JP7196460B2 - Two-component acrylic adhesive composition, and bonded body bonded by the same - Google Patents
Two-component acrylic adhesive composition, and bonded body bonded by the same Download PDFInfo
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- JP7196460B2 JP7196460B2 JP2018153237A JP2018153237A JP7196460B2 JP 7196460 B2 JP7196460 B2 JP 7196460B2 JP 2018153237 A JP2018153237 A JP 2018153237A JP 2018153237 A JP2018153237 A JP 2018153237A JP 7196460 B2 JP7196460 B2 JP 7196460B2
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- Prior art keywords
- meth
- acrylate
- component
- adhesive composition
- component acrylic
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- 239000000203 mixture Substances 0.000 title claims description 71
- 239000003522 acrylic cement Substances 0.000 title claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 66
- 239000000853 adhesive Substances 0.000 claims description 51
- 230000001070 adhesive effect Effects 0.000 claims description 51
- 239000000178 monomer Substances 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 claims description 21
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 14
- 229920001971 elastomer Polymers 0.000 claims description 11
- 239000012188 paraffin wax Substances 0.000 claims description 10
- 239000000806 elastomer Substances 0.000 claims description 9
- 235000019809 paraffin wax Nutrition 0.000 claims description 9
- 235000019271 petrolatum Nutrition 0.000 claims description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- 229920000459 Nitrile rubber Polymers 0.000 claims description 7
- 239000003505 polymerization initiator Substances 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical group [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical group COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 2
- -1 2-ethylhexyl Chemical group 0.000 description 20
- 238000002156 mixing Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229920006332 epoxy adhesive Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- 229920001651 Cyanoacrylate Polymers 0.000 description 2
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 2
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 150000003585 thioureas Chemical class 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 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
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 description 1
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- NWFVONWTBGQHGT-UHFFFAOYSA-N 1,3-didodecylthiourea Chemical compound CCCCCCCCCCCCNC(=S)NCCCCCCCCCCCC NWFVONWTBGQHGT-UHFFFAOYSA-N 0.000 description 1
- AUXGIIVHLRLBSG-UHFFFAOYSA-N 1,3-dipropylthiourea Chemical compound CCCNC(=S)NCCC AUXGIIVHLRLBSG-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- IEQWWMKDFZUMMU-UHFFFAOYSA-N 2-(2-prop-2-enoyloxyethyl)butanedioic acid Chemical compound OC(=O)CC(C(O)=O)CCOC(=O)C=C IEQWWMKDFZUMMU-UHFFFAOYSA-N 0.000 description 1
- JUVSRZCUMWZBFK-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)-4-methylanilino]ethanol Chemical compound CC1=CC=C(N(CCO)CCO)C=C1 JUVSRZCUMWZBFK-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- KRHMGQFGGUBDJI-UHFFFAOYSA-N 4-ethyl-1-(2-hydroxyethoxy)octan-2-ol Chemical compound CCCCC(CC)CC(O)COCCO KRHMGQFGGUBDJI-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- YHAUWIDCXVQMPN-UHFFFAOYSA-N 4-methyl-n,n-di(propan-2-yl)aniline Chemical compound CC(C)N(C(C)C)C1=CC=C(C)C=C1 YHAUWIDCXVQMPN-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 description 1
- KFFQABQEJATQAT-UHFFFAOYSA-N N,N'-dibutylthiourea Chemical compound CCCCNC(=S)NCCCC KFFQABQEJATQAT-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- IPCRBOOJBPETMF-UHFFFAOYSA-N N-acetylthiourea Chemical compound CC(=O)NC(N)=S IPCRBOOJBPETMF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 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
- 125000002704 decyl group Chemical group [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])* 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 1
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- DQMWMUMCNOJLSI-UHFFFAOYSA-N n-carbamothioylbenzamide Chemical compound NC(=S)NC(=O)C1=CC=CC=C1 DQMWMUMCNOJLSI-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000000243 solution 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
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012719 thermal polymerization Methods 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
- 239000001993 wax Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、高速硬化性に優れる二剤型アクリル系接着剤組成物、及びそれにより接合された接合体に関する。 TECHNICAL FIELD The present invention relates to a two-component acrylic adhesive composition that is excellent in high-speed curing properties, and a bonded article bonded by the composition.
近年、工場における組立ラインにおいて、高効率化のために速硬化型の接着剤を用いる
ことが多くなってきている。このような用途には加熱炉などの装置を用いずとも硬化可能
な常温速硬化型の接着剤が適している。常温速硬化型の接着剤としては、二剤速硬化型エポキシ接着剤、シアノアクリレート系瞬間接着剤、第二世代アクリル系接着剤（以下、「ＳＧＡ」という。）等が知られている。
2. Description of the Related Art In recent years, fast-curing adhesives have been increasingly used in assembly lines in factories in order to improve efficiency. For such applications, a room-temperature fast-curing adhesive that can be cured without using a device such as a heating furnace is suitable. As room-temperature fast-curing adhesives, two-component fast-curing epoxy adhesives, cyanoacrylate instant adhesives, second-generation acrylic adhesives (hereinafter referred to as "SGA"), and the like are known.
二剤速硬化型エポキシ接着剤は、第一剤と第二剤を正確に計量して混合しなければ接着性能が著しく低下するので作業性が悪い。また、シアノアクリレート系瞬間接着剤は、その硬化物が硬く脆いために衝撃強度が低いので組立ラインなどで使用するには不向きである。 A two-component fast-curing type epoxy adhesive is poor in workability because the adhesion performance is remarkably lowered unless the first component and the second component are accurately weighed and mixed. In addition, cyanoacrylate-based instant adhesives are hard and brittle, and their impact strength is low, so they are unsuitable for use in assembly lines and the like.
