JP2006096834A - Adhesive composition including epoxy resin - Google Patents
Adhesive composition including epoxy resin Download PDFInfo
- Publication number
- JP2006096834A JP2006096834A JP2004283210A JP2004283210A JP2006096834A JP 2006096834 A JP2006096834 A JP 2006096834A JP 2004283210 A JP2004283210 A JP 2004283210A JP 2004283210 A JP2004283210 A JP 2004283210A JP 2006096834 A JP2006096834 A JP 2006096834A
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- meth
- copolymer
- adhesive composition
- epoxy group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 51
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 48
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 239000000853 adhesive Substances 0.000 title claims abstract description 33
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 33
- 229920001577 copolymer Polymers 0.000 claims abstract description 20
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 20
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- 239000000470 constituent Substances 0.000 claims description 3
- 230000009477 glass transition Effects 0.000 claims description 2
- 239000004593 Epoxy Substances 0.000 abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 22
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 16
- -1 2-ethylhexyl Chemical group 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229920000058 polyacrylate Polymers 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical group CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000004658 ketimines Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- KFUSXMDYOPXKKT-VIFPVBQESA-N (2s)-2-[(2-methylphenoxy)methyl]oxirane Chemical compound CC1=CC=CC=C1OC[C@H]1OC1 KFUSXMDYOPXKKT-VIFPVBQESA-N 0.000 description 1
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-UHFFFAOYSA-N 0.000 description 1
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- OVEUFHOBGCSKSH-UHFFFAOYSA-N 2-methyl-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound CC1=CC=CC=C1N(CC1OC1)CC1OC1 OVEUFHOBGCSKSH-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- WADSJYLPJPTMLN-UHFFFAOYSA-N 3-(cycloundecen-1-yl)-1,2-diazacycloundec-2-ene Chemical compound C1CCCCCCCCC=C1C1=NNCCCCCCCC1 WADSJYLPJPTMLN-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- NFVPEIKDMMISQO-UHFFFAOYSA-N 4-[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC=C(O)C=C1 NFVPEIKDMMISQO-UHFFFAOYSA-N 0.000 description 1
- VNGLVZLEUDIDQH-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;2-methyloxirane Chemical compound CC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 VNGLVZLEUDIDQH-UHFFFAOYSA-N 0.000 description 1
- AHZMKQOTAXPZDC-UHFFFAOYSA-N 4-methyl-n-propylpentan-2-imine Chemical compound CCCN=C(C)CC(C)C AHZMKQOTAXPZDC-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Chemical group 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical group CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- FYYIUODUDSPAJQ-XVBQNVSMSA-N [(1S,6R)-7-oxabicyclo[4.1.0]heptan-3-yl]methyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1CC[C@H]2O[C@H]2C1 FYYIUODUDSPAJQ-XVBQNVSMSA-N 0.000 description 1
- DZCVLTAQZZDCMH-UHFFFAOYSA-N [1-(oxiran-2-ylmethoxymethyl)cyclohexyl]methanol Chemical compound C1OC1COCC1(CO)CCCCC1 DZCVLTAQZZDCMH-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- DTGWMJJKPLJKQD-UHFFFAOYSA-N butyl 2,2-dimethylpropaneperoxoate Chemical group CCCCOOC(=O)C(C)(C)C DTGWMJJKPLJKQD-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- KEIQPMUPONZJJH-UHFFFAOYSA-N dicyclohexylmethanediamine Chemical compound C1CCCCC1C(N)(N)C1CCCCC1 KEIQPMUPONZJJH-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- QHDRKFYEGYYIIK-UHFFFAOYSA-N isovaleronitrile Chemical compound CC(C)CC#N QHDRKFYEGYYIIK-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、エポキシ樹脂を含有する接着剤組成物(以下、エポキシ樹脂系接着剤組成物ともいう。)に関するものである。
The present invention relates to an adhesive composition containing an epoxy resin (hereinafter also referred to as an epoxy resin-based adhesive composition).
ビスフェノール骨格を有するエポキシ樹脂(以下、ビスフェノール系エポキシ樹脂ともいう。)は、高強度の接着剤や、防錆プライマーに使用されている。かかるエポキシ樹脂の改質を目的に、各種化合物のブレンドが検討されており、例えば、初期粘着性の付与やイオン性不純物の低減、塗料密着性を向上させるため、アクリルポリマーをブレンドすることが知られている(特許文献1、2、3)。
エポキシ基を有するアクリルポリマーおよびエポキシ樹脂を含有する組成物、および概組成物は自己固定接着剤として有効であることが知られている(特許文献4)。エポキシ基を有するアクリルポリマーおよびエポキシ樹脂を含有する組成物はフレキシブルプリント基板と銅箔や半導体チップの接着に有用であることも知られている(特許文献5、6)。
しかしながら、上記発明に使用されるアクリルポリマーは、ブレンドして使用する場合には、エポキシ樹脂への分散性が不十分であって、接着性を向上させにくい場合があった。
また、エポキシ樹脂は高粘度の液状または固体であり、エポキシ樹脂を主成分とする組成物は取り扱い作業性が悪いため、溶剤や可塑剤の添加による低粘度化が検討されたが、溶剤や低分子可塑剤による接着剤層の発泡、強度低下や耐熱性低下が生じ、好ましいものではなかった。
反応性希釈剤として、エポキシ基を有する低分子化合物も知られているが(非特許文献1)、かかる反応性希釈剤は、粘度低下に効果はあるが、耐熱性や耐候性が低下するために使用が制限された。
Epoxy resins having a bisphenol skeleton (hereinafter also referred to as bisphenol-based epoxy resins) are used for high-strength adhesives and rust prevention primers. For the purpose of modifying such epoxy resins, blends of various compounds have been studied. For example, it is known to blend acrylic polymers to impart initial tackiness, reduce ionic impurities, and improve paint adhesion. (Patent Documents 1, 2, and 3).
