 2022-01-25 | 株式会社Adeka | Curable composition, method for producing cured product, and cured product thereof |
| KR102631774B1 (en) * | 2016-06-21 | 2024-01-30 | 가부시키가이샤 아데카 | Curable composition, method for producing cured product, and cured product of same |
| KR20190029612A (en) * | 2016-07-21 | 2019-03-20 | 스미또모 가가꾸 가부시키가이샤 | Polarizer |
| JP6742253B2 (en) * | 2017-02-06 | 2020-08-19 | アイカ工業株式会社 | Adhesive for fixing optical components |
| JP6810681B2 (en) * | 2017-07-28 | 2021-01-06 | 株式会社ダイセル | Monomer mixture and curable composition containing it |
| US11339245B2 (en) * | 2017-07-28 | 2022-05-24 | Daicel Corporation | Monomer mixture and curable composition containing same |
| CN110945051A (en) * | 2017-08-29 | 2020-03-31 | 三菱重工业株式会社 | Curable composition, curable paste material, curable sheet, curable molding material, curing method, and cured product |
| TWI654218B (en) * | 2018-01-08 | 2019-03-21 | 財團法人工業技術研究院 | Method for forming resin composition and heat conductive material |
| JP2019137727A (en) * | 2018-02-06 | 2019-08-22 | 株式会社Adeka | Coating composition |
| KR20210053885A (en) * | 2018-08-31 | 2021-05-12 | 가부시키가이샤 아데카 | Composition, adhesive containing the same, cured product thereof, and manufacturing method thereof |
| JP2020041060A (en) * | 2018-09-11 | 2020-03-19 | 株式会社ダイセル | Automotive parts and method for producing the same |
| CN111286291A (en) * | 2018-12-10 | 2020-06-16 | 新应材股份有限公司 | Flexible packaging material, preparation method thereof and packaging method using material |
| TWI691521B (en) | 2018-12-10 | 2020-04-21 | 新應材股份有限公司 | Flexible encapsulating material, process for preparing the same and encapsulating method using the same |
| JP2020100796A (en) * | 2018-12-25 | 2020-07-02 | 株式会社Adeka | Composition, adhesive using the same, its cured product, and manufacturing method of cured product |
| CN112574650B (en) * | 2019-09-29 | 2022-06-17 | 常州格林感光新材料有限公司 | Cationically curable compositions for metal substrates, coatings, metal articles and applications |
| JP2021147584A (en) * | 2020-03-23 | 2021-09-27 | ヘンケルジャパン株式会社 | Dual-curing adhesive composition |
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| JP2004010674A (en) * | 2002-06-04 | 2004-01-15 | Nitto Denko Corp | Ultraviolet light-curable adhesive |
| KR20080111584A (en) | 2007-06-19 | 2008-12-24 | 오성묵 | Sanitation straw |
| CN102471660B (en) * | 2009-08-21 | 2014-04-09 | Dic株式会社 | Cationically polymerizable adhesive and polarizing plate obtained using same |
| WO2011136084A1 (en) * | 2010-04-29 | 2011-11-03 | ダイセル化学工業株式会社 | Curable resin composition for screen printing and printed wiring board |
| JP2011236389A (en) | 2010-05-13 | 2011-11-24 | Toyo Ink Sc Holdings Co Ltd | Photosetting adhesive for forming polarizing plate, and polarizing plate |
| KR101541184B1 (en) * | 2010-09-24 | 2015-07-31 | 덴끼 가가꾸 고교 가부시키가이샤 | Energy-ray-curable resin composition, adhesive comprising same, and cured object obtained therefrom |
| JP5306315B2 (en) * | 2010-12-28 | 2013-10-02 | 日東電工株式会社 | Photocurable resin composition and optical material |
| JP5640030B2 (en) | 2012-03-08 | 2014-12-10 | 協立化学産業株式会社 | Method for producing laminated film |
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| JPWO2015005211A1 (en) | 2017-03-02 |
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| KR102219443B1 (en) | 2021-02-25 |
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