一方、ＳＧＡも二剤型ではあるが、第一剤と第二剤の配合比が二剤速硬化型エポキシ接着剤に比べて厳密ではなく、所定の配合比から少々外れた場合でも接着性能が大きく低下することがないので、作業性に優れている。また、ＳＧＡは衝撃強度や剥離強度が強いという利点を有する。さらに、ＳＧＡは常温で数分から数十分で硬化するため、常温速硬化型接着剤として電子部品、土木建築材料、自動車部材等の組立てにおいて使用されている。 On the other hand, although SGA is also a two-component type, the compounding ratio of the first component and the second component is not as strict as the two-component fast-curing epoxy adhesive, and even if the compounding ratio slightly deviates from the predetermined compounding ratio, the adhesive performance will not improve. It is excellent in workability because it does not greatly decrease. In addition, SGA has the advantage of high impact strength and peel strength. Furthermore, since SGA cures at room temperature in a few minutes to several tens of minutes, it is used as a room-temperature quick-curing adhesive in the assembly of electronic parts, civil engineering and construction materials, automobile parts, and the like.
近年、組立ラインの高効率化の観点から、上記のＳＧＡの利点に加え、接着強度が優れたＳＧＡが求められている。ＳＧＡとして、例えば、特許文献１ではニトリルブタジエンラバー、ＭＢＳ樹脂、さらには（メタ）アクリル系重合性単量体を用いた接着剤組成物が提案されている。 In recent years, from the viewpoint of increasing the efficiency of assembly lines, in addition to the above advantages of SGA, SGA with excellent adhesive strength is desired. As SGA, for example, Patent Document 1 proposes an adhesive composition using a nitrile-butadiene rubber, an MBS resin, and a (meth)acrylic polymerizable monomer.
しかし、特許文献１に具体的に開示されている接着剤組成物では接着強度が十分ではなく、さらなる改良が望まれていた。 However, the adhesive composition specifically disclosed in Patent Document 1 does not have sufficient adhesive strength, and further improvement has been desired.
本発明は、常温において素早く硬化することで部材を短時間で固定でき、その場合にも接着強度の優れる接着剤組成物を提供することを目的とする。 SUMMARY OF THE INVENTION An object of the present invention is to provide an adhesive composition capable of fixing members in a short period of time by curing rapidly at room temperature and having excellent adhesive strength even in such a case.
本発明は、（１）（メタ）アクリロイル基を有する重合性単量体、（２）重合開始剤、
（３）還元剤、（４）ポリオルガノシロキサンおよびポリアルキル（メタ）アクリレート
を含む重合体、（５）（メタ）アクリル酸エステル単量体に可溶なエラストマー及び、複
数種類のパラフィンワックスを含有してなるアクリル系接着剤組成物であって、前記ポリ
オルガノシロキサンおよびポリアルキル（メタ）アクリレートを含む重合体が前記（メタ
）アクリロイル基を有する重合性単量体に膨潤可能であることを特徴とする二剤型アクリ
ル系接着剤組成物であり、さらにこの組成物により２つの被着体を接合してなる接合体で
ある。
The present invention provides (1) a polymerizable monomer having a (meth)acryloyl group, (2) a polymerization initiator,
(3) a reducing agent, (4) a polymer containing a polyorganosiloxane and a polyalkyl(meth)acrylate, (5) an elastomer soluble in a (meth)acrylate monomer , and a complex
An acrylic adhesive composition containing several kinds of paraffin waxes , wherein the polymer containing the polyorganosiloxane and the polyalkyl (meth)acrylate swells with the polymerizable monomer having the (meth)acryloyl group. A two-component acrylic adhesive composition characterized in that it is possible to bond two adherends together with this composition.
本発明の接着剤組成物は常温において素早く硬化することで部材を短時間で固定でき、その場合にも接着強度に優れる。そのため当該組成物を用いると接着強度に優れた接合体を短時間で製造することができる。 The adhesive composition of the present invention cures quickly at room temperature, so that members can be fixed in a short period of time, and even in that case, the adhesive strength is excellent. Therefore, by using the composition, a joined body having excellent adhesive strength can be produced in a short period of time.
本発明の二剤型アクリル系接着剤組成物は、（１）（メタ）アクリロイル基を有する重合性単量体、（２）重合開始剤、（３）還元剤、（４）ポリオルガノシロキサンおよびポリアルキル（メタ）アクリレートを含む重合体、（５）（メタ）アクリル酸エステル単量体に可溶なエラストマー、の五つの成分を含有する。本組成物は、（２）成分を含み（３）成分を含まない第一剤と、（３）成分を含み（２）成分を含まない第二剤を混合して得られる。以下、各成分について詳細に説明する。
なお本発明において、「（メタ）アクリル」は「アクリル」及び「メタクリル」の総称であり、「（メタ）アクリレート」は「アクリレート」及び「メタクリレート」の総称である。また、「（メタ）アクリロイル基」は「アクリロイル基」及び「メタクリロイル基」の総称であり、化学式
ＣＨ２＝Ｃ（Ｒ）－Ｃ（＝Ｏ）－（Ｒは水素原子又はメチル基）
で表される官能基である。
The two-component acrylic adhesive composition of the present invention comprises (1) a polymerizable monomer having a (meth)acryloyl group, (2) a polymerization initiator, (3) a reducing agent, (4) a polyorganosiloxane and It contains five components: a polymer containing polyalkyl (meth)acrylate, and (5) an elastomer soluble in (meth)acrylic acid ester monomers. The present composition is obtained by mixing a first agent containing component (2) but not containing component (3) and a second agent containing component (3) but not containing component (2). Each component will be described in detail below.