It is known that a composition containing an acrylic polymer having an epoxy group and an epoxy resin, and a general composition are effective as a self-fixing adhesive (Patent Document 4). It is also known that a composition containing an acrylic polymer having an epoxy group and an epoxy resin is useful for bonding a flexible printed board to a copper foil or a semiconductor chip (Patent Documents 5 and 6).
However, when the acrylic polymer used in the above invention is blended, the dispersibility in the epoxy resin is insufficient, and it may be difficult to improve the adhesion.
In addition, epoxy resins are highly viscous liquids or solids, and compositions with an epoxy resin as the main component have poor handling workability. Therefore, low viscosity by adding a solvent or plasticizer has been studied. Foaming of the adhesive layer due to the molecular plasticizer, reduction in strength and reduction in heat resistance occurred, which was not preferable.
Although low molecular weight compounds having an epoxy group are also known as reactive diluents (Non-patent Document 1), such reactive diluents are effective in reducing viscosity, but heat resistance and weather resistance are reduced. Limited use.
本発明の課題は、接着強度が大きいのみならず耐熱性や耐候性に優れ、低粘度であって取り扱い作業性に優れたエポキシ樹脂系接着剤組成物を提供することである。
An object of the present invention is to provide an epoxy resin adhesive composition having not only high adhesive strength but also excellent heat resistance and weather resistance, low viscosity and excellent handling workability.
上記課題を解決するため、本発明の接着剤組成物は、エポキシ基を有する単量体単位およびエポキシ基を有さない(メタ)アクリル酸エステル単位を構成単位として含み重量平均分子量が500〜5000である共重合体およびエポキシ樹脂を含有するものである。
In order to solve the above problems, the adhesive composition of the present invention includes a monomer unit having an epoxy group and a (meth) acrylic acid ester unit having no epoxy group as a constituent unit, and a weight average molecular weight of 500 to 5,000. It contains a copolymer and an epoxy resin.
本発明の組成物は、接着強度が大きく、耐熱性や耐候性に優れ、取り扱い作業性に優れており、接着剤組成物として好適である。
The composition of the present invention has a high adhesive strength, is excellent in heat resistance and weather resistance, is excellent in handling workability, and is suitable as an adhesive composition.
本発明の共重合体は、重量平均分子量が500〜5000であり、1000〜4000が好ましく、1500〜3000が特に好ましい。500未満では接着剤が発泡しやすく、5000以上では接着剤の粘度が低下せず、いずれも好ましくない。 The copolymer of the present invention has a weight average molecular weight of 500 to 5000, preferably 1000 to 4000, and particularly preferably 1500 to 3000. If it is less than 500, the adhesive tends to foam, and if it is 5000 or more, the viscosity of the adhesive does not decrease, which is not preferable.
エポキシ基を有する単量体としては、(メタ)アクリル酸グリシジル、(メタ)アクリル酸エポキシシクロヘキシル、(メタ)アクリル酸エポキシシクロヘキサンメチル、アリルグリシジルエーテル、ビニルグリシジルエーテル等が例示される。入手が容易であって接着強度が向上しやすいメタクリル酸グリシジルが好ましい。 Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, epoxycyclohexyl (meth) acrylate, epoxycyclohexanemethyl (meth) acrylate, allyl glycidyl ether, and vinyl glycidyl ether. Glycidyl methacrylate, which is easily available and easily improves the adhesive strength, is preferred.
エポキシ基を有さない(メタ)アクリル酸エステルとしては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸プロピル、(メタ)アクリル酸イソプロピル、(メタ)アクリル酸ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸s−ブチル、(メタ)アクリル酸t−ブチル、(メタ)アクリル酸ネオペンチル、(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸イソデシル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸トリデシルおよび(メタ)アクリル酸ステアリル等の(メタ)アクリル酸アルキル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸イソボルニルおよび(メタ)アクリル酸トリシクロデシニル等の(メタ)アクリル酸脂環式アルキル、(メタ)アクリル酸2−メトキシエチル、(メタ)アクリル酸ジメチルアミノエチル、(メタ)アクリル酸クロロエチル、(メタ)アクリル酸トリフルオロエチルおよび(メタ)アクリル酸テトラヒドロフルフリル等のヘテロ原子含有(メタ)アクリル酸エステル類が挙げられる。これら単量体は、1種類または2種類以上用いることが可能である。
得られる共重合体のTgが低く、粘度低下が期待できるため、該単量体の合計の中で炭素数4〜8のアクリル酸エステルの割合が70質量%以上であることが好ましい。
Examples of the (meth) acrylic acid ester having no epoxy group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, Isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, neopentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, (meta ) Alkyl (meth) acrylates such as lauryl acrylate, tridecyl (meth) acrylate and stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and tricyclodecynyl (meth) acrylate (Meth) acrylic acid alicyclic alkyl, (meth) acrylic Heteroatom-containing (meth) acrylates such as 2-methoxyethyl, dimethylaminoethyl (meth) acrylate, chloroethyl (meth) acrylate, trifluoroethyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate Is mentioned. These monomers can be used alone or in combination of two or more.