In the present invention, "(meth)acryl" is a generic term for "acryl" and "methacrylic", and "(meth)acrylate" is a generic term for "acrylate" and "methacrylate". In addition, "(meth)acryloyl group" is a generic term for "acryloyl group" and "methacryloyl group", and has the chemical formula CH2=C(R)-C(=O)-(R is a hydrogen atom or a methyl group)
is a functional group represented by
（１）（メタ）アクリロイル基を有する重合性単量体
本アクリル系接着剤組成物（以下、「本組成物」ともいう。）に配合される（メタ）アクリロイル基を有する重合性単量体（１）は、本組成物の粘度や接着力を調整するための成分である。（１）成分としては、例えば以下の単量体が挙げられる。メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｉ－プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｉ－ブチル（メタ）アクリレート、ｔ－ブチル（メタ）アクリレート、ヘプチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ｎ－ノニル（メタ）アクリレート、イソノニル（メタ）アクリレート、デシル（メタ）アクリレート、ラウリル（メタ）アクリレート、トリデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェニル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、ジシクロペンテニル（メタ）アクリレート、ジシクロペンテニルオキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート及びアダマンチル（メタ）アクリレート等のアルキル（メタ）アクリレート；メトキシエチル（メタ）アクリレート、エトキシエチル（メタ）アクリレート及びブトキシエチル（メタ）アクリレート等のアルコキシアルキル（メタ）アクリレート；２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシ－３－フェノキシプロピル（メタ）アクリレート等の水酸基含有（メタ）アクリレート；（メタ）アクリル酸；ω－カルボキシ－ポリカプロラクトンモノ（メタ）アクリレート等のポリカプロラクトン変性（メタ）アクリル酸エステル；２－（メタ）アクリロイルオキシエチルコハク酸モノエステル、２－（メタ）アクリロイルオキシエチルヘキサヒドロフタル酸モノエステル、２－（メタ）アクリロイルオキシエチルフタル酸モノエステル、２－（メタ）アクリロイルオキシエチル－２－ヒドロキシエチル－フタル酸モノエステル及び２－（メタ）アクリロイルオキシエチル－２－ヒドロキシプロピル－フタル酸モノエステル等の（メタ）アクリロイルオキシアルキルジカルボン酸モノエステル；２－エチルヘキシルジエチレングリコール（メタ）アクリレート等のアルキレングリコール変性（メタ）アクリレート；フェノキシポリエチレングリコール（メタ）アクリレート及びノニルフェノキシポリエチレングリコール（メタ）アクリレート等のアルコキシポリアルキレングリコール変性（メタ）アクリレート；エチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、１，３－プロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、１，３－ブチレングリコールジ（メタ）アクリレート、１，４－ブチレングリコールジ（メタ）アクリレート、ポリブチレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、ポリカーボネートジオールジ（メタ）アクリレート、ε－カプロラクトン変性トリス（（メタ）アクリロキシエチル）イソシアヌレート、ビスフェノールＡエチレンオキサイド付加物ジ（メタ）アクリレート及びポリエステルジオールジ（メタ）アクリレート等の多官能性（メタ）アクリレート；グリシジル（メタ）アクリレート、アクリロイルモルホリン及びテトラヒドロフルフリル（メタ）アクリレート等のヘテロ環構造を有する（メタ）アクリレート；３－（メタ）アクリロキシプロピルトリメトキシシラン等の重合性（メタ）アクリロイル基を有するアルコキシシラン；２－メタクリロイルオキシエチルアシッドホスフェート及び２－ヒドロキシエチル（メタ）アクリレートの６－ヘキサノリド付加重合物と無水リン酸との反応生成物等のリン酸エステル系重合性単量体；（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド及びＮ，Ｎ－ジメチルアクリルアミド等の（メタ）アクリルアミド系重合性単量体等が挙げられる。これらは１種単独で又は２種以上を組み合わせて使用することができる。
(1) Polymerizable monomer having a (meth)acryloyl group Polymerizable monomer having a (meth)acryloyl group to be blended in the present acrylic adhesive composition (hereinafter also referred to as "the present composition") (1) is a component for adjusting the viscosity and adhesive strength of the present composition. (1) As a component, the following monomers are mentioned, for example. methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylates, heptyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, n-nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, Lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate , dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate and adamantyl (meth)acrylate; methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate; ) acrylates and alkoxyalkyl (meth)acrylates such as butoxyethyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3 - hydroxyl group-containing (meth)acrylates such as phenoxypropyl (meth)acrylate; (meth)acrylic acid; polycaprolactone-modified (meth)acrylic acid esters such as ω-carboxy-polycaprolactone mono(meth)acrylate; 2-(meth) Acryloyloxyethyl succinic acid monoester, 2-(meth)acryloyloxyethyl hexahydrophthalic acid monoester, 2-(meth)acryloyloxyethyl phthalic acid monoester, 2-(meth)acryloyloxyethyl-2-hydroxyethyl- (meth)acryloyloxyalkyldicarboxylic acid monoesters such as phthalic acid monoesters and 2-(meth)acryloyloxyethyl-2-hydroxypropyl-phthalic acid monoesters; alkylene glycol-modified (such as 2-ethylhexyldiethylene glycol (meth)acrylates); meth)acrylates; phenoxypolyethylene glycol (meth)acrylates and Alkoxypolyalkylene glycol-modified (meth)acrylates such as nylphenoxypolyethylene glycol (meth)acrylate; ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,3-propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, polybutylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1, 6-hexanediol di(meth)acrylate, polycarbonate diol di(meth)acrylate, ε-caprolactone-modified tris((meth)acryloxyethyl)isocyanurate, bisphenol A ethylene oxide adduct di(meth)acrylate and polyester diol di( Polyfunctional (meth)acrylates such as meth)acrylate; (meth)acrylates having a heterocyclic structure such as glycidyl (meth)acrylate, acryloylmorpholine and tetrahydrofurfuryl (meth)acrylate; 3-(meth)acryloxypropyltri Alkoxysilanes having a polymerizable (meth)acryloyl group such as methoxysilane; reaction products of 6-hexanolide addition polymer of 2-methacryloyloxyethyl acid phosphate and 2-hydroxyethyl (meth)acrylate with phosphoric anhydride, etc. Phosphate ester polymerizable monomers; (meth)acrylamide polymerizable monomers such as (meth)acrylamide, N-methylol(meth)acrylamide and N,N-dimethylacrylamide; These can be used individually by 1 type or in combination of 2 or more types.