Since the resulting copolymer has a low Tg and a decrease in viscosity can be expected, the proportion of the acrylic acid ester having 4 to 8 carbon atoms in the total of the monomers is preferably 70% by mass or more.
エポキシ基を有する単量体およびエポキシ基を有さない(メタ)アクリル酸エステルの割合は、両者の合計量100質量部を基準として、それぞれ5〜50質量部および50〜95質量部が好ましく、それぞれ10〜30質量部および70〜90質量部がより好ましい。エポキシ基を有する単量体の割合が5質量部未満では、粘度低下効果が少なく、接着強度も向上しない場合がある。エポキシ基を有する単量体の割合が50質量部を越えると、得られる共重合体とエポキシ樹脂との相溶性が増し、接着強度が低下する場合がある。 The proportion of the monomer having an epoxy group and the (meth) acrylic acid ester having no epoxy group is preferably 5 to 50 parts by mass and 50 to 95 parts by mass, respectively, based on the total amount of 100 parts by mass of both. 10-30 mass parts and 70-90 mass parts are respectively more preferable. When the proportion of the monomer having an epoxy group is less than 5 parts by mass, the effect of decreasing the viscosity is small and the adhesive strength may not be improved. When the proportion of the monomer having an epoxy group exceeds 50 parts by mass, the compatibility between the obtained copolymer and the epoxy resin increases, and the adhesive strength may decrease.
共重合体の構成単位としてその他に使用できる単量体には特に制限はなく、例えば、(メタ)アクリル酸、(メタ)アクリル酸ヒドロキシエチル、スチレン、α−メチルスチレン、アクリロニトリル、酢酸ビニルなどが挙げられる。
本発明の共重合体は、硬化後の状態でエポキシ樹脂と非相溶であり、エポキシ樹脂の相中でミクロドメインを作ることにより硬化時の応力を緩和して、接着強度を向上させることができる。したがって、芳香族基を含有する(メタ)アクリル酸エステルは、エポキシ樹脂との相溶性を向上させるが、接着強度を低下させるので使用しないことが好ましい。
There are no particular restrictions on the other monomers that can be used as the constituent unit of the copolymer, such as (meth) acrylic acid, hydroxyethyl (meth) acrylate, styrene, α-methylstyrene, acrylonitrile, vinyl acetate, and the like. Can be mentioned.
The copolymer of the present invention is incompatible with the epoxy resin in the cured state, and can relieve stress at the time of curing by making microdomains in the phase of the epoxy resin, thereby improving the adhesive strength. it can. Therefore, the (meth) acrylic acid ester containing an aromatic group improves compatibility with the epoxy resin, but it is preferable not to use it because it lowers the adhesive strength.
共重合体のガラス転移温度(以下、Tgともいう。)は、−10℃以下であることが好ましい。−10℃を越える場合は接着剤の粘度低下効果が少ない場合がある。 The glass transition temperature (hereinafter also referred to as Tg) of the copolymer is preferably −10 ° C. or lower. When it exceeds −10 ° C., the effect of reducing the viscosity of the adhesive may be small.
本発明の共重合体は、目的に応じて選択された単量体を公知の方法で重合させて得ることができる。溶液重合、塊状重合、乳化重合、懸濁重合などのいずれであってもよい。溶液重合を採用する場合、有機溶媒としては、通常溶媒として用いられるものでよく、例えばテトラヒドロフランおよびジオキサン等の環状エーテル類、ベンゼン、トルエンおよびキシレン等の芳香族炭化水素化合物、酢酸エチルおよび酢酸ブチル等のエステル類、アセトン、メチルエチルケトンおよびシクロヘキサノン等のケトン類、メタノール、エタノールおよびイソプロパノール等のアルコール類等があげられ、これらの1種または2種以上を用いることができる。 The copolymer of the present invention can be obtained by polymerizing a monomer selected according to the purpose by a known method. Any of solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like may be used. When adopting solution polymerization, the organic solvent may be one usually used as a solvent, for example, cyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbon compounds such as benzene, toluene and xylene, ethyl acetate and butyl acetate, etc. Esters, ketones such as acetone, methyl ethyl ketone and cyclohexanone, alcohols such as methanol, ethanol and isopropanol, and the like, and one or more of these can be used.