（１）成分としては、（４）及び（５）成分との相溶性の点から、アルキル（メタ）アクリレート、水酸基含有（メタ）アクリレート、リン酸エステル系重合性単量体が好ましい。 As component (1), from the viewpoint of compatibility with components (4) and (5), alkyl (meth)acrylates, hydroxyl group-containing (meth)acrylates, and phosphoric acid ester polymerizable monomers are preferred.
（２）重合開始剤
本組成物に含まれる（２）は、本組成物の硬化剤であり、（３）と反応してラジカルを発生する。本組成物でラジカルが発生し（１）が重合する。（２）成分としては、例えば、ハイドロパーオキサイド、ジアシルパーオキサイド、パーオキシエステル、ジアルキルパーオキサイド、ケトンパーオキサイド、パーオキシケタール、アルキルパーエステル、パーカーボネート挙げられる。これらは単独で又は２種以上を併せて使用することができる。本組成物の硬化速度の点から、クメンハイドロパーオキサイドが好ましい。
(2) Polymerization Initiator (2) contained in the present composition is a curing agent for the present composition, and reacts with (3) to generate radicals. Radicals are generated in this composition and (1) is polymerized. Component (2) includes, for example, hydroperoxides, diacyl peroxides, peroxyesters, dialkyl peroxides, ketone peroxides, peroxyketals, alkyl peresters and percarbonates. These can be used alone or in combination of two or more. Cumene hydroperoxide is preferred from the viewpoint of the curing speed of the present composition.
本組成物における（２）成分の含有量は、（１）～（５）成分の合計量を１００質量部としたとき、０．１質量部以上であることが好ましく、１質量部以上であることがより好ましい。また２０質量部以下であることが好ましく、１５質量部以下であることがより好ましい。（２）の含有量は多いほど硬化速度が速くなり、少ないほど（２）を含む第一剤の貯蔵安定性が良好となる。 The content of component (2) in the present composition is preferably 0.1 parts by mass or more, and is 1 part by mass or more when the total amount of components (1) to (5) is 100 parts by mass. is more preferable. Moreover, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less. The higher the content of (2), the faster the curing rate, and the lower the content, the better the storage stability of the primary agent containing (2).
（３）還元剤
本組成物に含まれる（３）は、本組成物の硬化促進剤であり、（２）と反応してラジカルを発生する。（３）成分としては、例えば、遷移金属塩、チオ尿素化合物が挙げられる。遷移金属塩の具体例としては、バナジルアセチルアセトネート、バナジウムアセチルアセトネート、ナフテン酸銅、ナフテン酸コバルトが挙げられる。チオ尿素化合物の具体例としては、チオ尿素、エチレンチオ尿素、Ｎ，Ｎ’－ジメチルチオ尿素、Ｎ，Ｎ’－ジエチルチオ尿素、Ｎ，Ｎ’－ジプロピルチオ尿素、Ｎ，Ｎ’－ジ－ｎ－ブチルチオ尿素、Ｎ，Ｎ’－ジラウリルチオ尿素、Ｎ，Ｎ’－ジフェニルチオ尿素、トリメチルチオ尿素、１－アセチル－２－チオ尿素、１－ベンゾイル－２－チオ尿素が挙げられる。反応性の点から、遷移金属塩が好ましく、中でもバナジルアセチルアセトネートがより好ましい。
(3) Reducing agent (3) contained in the present composition is a curing accelerator for the present composition, and reacts with (2) to generate radicals. (3) Components include, for example, transition metal salts and thiourea compounds. Specific examples of transition metal salts include vanadyl acetylacetonate, vanadium acetylacetonate, copper naphthenate, and cobalt naphthenate. Specific examples of thiourea compounds include thiourea, ethylenethiourea, N,N'-dimethylthiourea, N,N'-diethylthiourea, N,N'-dipropylthiourea, and N,N'-di-n-butylthiourea. , N,N′-dilaurylthiourea, N,N′-diphenylthiourea, trimethylthiourea, 1-acetyl-2-thiourea, 1-benzoyl-2-thiourea. From the viewpoint of reactivity, transition metal salts are preferred, and vanadyl acetylacetonate is more preferred.
本組成物における（３）成分の含有量は、（１）～（５）成分の合計量を１００質量部としたとき、０．０５質量部以上であることが好ましく、０．１質量部以上であることがより好ましい。また１０質量部以下であることが好ましく、５質量部以下であることがより好ましい。（３）成分の含有量は多いほど硬化速度が速くなり、少ないほど（３）成分を含む第二剤の貯蔵安定性が良好となる。 The content of component (3) in the present composition is preferably 0.05 parts by mass or more, and 0.1 parts by mass or more when the total amount of components (1) to (5) is 100 parts by mass. is more preferable. Moreover, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less. The higher the content of component (3), the faster the curing speed, and the lower the content of component (3), the better the storage stability of the second agent containing component (3).