ラジカル重合開始剤としては、ジイソプロピルパーオキシジカーボネート、ターシャリーブチルパーオキシピバレート、ベンゾイルパーオキサイド、ラウロイルパーオキサイドおよびジターシャリーブチルパーオキサイド等の過酸化物、またはアゾビスイソブチロニトリル、アゾビスイソバレロニトリル等のアゾ化合物、過硫酸アンモニウム、過硫酸カリウム等の無機過酸化物が使用できる。また、アルコールやメルカプタン系化合物などの連鎖移動剤も用いて良いが、臭気が強く環境に悪影響を与え、耐候性の低下にもつながるため、用いないことが好ましい。 As radical polymerization initiators, peroxides such as diisopropyl peroxydicarbonate, tertiary butyl peroxypivalate, benzoyl peroxide, lauroyl peroxide and ditertiary butyl peroxide, or azobisisobutyronitrile, azobis An azo compound such as isovaleronitrile and an inorganic peroxide such as ammonium persulfate and potassium persulfate can be used. A chain transfer agent such as an alcohol or a mercaptan-based compound may also be used, but it is preferably not used because it has a strong odor and adversely affects the environment, leading to a decrease in weather resistance.
単量体を150〜350℃の温度で重合させて得られる共重合体は、不純物がほとんどなく接着強度や耐候性の優れたものとなりやすいために好ましい。重合温度は180〜320℃がより好ましく、200〜300℃がさらに好ましい。バッチ重合、セミ連続重合、連続重合などのいずれも採用できるが、撹拌槽型反応器を使用する連続重合は、生産性が優れるために特に好ましい。このような高温連続重合は公知である(特表昭57−502171号公報、特開昭59−6207号公報、特開昭60−511992号公報)。 A copolymer obtained by polymerizing a monomer at a temperature of 150 to 350 ° C. is preferable because it has almost no impurities and tends to have excellent adhesive strength and weather resistance. The polymerization temperature is more preferably 180 to 320 ° C, further preferably 200 to 300 ° C. Any of batch polymerization, semi-continuous polymerization, continuous polymerization and the like can be adopted, but continuous polymerization using a stirred tank reactor is particularly preferable because of excellent productivity. Such high-temperature continuous polymerization is known (Japanese Patent Publication No. 57-502171, Japanese Patent Publication No. 59-6207, Japanese Patent Publication No. 60-511992).
本発明のエポキシ樹脂は、公知のものが採用される。係るエポキシ樹脂としては、エピクロルヒドリン−ビスフェノールA型エポキシ樹脂、エピクロルヒドリン−ビスフェノールF型エポキシ樹脂、テトラブロモビスフェノールAのグリシジルエーテルなどの難燃型エポキシ樹脂、ノボラック型エポキシ樹脂、水添ビスフェノールA型エポキシ樹脂、ビスフェノールAプロピレンオキシド付加物のグリシジルエーテル型エポキシ樹脂、p−オキシ安息香酸グリシジルエーテルエステル型エポキシ樹脂、m−アミノフェノール系エポキシ樹脂、ジアミノジフェニルメタン系エポキシ樹脂、ウレタン変性エポキシ樹脂、各種脂環式エポキシ樹脂、N,N−ジグリシジルアニリン、N,N−ジグリシジル−o−トルイジン、トリグリシジルイソシアヌレート、ポリアルキレングリコールジグリシジルエーテル、グリセリンなどのごとき多価アルコールのグリシジルエーテル、ヒダントイン型エポキシ樹脂、石油樹脂などのごとき不飽和重合体のエポキシ化物などが例示されるが、これらに限定されるものではなく、一般に使用されているエポキシ樹脂が使用されうる。これらのエポキシ樹脂のうちではとくにエポキシ基を少なくとも分子中に2個含有するものが、硬化に際し反応性が高く、また硬化物が3次元的網目をつくりやすいなどの点から好ましい。これらの中でも耐熱性の点からビスフェノールA型エポキシ樹脂が好ましい。
ビスフェノールA型エポキシ樹脂のなかでもエポキシ当量が170〜270(g/eq)である液状樹脂が特に好ましい。
A well-known thing is employ | adopted for the epoxy resin of this invention. Examples of such epoxy resins include epichlorohydrin-bisphenol A type epoxy resins, epichlorohydrin-bisphenol F type epoxy resins, flame retardant epoxy resins such as tetrabromobisphenol A glycidyl ether, novolac type epoxy resins, hydrogenated bisphenol A type epoxy resins, Bisphenol A propylene oxide adduct glycidyl ether type epoxy resin, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ester Examples include glycidyl ethers of polyhydric alcohols such as tellurium and glycerin, epoxidized products of unsaturated polymers such as hydantoin type epoxy resins and petroleum resins, but are not limited to these and are generally used. Any epoxy resin can be used. Of these epoxy resins, those containing at least two epoxy groups in the molecule are particularly preferred because they are highly reactive during curing and the cured product easily forms a three-dimensional network. Among these, bisphenol A type epoxy resin is preferable from the viewpoint of heat resistance.
Among the bisphenol A type epoxy resins, liquid resins having an epoxy equivalent of 170 to 270 (g / eq) are particularly preferable.
ビスフェノールA型エポキシ樹脂(X)と上記共重合体(Y)の比率(質量比)は、両者の合計100を基準として、X/Y=60〜95/5〜40が好ましく、70〜90/10〜30がより好ましい。Xが60質量%未満では接着強度が低下する場合があり、95質量%を越えると効果的に粘度が低下せず、接着強度が向上しない場合がある。 The ratio (mass ratio) between the bisphenol A type epoxy resin (X) and the copolymer (Y) is preferably X / Y = 60 to 95/5 to 40, based on the total of both 100, and 70 to 90 / 10-30 are more preferable. When X is less than 60% by mass, the adhesive strength may be reduced, and when it exceeds 95% by mass, the viscosity is not effectively reduced and the adhesive strength may not be improved.