（４）ポリオルガノシロキサンおよびポリアルキル（メタ）アクリレートを含む重合体
本組成物に含まれる（４）は、本組成物において粘度を調整するための成分である。また、この成分は本組成物を硬化してなる硬化物のせん断接着強度と剥離強度を両立させるための成分である。（４）であるポリオルガノシロキサンおよびポリアルキル（メタ）アクリレートを含む重合体とは、ビニル重合性官能基を有するポリオルガノシロキサンと、必要に応じてシロキサン系架橋剤とを重合させることで得られるシリコーンゴムに（メタ）アクリレートを重合して得られる重合体である。そしてこの（４）成分は、前記（１）成分に膨潤可能であることを要する。ここで「膨潤」とは樹脂が溶剤を吸収して膨れている状態のことをいう。トルエンなどの溶剤を樹脂に加え、体積膨張した樹脂を篩別し篩上に残った樹脂重量を測定することにより、膨潤の度合を「膨潤度」という指標で表すこともできる。（４）成分としては、例えば、三菱ケミカル株式会社製のメタブレンＳタイプ（商品名）やダイヤナールＬＰ－４２００（商品名）が挙げられる。これらは単独で又は２種以上を併せて使用することができる。
(4) Polymer Containing Polyorganosiloxane and Polyalkyl(meth)acrylate (4) contained in the present composition is a component for adjusting the viscosity of the present composition. Further, this component is a component for achieving both shear adhesive strength and peel strength of a cured product obtained by curing the present composition. The polymer containing polyorganosiloxane and polyalkyl (meth)acrylate, which is (4), is obtained by polymerizing polyorganosiloxane having a vinyl polymerizable functional group and, if necessary, a siloxane-based cross-linking agent. It is a polymer obtained by polymerizing (meth)acrylate on silicone rubber. The component (4) must be able to swell with the component (1). Here, "swelling" refers to a state in which the resin absorbs the solvent and swells. A solvent such as toluene is added to the resin, the volume-expanded resin is sieved, and the weight of the resin remaining on the sieve is measured. Component (4) includes, for example, Metabrene S Type (trade name) and Dianal LP-4200 (trade name) manufactured by Mitsubishi Chemical Corporation. These can be used alone or in combination of two or more.
本組成物における（４）成分の配合量は、（１）～（５）成分の合計１００質量部に対して１質量部以上であることが好ましく、３質量部以上であることがより好ましい。また１４質量部以下であることが好ましく、１０質量部以下であることがより好ましい。（４）成分の配合量は多いほど本引張せん断接着強度が高くなり、少ないほどＴ型剥離接着強度が高くなる。 The amount of component (4) in the present composition is preferably 1 part by mass or more, more preferably 3 parts by mass or more per 100 parts by mass in total of components (1) to (5). Moreover, it is preferably 14 parts by mass or less, more preferably 10 parts by mass or less. The larger the content of component (4), the higher the tensile shear bond strength, and the smaller the content, the higher the T-peel bond strength.
（５）（メタ）アクリロイル基を有する重合性単量体に可溶なエラストマー
本組成物に含まれる（５）は、本組成物において粘度を調整するための成分である。また、この成分は接着剤組成物を硬化してなる硬化物の柔軟性を向上させるための成分である。（５）成分であるエラストマーとは、２５℃でゴム弾性を有する高分子量体である。（５）としては、例えば、ポリウレタン樹脂、シリコーン樹脂、アクリロニトリル－ブタジエン－スチレン共重合体、アクリロニトリル－スチレン共重合体、（メタ）アクリル酸エステル－ブタジエン共重合体、（メタ）アクリル酸エステル－ブタジエン－スチレン共重合体、（メタ）アクリル酸エステル－ブタジエン－アクリロニトリル－スチレン共重合体、スチレン－ブタジエンゴム、ポリブタジエンゴム、クロロプレンゴム、アクリロニトリル－ブタジエンゴムが挙げられる。これらは１種単独で又は２種以上を併せて使用してもよい。
(5) Elastomer soluble in polymerizable monomer having (meth)acryloyl group (5) contained in the present composition is a component for adjusting the viscosity of the present composition. Also, this component is a component for improving the flexibility of the cured product obtained by curing the adhesive composition. The elastomer as the component (5) is a high molecular weight material having rubber elasticity at 25°C. (5) includes, for example, polyurethane resins, silicone resins, acrylonitrile-butadiene-styrene copolymers, acrylonitrile-styrene copolymers, (meth)acrylate-butadiene copolymers, (meth)acrylate-butadiene -styrene copolymer, (meth)acrylic acid ester-butadiene-acrylonitrile-styrene copolymer, styrene-butadiene rubber, polybutadiene rubber, chloroprene rubber, acrylonitrile-butadiene rubber. These may be used individually by 1 type or in combination of 2 or more types.
（５）成分としては、（１）成分との相溶性の点から、アクリロニトリルの含有量が１５重量％以上のアクリロニトリルブタジエンゴムが好ましい。（５）成分の構造は、例えば、直鎖状、分岐鎖状、グラフト状が挙げられる。 As component (5), acrylonitrile-butadiene rubber having an acrylonitrile content of 15% by weight or more is preferable from the viewpoint of compatibility with component (1). The structure of the component (5) includes, for example, linear, branched, and grafted structures.
本組成物における（５）成分の配合量は、（１）～（５）成分の合計１００質量部に対して１質量部以上であることが好ましく、３質量部以上であることがより好ましい。また１４質量部以下であることが好ましく、１０質量部以下であることがより好ましい。（５）成分の配合量は多いほどＴ型剥離接着強度が高くなり、少ないほど本組成物の粘度が低下するので作業性が良好となる。 The amount of component (5) in the present composition is preferably 1 part by mass or more, more preferably 3 parts by mass or more, per 100 parts by mass of components (1) to (5). Moreover, it is preferably 14 parts by mass or less, more preferably 10 parts by mass or less. The larger the amount of component (5), the higher the T-peel adhesive strength, and the smaller the amount, the lower the viscosity of the composition and the better the workability.