本発明の接着剤組成物は、エポキシ樹脂用の硬化剤が添加されたものであることが好ましい。エポキシ樹脂用の硬化剤としては、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ヘキサメチレンジアミン、ジエチルアミノプロピルアミン、N−アミノエチルピペラジン、イソホロンジアミン、ジアミノジシクロヘキシルメタン、m−キシレンジアミン、m−フェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン等の1級アミン、(CH3)2N(CH2)nN(CH3)2(式中nは1〜10の整数)で示される直鎖状ジアミン、(CH3)2−N(CH2)n−CH3(式中nは0〜10の整数)で示される直鎖第3級アミン、テトラメチルグアニジン、N{(CH2)nCH3}3(式中nは1〜10の整数)で示されるアルキル第3級モノアミン、トリスジメチルアミノメチルフェノール、トリエタノールアミン、ピペリジン、N,N’−ジメチルピペラジン、トリエチレンジアミン、ピリジン、ピコリン、ジアザビシクロウンデセン、ベンジルジメチルアミン、2−(ジメチルアミノメチル)フェノール、2,4,6−トリス(ジメチルアミノメチル)フェノール、BASF社製ラミロンC−260、CIBA社製Araldit HY−964およびロームアンドハース社製メンセンジアミン等の第2級または第3級アミン、1,2−エチレンビス(イソペンチリデンイミン)、1,2−ヘキシレンビス(イソペンチリデンイミン)、1,2−プロピレンビス(イソペンチリデンイミン)、p,p′−ビフェニレンビス(イソペンチリデンイミン)、1,2−エチレンビス(イソプロピリデンイミン)、1,3−プロピレンビス(イソプロピリデンイミン)、p−フェニレンビス(イソペンチリデンイミン)等のケチミン、無水フタル酸、無水トリメリット酸、無水ピロメリット酸、無水ベンゾフェノンテトラカルボン酸等の酸無水物、各種ポリアミド樹脂、ジシアンジアミドおよびその誘導体および各種イミダゾール類等が例示される。かかる硬化剤の使用量は、エポキシ樹脂100部に対し、5部〜100部が好ましい。
また、硬化剤の変わりに光開始剤を使用しても良い。係る光開始剤としては、オニウム塩またはカチオン有機金属類が例示される。
The adhesive composition of the present invention is preferably one to which a curing agent for epoxy resin is added. Curing agents for epoxy resins include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, diethylaminopropylamine, N-aminoethylpiperazine, isophoronediamine, diaminodicyclohexylmethane, m-xylenediamine, m- Primary amines such as phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, etc., linear diamines represented by (CH3) 2N (CH2) nN (CH3) 2 (where n is an integer from 1 to 10), (CH3) 2 Linear tertiary amine represented by -N (CH2) n-CH3 (wherein n is an integer of 0 to 10), tetramethylguanidine, N {(CH2) nCH3} 3 (wherein n is 1 to 10) An alkyl tertiary monoamine represented by an integer), trisdimethylamino Ruphenol, triethanolamine, piperidine, N, N'-dimethylpiperazine, triethylenediamine, pyridine, picoline, diazabicycloundecene, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris Secondary or tertiary amines such as (dimethylaminomethyl) phenol, BASF Ramilon C-260, CIBA Araldit HY-964, and Rohm and Haas Mensendiamine, 1,2-ethylenebis (iso Pentylideneimine), 1,2-hexylenebis (isopentylideneimine), 1,2-propylenebis (isopentylideneimine), p, p'-biphenylenebis (isopentylideneimine), 1,2-ethylenebis (Isopropylideneimine), 1,3-propylenebis (isopropylidene) Pyridenimine), p-phenylenebis (isopentylidenimine) and other ketimines, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride and other acid anhydrides, various polyamide resins, dicyandiamide and derivatives thereof And various imidazoles. The amount of the curing agent used is preferably 5 to 100 parts with respect to 100 parts of the epoxy resin.
Moreover, you may use a photoinitiator instead of a hardening | curing agent. Examples of such photoinitiators include onium salts or cationic organometallics.
本発明の組成物は、必要により反応性希釈剤が添加されたものであってもよい。かかる希釈剤としては、アルキルグリシジルエーテル、o-クレジルグリシジルエーテル、アルキルフェノールグリシジルエーテル、シクロヘキサンジメタノールモノグリシジルエーテル、臭素含有グリシジルエーテル、などの単官能の低分子グリシジルエーテルが例示される。 The composition of the present invention may be added with a reactive diluent as necessary. Examples of such diluents include monofunctional low molecular weight glycidyl ethers such as alkyl glycidyl ether, o-cresyl glycidyl ether, alkylphenol glycidyl ether, cyclohexanedimethanol monoglycidyl ether, and bromine-containing glycidyl ether.
本発明の組成物は、基材との接着性を高めるために接着性増強剤を添加されたものであってもよい。その具体例としては、例えばN−(β−アミノエチル)−γ−アミノプロピルトリメトキシシラン、N−(β−アミノエチル)−γ−アミノプロピルメチルジメトキシシラン、N−(β−アミノエチル)−γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリメトキシシランおよびγ−アミノプロピルトリエトキシシラン、γートリエトキシシリルーN(1,3−ジメチルブチリデン)プロピルアミン等が例示される。 The composition of the present invention may be one to which an adhesion enhancer has been added in order to enhance the adhesion to the substrate. Specific examples thereof include N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl)- Examples include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane, γ-triethoxysilyl-N (1,3-dimethylbutylidene) propylamine, and the like.
本発明の組成物は、硬化速度を調整するため、フェノールやビスフェノールA、フェノール樹脂などが添加されたものであっても良い。作業性を調整するためにエポキシ基やイソシアネート基、ビニル基を含有するシランカップリング剤、シリカなどのチクソ性付与剤、紫外線吸収剤、艶消し剤、顔料、充填剤などが添加されたものであっても良い。
The composition of the present invention may be added with phenol, bisphenol A, phenol resin or the like in order to adjust the curing rate. In order to adjust workability, silane coupling agents containing epoxy groups, isocyanate groups, vinyl groups, thixotropic agents such as silica, UV absorbers, matting agents, pigments, fillers, etc. are added. There may be.
<製造例1>
電熱式ヒーターを備えた容量1000mlの加圧式攪拌槽型反応器を、温度230℃に保った。次いで、反応器の圧力を一定に保ちながら、表1に示す単量体混合物100部、MEK10部、重合開始剤としてジターシャリーブチルパーオキサイド1部からなる原料混合物を、一定の供給速度(80g/分、滞留時間:12分)で原料タンクから反応器に連続供給を行い、原料混合物の供給量に相当する反応液を出口から連続的に抜き出した。反応開始直後に、一旦反応温度が低下した後、重合熱による温度上昇が認められたが、ヒータを制御することにより、反応温度245℃を保持した。原料混合物の供給開始から温度が安定した時点を、反応液の採取開始点とし、これから25分かけて2kgの原料混合液を供給し、1.9kgの反応液を回収した。その後反応液を薄膜蒸発器に導入して、未反応モノマー等の揮発成分を分離して濃縮液を得た。ガスクロマトグラフ分析より、濃縮液中には未反応モノマーは存在していなかった。溶媒としてテトラヒドロフランを使用し、ゲルパーミエーションクロマトグラフ(以下、GPCという。)で測定したポリスチレン換算の重量平均分子量(以下、Mwという。)は1800であった。上記濃縮液の成分である共重合体を「重合体1」という。
<Production Example 1>
A 1000 ml capacity pressurized stirred tank reactor equipped with an electric heater was maintained at a temperature of 230 ° C. Next, while maintaining the reactor pressure constant, a raw material mixture comprising 100 parts of the monomer mixture shown in Table 1, 10 parts of MEK, and 1 part of ditertiary butyl peroxide as a polymerization initiator was supplied at a constant feed rate (80 g / Min., Residence time: 12 minutes), the raw material tank was continuously supplied to the reactor, and the reaction liquid corresponding to the supply amount of the raw material mixture was continuously extracted from the outlet. Immediately after the start of the reaction, once the reaction temperature decreased, a temperature increase due to the heat of polymerization was observed, but the reaction temperature was maintained at 245 ° C. by controlling the heater. The time when the temperature was stabilized from the start of the supply of the raw material mixture was taken as the starting point for collecting the reaction liquid, and 2 kg of the raw material mixture liquid was supplied over 25 minutes, and 1.9 kg of the reaction liquid was recovered. Thereafter, the reaction solution was introduced into a thin film evaporator to separate volatile components such as unreacted monomers to obtain a concentrated solution. From the gas chromatographic analysis, no unreacted monomer was present in the concentrate. Tetrahydrofuran was used as a solvent, and the weight average molecular weight in terms of polystyrene (hereinafter referred to as Mw) measured by gel permeation chromatography (hereinafter referred to as GPC) was 1800. The copolymer that is a component of the concentrated solution is referred to as “polymer 1”.
<製造例2〜5>条件を表1のように変更する以外は製造例1と同様に重合および処理を行い、共重合体を製造した。得られた重合体をそれぞれ重合体2〜5という。これらの分析結果を表1に示す。 <Manufacture examples 2-5> Except having changed conditions as Table 1, superposition | polymerization and the process were performed similarly to manufacture example 1, and the copolymer was manufactured. The obtained polymers are referred to as polymers 2 to 5, respectively. The results of these analyzes are shown in Table 1.
表1における略号の意味は以下のとおりである。
MMA:メタアクリル酸メチル
BA:アクリル酸ブチル
HA:アクリル酸2−エチルへキシル
GMA:メタアクリル酸グリシジル
M100:メタアクリル酸エポキシシクロヘキシルメチル(ダイセル製 サイクロマーM100)
The meanings of the abbreviations in Table 1 are as follows.