・その他の成分
本組成物には、本発明の効果を損なわない範囲で、（１）～（５）成分以外のその他の成分（以下、「その他の成分」という。）を含んでもよい。その他の成分の具体例としては、ビニル系モノマー等のアクリル系以外のラジカル重合性単量体や、酸化防止剤、可塑剤、紫外線吸収剤、シランカップリング剤、消泡剤、重合禁止剤、無機微粒子等の各種添加剤が挙げられる。
· Other components The present composition may contain other components (hereinafter referred to as "other components") other than the components (1) to (5) within a range that does not impair the effects of the present invention. Specific examples of other components include non-acrylic radically polymerizable monomers such as vinyl monomers, antioxidants, plasticizers, ultraviolet absorbers, silane coupling agents, antifoaming agents, polymerization inhibitors, Various additives such as inorganic fine particles may be used.
その他の成分としては、本硬化物の強度向上のために、加熱によりラジカルを発生する熱重合開始剤（２）成分以外の過酸化物、アゾ化合物等、紫外線等の活性エネルギー線の照射によりラジカルを発生する光重合開始剤（１－ヒドロキシシクロヘキシルフェニルケトン等）を加えてもよい。 As other components, in order to improve the strength of the cured product, a thermal polymerization initiator other than the component (2) that generates radicals by heating, such as a peroxide, an azo compound, etc., can be radicalized by irradiation with an active energy ray such as ultraviolet rays. A photopolymerization initiator (1-hydroxycyclohexylphenyl ketone, etc.) that generates a may be added.
その他の成分としては、硬化時間を短縮するために、Ｎ，Ｎ－ジメチル－ｐ－トルイジン、Ｎ，Ｎ－ジイソプロピル－ｐ－トルイジン、Ｎ，Ｎ－ジ(２－ヒドロキシエチル)－ｐ－トルイジン等の第３級アミン化合物を加えてもよい。 Other components include N,N-dimethyl-p-toluidine, N,N-diisopropyl-p-toluidine, N,N-di(2-hydroxyethyl)-p-toluidine, etc., in order to shorten the curing time. of tertiary amine compounds may be added.
その他の成分の含有量は、特に限定されないが、（１）～（５）成分の合計１００質量部に対して、１０質量部以下が好ましく、５質量部以下がより好ましい。その他の成分の含有量は多すぎると、本組成物の常温における高速硬化性、接着強度が損なわれる場合がある。 The content of the other components is not particularly limited, but is preferably 10 parts by mass or less, more preferably 5 parts by mass or less with respect to 100 parts by mass in total of components (1) to (5). If the content of other components is too high, the high-speed curability and adhesive strength of the present composition at room temperature may be impaired.
・接着剤組成物
本組成物は、（２）成分を含み（３）成分を含まない第一剤と（３）成分を含み（２）成分を含まない第二剤を混合して得られる。このような混合は、通常は接着直前に行われる。第一剤と第二剤は混合してから被着体に塗布してもよいが、本組成物は硬化速度が速いことから、第一剤を一方の被着体に塗布し、第二剤をもう一方の被着体に塗布して、第一剤と第二剤が混ざるように両者を圧着することが好ましい。
- Adhesive composition This composition is obtained by mixing a first agent containing the component (2) and not containing the component (3) and a second agent containing the component (3) but not containing the component (2). Such mixing is usually done just prior to bonding. The first agent and the second agent may be mixed and then applied to the adherend. is applied to the other adherend, and the two are preferably pressed together so that the first agent and the second agent are mixed.
第一剤と第二剤の組み合わせの具体例としては、（１）、（４）及び（５）成分の混合物に（２）成分を加えた第一剤と、（１）、（４）及び（５）成分の混合物に（３）成分を加えた第二剤との二剤型、（１）成分の混合物に（２）成分を加えた第一剤と、（３）成分からなる第二剤との二剤型、（２）成分からなる第一剤と、（１）、（４）及び（５）成分の混合物に（３）成分が溶解した第二剤との二剤型が挙げられる。 Specific examples of the combination of the first agent and the second agent include the first agent obtained by adding the (2) component to the mixture of the (1), (4) and (5) components, and (1), (4) and (5) A two-dose type consisting of a mixture of components (3) and a second dose, a mixture of (1) with (2) added to the second dose, and a second dose consisting of (3) and a two-part type consisting of a first part consisting of component (2) and a second part in which component (3) is dissolved in a mixture of components (1), (4) and (5). be done.
本組成物の製造方法としては、（１）、（４）及び（５）成分を加熱混合することで相溶した後に、常温まで冷却し、第一剤に（２）成分、第二剤に（３）及び（４）成分を混合する手法や、（１）、（４）及び（５）成分をプラネタリーミキサー等でせん断力を加えることで相溶した後、第一剤に（２）成分、第二剤に（３）成分を配合し、常温で混合する手法等が挙げられる。本硬化物は、二剤を混合し、重合反応を起こすことにより得られる。また、本発明の接合体は、第一剤、第二剤を混合したものを被着体に塗布する接着方法や、第一剤、第二剤を別々に塗布した被着体を貼り合わせる接着方法などで得られる。また、先端で二剤を混合できるような構造を有する２剤型接着剤塗布機を用いることもできる。
・被着体
本組成物により二つの被着体を接合したものは、接着強度に優れる。被着体としては特に限定されないが、例えば、金属、紙、木材、セラミック、ガラス、陶磁器、ゴム、プラスチック、モルタル、コンクリート等が挙げられるが、特に接着強度が高い点で金属が好ましい。前記二つの被着体を複数組み合わせた構造体としてもよい。
As a method for producing the present composition, the components (1), (4) and (5) are mixed by heating to dissolve, and then cooled to room temperature, and the first component is the component (2), and the second component is A method of mixing components (3) and (4), and a method of mixing components (1), (4) and (5) by applying a shearing force with a planetary mixer or the like to dissolve them, and then adding (2) to the first agent. A method of blending the component (3) with the component and the second agent, and mixing at room temperature. The hardened product is obtained by mixing the two components and causing a polymerization reaction. In addition, the joined body of the present invention can be obtained by a bonding method in which a mixture of the first agent and the second agent is applied to the adherend, or by bonding the adherends to which the first agent and the second agent are separately applied. obtained by the method. Also, a two-component adhesive applicator having a structure that allows the two components to be mixed at the tip can be used.