MMA: Methyl methacrylate BA: Butyl acrylate HA: 2-ethylhexyl acrylate GMA: Glycidyl methacrylate M100: Epoxycyclohexylmethyl methacrylate (Daicel Cyclomer M100)
<実施例1〜6>
重合体1〜5を表2の条件で配合して組成物を調製した。予めサンドペ−パーで磨いた後、アセトン拭きをおこなった冷間圧延ステンレス鋼板(SUS304)に、上記組成物を塗布した後、2枚を張り合わせて、引張せん断試験用サンプル(ASTM D1002−53T準拠)を作成した。表2の配合は質量比である。23℃で2日および50℃で3日硬化後、引張せん断強度を測定した。結果を表3に示す。
また、膜厚1mmになるように硬化物のシートを作成し、耐候性試験に用いた。
<Examples 1-6>
Polymers 1 to 5 were blended under the conditions shown in Table 2 to prepare a composition. After applying the above composition to a cold-rolled stainless steel plate (SUS304) that has been polished with a sandpaper in advance and then wiped with acetone, the two pieces are bonded together, and a sample for tensile shear test (according to ASTM D1002-53T) It was created. The formulation in Table 2 is a mass ratio. After curing at 23 ° C. for 2 days and at 50 ° C. for 3 days, the tensile shear strength was measured. The results are shown in Table 3.
Moreover, the sheet | seat of hardened | cured material was created so that it might become a film thickness of 1 mm, and it used for the weather resistance test.
<比較例1〜3>表2の条件で配合して比較用の組成物を調製し、実施例と同様の試験をおこなった。 <Comparative Examples 1-3> A composition for comparison was prepared by blending under the conditions shown in Table 2, and the same tests as in Examples were conducted.
表2における配合成分として重合体1〜5以外に使用したものは以下のとおりである。
へロキシ8:ジャパンエポキシレジン社製反応性希釈剤
ARUFON UP1110:東亞合成製無官能アクリルポリマー(Mw=2600)
エピコート828:ジャパンエポキシレジン社製ビスフェノールA型エポキシ樹脂(エポキシ当量189g/eq)
エピキュアH30:ジャパンエポキシレジン社製ケチミン型硬化剤
What was used other than the polymers 1-5 as a compounding component in Table 2 is as follows.
HEROXY 8: Reactive Diluent ARUFON UP1110 manufactured by Japan Epoxy Resin Co., Ltd. Non-functional acrylic polymer (Mw = 2600) manufactured by Toagosei
Epicoat 828: Bisphenol A type epoxy resin manufactured by Japan Epoxy Resin Co., Ltd. (epoxy equivalent 189 g / eq)
EpiCure H30: Ketimine type curing agent manufactured by Japan Epoxy Resin Co., Ltd.
表2に示す組成物を用いて、下記の試験をおこなった。
<接着性>
硬化後のせん断引張試験サンプルを用いて、テンシロン200(東洋精機製)にて50mm/分で引張り、破断時の強度を測定した。
<耐熱性>
せん断引張試験サンプルを70℃に設定された恒温槽に投入し、1時間後に引張試験をおこなった。
<耐候性>
硬化シートをメタルウェザー耐候性試験機(ダイプラウィンテス製)に設置し、100時間試験後の外観を観察した。
<作業性>
表2に記載の重合体、エポキシ樹脂、硬化剤よりなる配合物を、ヘラで10cm×10cmに塗り広げ、そのヘラ捌きを評価した。
結果を表3に示す。
The following tests were conducted using the compositions shown in Table 2.
<Adhesiveness>
Tensileon 200 (manufactured by Toyo Seiki Co., Ltd.) was used to pull the cured tensile test sample after curing, and the strength at break was measured.
<Heat resistance>
The shear tensile test sample was put into a thermostat set at 70 ° C., and a tensile test was conducted after 1 hour.
<Weather resistance>
The cured sheet was placed in a metal weather weathering tester (manufactured by Daipurwines), and the appearance after the 100-hour test was observed.
<Workability>
A blend of a polymer, an epoxy resin and a curing agent described in Table 2 was applied to a 10 cm × 10 cm with a spatula, and the spatula was evaluated.
The results are shown in Table 3.
本発明の組成物は接着強度が大きいのみならず、耐熱性や耐候性に優れ、低粘度であって、取り扱い作業性も良好であり、接着剤として有用である。 The composition of the present invention is not only high in adhesive strength but also excellent in heat resistance and weather resistance, low viscosity, good handling workability, and useful as an adhesive.