- Adherend A bond obtained by bonding two adherends with the present composition exhibits excellent adhesive strength. The adherend is not particularly limited, and examples thereof include metal, paper, wood, ceramics, glass, ceramics, rubber, plastic, mortar, and concrete. Metals are particularly preferred because of their high adhesive strength. A structure may be formed by combining a plurality of the two adherends.
以下、本発明を実施例により説明する。以下において、「部」は「質量部」を意味する。実施例及び比較例における接着強度の評価は、以下の方法で実施した。各種測定及び評価方法は以下の通りである。 EXAMPLES The present invention will now be described with reference to examples. In the following, "parts" means "mass parts". Evaluation of adhesive strength in Examples and Comparative Examples was carried out by the following method. Various measurement and evaluation methods are as follows.
[引張せん断接着強度の評価]
ＪＩＳＫ６８５０に準じて評価した。２枚のＳＰＣＣ板（長さ１００ｍｍ×幅２５ｍｍ×厚み１．６ｍｍ）の表面をアセトンによって脱脂した。各例の第一剤及び第二剤を等量（各１０ｇ）混合した接着剤組成物を調製した。
この接着剤組成物を用いて、ＪＩＳＫ６８５０に記載の通り、２枚のＳＰＣＣ板の短辺同士を重ね合わせるようにして、被着面積が１２．５ｍｍ×２５ｍｍとなるように貼り合わせ、クリップで固定した。はみ出した接着剤組成物を取り除いた後、２３℃で２４時間養生後、クリップを取り除いて、接着試験体を得た。得られた試験体を引張り速度１ｍｍ／分で引張り、引張せん断接着力（単位：Ｎ）を測定し、得られた接着力を被着面積で除して、せん断接着強度（単位：ＭＰａ）として記録した。
得られた測定値から、下記基準にて引張せん断接着強度を判定した。引張せん断接着強度は１８．０ＭＰａ以上あれば良好である。
○：２０．０ＭＰａ以上
△：１８．０ＭＰａ以上２０．０ＭＰａ未満
×：１８．０ＭＰａ未満
○優良、△良、×不可
[Evaluation of tensile shear bond strength]
It was evaluated according to JISK6850. The surfaces of two SPCC plates (length 100 mm×width 25 mm×thickness 1.6 mm) were degreased with acetone. An adhesive composition was prepared by mixing equal amounts (10 g each) of the first agent and the second agent of each example.
Using this adhesive composition, as described in JISK6850, two SPCC plates are laminated so that the short sides are overlapped so that the adhesion area is 12.5 mm × 25 mm, and fixed with a clip. did. After removing the protruding adhesive composition, after curing at 23° C. for 24 hours, the clip was removed to obtain an adhesion test specimen. The obtained test piece is pulled at a tensile speed of 1 mm / min, the tensile shear adhesive strength (unit: N) is measured, and the obtained adhesive strength is divided by the adhesion area to obtain the shear adhesive strength (unit: MPa). Recorded.
From the measured values obtained, the tensile shear bond strength was determined according to the following criteria. A tensile shear bond strength of 18.0 MPa or more is satisfactory.
○: 20.0 MPa or more △: 18.0 MPa or more and less than 20.0 MPa ×: Less than 18.0 MPa ○ Excellent, △ Good, × Impossible
[Ｔ型剥離接着の評価]
ＪＩＳＫ６８５４－３に準じて評価した。２枚のＳＰＣＣ板（長さ２００ｍｍ×幅２５ｍｍ×厚み０．３ｍｍ）の表面をアセトンによって脱脂した。各例の第一剤及び第二剤を等量（各１０ｇ）混合した接着剤組成物を調製した。
この接着剤組成物を用いて、ＪＩＳＫ６８５４－３に記載の通り、２枚のＳＰＣＣ板の重ね合わせるようにして、被着面積が１５０ｍｍ×２５ｍｍとなるように貼り合わせ、クリップで固定した。はみ出した接着剤組成物を取り除いた後、２３℃で２４時間養生後、クリップを取り除いて、接着試験体を得た。
得られた試験体を引張り速度１００ｍｍ／分で引張り、最初の２５ｍｍと最後の２５ｍｍを除いたＴ型剥離接着力（単位：Ｎ）を記録した曲線から平均剥離接着力を読み取る。得られた平均剥離接着力を２５ｍｍで除して、Ｔ型剥離接着強度（単位：ｋＮ／ｍ）として記録した。
得られた測定値から、下記基準にてＴ型剥離接着強度を判定した。Ｔ型剥離接着強度は３．０ｋＮ／ｍ以上あれば良好である。
○：４．０ｋＮ／ｍ以上
△：３．０ｋＮ／ｍ以上４．０ｋＮ／ｍ未満
×：３．０ｋＮ／ｍ未満
○優良、△良、×不可
[Evaluation of T-type peel adhesion]
It was evaluated according to JISK6854-3. The surfaces of two SPCC plates (length 200 mm×width 25 mm×thickness 0.3 mm) were degreased with acetone. An adhesive composition was prepared by mixing equal amounts (10 g each) of the first agent and the second agent of each example.