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008222809A (en) * | 2007-03-12 | 2008-09-25 | Sumitomo Bakelite Co Ltd | Liquid resin composition and semiconductor device manufactured using the liquid resin composition |
JP2011202158A (en) * | 2010-03-03 | 2011-10-13 | Dainippon Printing Co Ltd | Adhesive composition and method for producing curable pressure-sensitive adhesive sheet |
US20120168814A1 (en) * | 2009-11-09 | 2012-07-05 | Sony Chemical & Information Device Corporation | Adhesive composition |
JPWO2011086680A1 (en) * | 2010-01-15 | 2013-05-16 | デクセリアルズ株式会社 | Anisotropic conductive adhesive |
CN104559885A (en) * | 2014-12-17 | 2015-04-29 | 唐华烨 | Phenol propane epoxy resin adhesive |
JP2015180726A (en) * | 2015-03-24 | 2015-10-15 | デクセリアルズ株式会社 | adhesive composition |
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JP2017226824A (en) * | 2016-06-16 | 2017-12-28 | 信越化学工業株式会社 | Epoxy resin composition |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55147578A (en) * | 1979-05-09 | 1980-11-17 | Nippon Carbide Ind Co Ltd | Adhesive composition |
JPS6173726A (en) * | 1984-09-19 | 1986-04-15 | Nippon Oil & Fats Co Ltd | Production of nonaqueous epoxy resin dispersion |
JPH01271408A (en) * | 1988-04-21 | 1989-10-30 | Shinnakamura Kagaku Kogyo Kk | Composition for pressure-sensitive adhesive |
JP2002188070A (en) * | 2001-09-28 | 2002-07-05 | Hitachi Chem Co Ltd | Adhesive composition for circuit connection |
JP2002531671A (en) * | 1998-12-11 | 2002-09-24 | スリーエム イノベイティブ プロパティズ カンパニー | Acrylic terpolymer for use as self-fixating adhesive |
JP2003327774A (en) * | 2002-05-10 | 2003-11-19 | Toagosei Co Ltd | Aqueous polymer composition |
-
2004
- 2004-09-29 JP JP2004283210A patent/JP4576966B2/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS55147578A (en) * | 1979-05-09 | 1980-11-17 | Nippon Carbide Ind Co Ltd | Adhesive composition |
JPS6173726A (en) * | 1984-09-19 | 1986-04-15 | Nippon Oil & Fats Co Ltd | Production of nonaqueous epoxy resin dispersion |
JPH01271408A (en) * | 1988-04-21 | 1989-10-30 | Shinnakamura Kagaku Kogyo Kk | Composition for pressure-sensitive adhesive |
JP2002531671A (en) * | 1998-12-11 | 2002-09-24 | スリーエム イノベイティブ プロパティズ カンパニー | Acrylic terpolymer for use as self-fixating adhesive |
JP2002188070A (en) * | 2001-09-28 | 2002-07-05 | Hitachi Chem Co Ltd | Adhesive composition for circuit connection |
JP2003327774A (en) * | 2002-05-10 | 2003-11-19 | Toagosei Co Ltd | Aqueous polymer composition |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2008222809A (en) * | 2007-03-12 | 2008-09-25 | Sumitomo Bakelite Co Ltd | Liquid resin composition and semiconductor device manufactured using the liquid resin composition |
US20120168814A1 (en) * | 2009-11-09 | 2012-07-05 | Sony Chemical & Information Device Corporation | Adhesive composition |
JPWO2011086680A1 (en) * | 2010-01-15 | 2013-05-16 | デクセリアルズ株式会社 | Anisotropic conductive adhesive |
US8790547B2 (en) | 2010-01-15 | 2014-07-29 | Dexerials Corporation | Anisotropic conductive adhesive |
JP2011202158A (en) * | 2010-03-03 | 2011-10-13 | Dainippon Printing Co Ltd | Adhesive composition and method for producing curable pressure-sensitive adhesive sheet |
KR20170066393A (en) * | 2014-09-29 | 2017-06-14 | 가부시키가이샤 아데카 | Photocurable adhesive, and polarizing plate, laminated optical member, and liquid crystal display device using same |
WO2016052244A1 (en) * | 2014-09-29 | 2016-04-07 | 株式会社Adeka | Photocurable adhesive, and polarizing plate, laminated optical member, and liquid crystal display device using same |
JPWO2016052244A1 (en) * | 2014-09-29 | 2017-07-13 | 株式会社Adeka | Photocurable adhesive, and polarizing plate, laminated optical member and liquid crystal display device using the same |
CN107076907A (en) * | 2014-09-29 | 2017-08-18 | 株式会社Adeka | Photo-curable adhesive and polarization plates, laminated optical component and the liquid crystal display device using the photo-curable adhesive |
TWI666284B (en) * | 2014-09-29 | 2019-07-21 | 日商Adeka股份有限公司 | Photocurable adhesive, polarizing plate using same, laminated optical member and liquid crystal display device |
KR102313276B1 (en) | 2014-09-29 | 2021-10-18 | 가부시키가이샤 아데카 | Photocurable adhesive, and polarizing plate, laminated optical member, and liquid crystal display device using same |
CN104559885A (en) * | 2014-12-17 | 2015-04-29 | 唐华烨 | Phenol propane epoxy resin adhesive |
JP2015180726A (en) * | 2015-03-24 | 2015-10-15 | デクセリアルズ株式会社 | adhesive composition |
JP2017226824A (en) * | 2016-06-16 | 2017-12-28 | 信越化学工業株式会社 | Epoxy resin composition |
JP2019073593A (en) * | 2017-10-13 | 2019-05-16 | Dic株式会社 | One-liquid type epoxy resin composition, cured product, and use therefor |
JP7167424B2 (en) | 2017-10-13 | 2022-11-09 | Dic株式会社 | One-liquid type epoxy resin composition, cured product, and use thereof |
JP2019099585A (en) * | 2017-11-28 | 2019-06-24 | Dic株式会社 | One pack type epoxy resin composition, cured article, and application thereof |
JP7024356B2 (en) | 2017-11-28 | 2022-02-24 | Dic株式会社 | One-component epoxy resin compositions, cured products, and their uses |
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