Using this adhesive composition, as described in JISK6854-3, two SPCC plates were superimposed so as to have an adhesion area of 150 mm×25 mm, and were fixed with a clip. After removing the protruding adhesive composition, after curing at 23° C. for 24 hours, the clip was removed to obtain an adhesion test specimen.
The obtained test piece is pulled at a pulling rate of 100 mm/min, and the average peel adhesion strength is read from the curve recording the T-type peel adhesion strength (unit: N) excluding the first 25 mm and the last 25 mm. The resulting average peel strength was divided by 25 mm and recorded as the T-type peel strength (unit: kN/m).
From the measured values obtained, the T-peel adhesive strength was determined according to the following criteria. A T-type peel adhesive strength of 3.0 kN/m or more is satisfactory.
○: 4.0 kN/m or more △: 3.0 kN/m or more and less than 4.0 kN/m ×: Less than 3.0 kN/m ○ Excellent, △ Good, × Impossible
[実施例１]
表１に示す配合で接着剤組成物第一剤と第二剤を調製した。具体的な調製方法を以下に示す。
[Example 1]
A first agent and a second agent of the adhesive composition were prepared according to the formulations shown in Table 1. A specific preparation method is shown below.
第一剤の調製
攪拌機、温度計、冷却管付きの１Ｌフラスコに（１）（メタ）アクリロイル基を有する重合性単量体としてメチルメタクリレート（三菱ケミカル社製、商品名：アクリエステルＭ）６５質量部、水酸基を含有する（メタ）アクリル酸エステル単量体として２－ヒドロキシエチルメタクリレート（三菱ケミカル社製、商品名：アクリエステルＨＯ）２０質量部、（４）ポリオルガノシロキサンおよびポリアルキルメタアクリレートを含む重合体としてダイヤナールＬＰ－４２００ ５質量部、（５）（メタ）アクリル酸エステル単量体に可溶なエラストマーとして、アクリロニトリルの含有量が１８重量％のアクリロニトリル－ブタジエンゴム（日本ゼオン社製、商品名：ＤＮ４０１ＬＬ）１０質量部、重合禁止剤として０．０５部のＢＨＴ、パラフィンワックスとしてＰ－１５０（日本精蝋社製、商品名：パラフィンワックス１５０）０．２質量部とＰ－１３０（日本精蝋社製、商品名：パラフィンワックス１３０）０．２質量部とＰ－１１５（日本精蝋社製、商品名：パラフィンワックス１１５）を配合した。
Preparation of the first agent In a 1 L flask equipped with a stirrer, a thermometer, and a cooling tube, (1) 65 masses of methyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester M) as a polymerizable monomer having a (meth)acryloyl group part, 20 parts by mass of 2-hydroxyethyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester HO) as a (meth) acrylic acid ester monomer containing a hydroxyl group, (4) polyorganosiloxane and polyalkyl methacrylate 5 parts by mass of Dianal LP-4200 as a polymer containing, (5) Acrylonitrile-butadiene rubber with an acrylonitrile content of 18% by weight as an elastomer soluble in (meth) acrylic acid ester monomers (manufactured by Zeon , trade name: DN401LL) 10 parts by mass, 0.05 parts of BHT as a polymerization inhibitor, P-150 as paraffin wax (manufactured by Nippon Seiro Co., Ltd., trade name: paraffin wax 150) 0.2 parts by mass and P-130 (manufactured by Nippon Seiro Co., Ltd., trade name: paraffin wax 130) and P-115 (manufactured by Nippon Seiro Co., Ltd., trade name: paraffin wax 115) were blended.
次いで、フラスコ内温を６０℃まで昇温して、２時間撹拌し、均一な乳白色分散液を得た。その後、フラスコ内を３０℃以下となるまで冷却した。冷却したフラスコ内に（２）重合開始剤としてクメンハイドロパーオキサイド（化薬アクゾ社製、商品名：カヤクメンＨ）５質量部を加え、室温で１時間撹拌を継続して均一化した接着剤組成物を得た。 Then, the temperature inside the flask was raised to 60° C. and the mixture was stirred for 2 hours to obtain a uniform milky white dispersion. After that, the inside of the flask was cooled to 30° C. or lower. (2) Add 5 parts by mass of cumene hydroperoxide (manufactured by Kayaku Akzo Co., Ltd., trade name: Kayakumen H) as a polymerization initiator into the cooled flask, and continue stirring at room temperature for 1 hour to homogenize the adhesive composition. got stuff
第２剤の調製
攪拌機、温度計、冷却管付きの１Ｌフラスコに（１）（メタ）アクリロイル基を有する重合性単量体としてメチルメタクリレート（三菱ケミカル社製、商品名：アクリエステルＭ）６５質量部、２－ヒドロキシエチルメタクリレート（三菱ケミカル社製、商品名：アクリエステルＨＯ）２０質量部、（４）ポリオルガノシロキサンおよびポリアルキルメタアクリレートを含む重合体としてダイヤナールＬＰ－４２００ ５質量部、（５）（メタ）アクリロイル基を有する重合性単量体に可溶なエラストマーとして、アクリロニトリルの含有量が１８重量％のアクリロニトリル－ブタジエンゴム（日本ゼオン社製、商品名：ＤＮ４０１ＬＬ）１０質量部、重合禁止剤として０．０５部のＢＨＴ、パラフィンワックスとしてＰ－１５０（日本精蝋社製、商品名：パラフィンワックス１５０）０．２質量部とＰ－１３０（日本精蝋社製、商品名：パラフィンワックス１３０）０．２質量部とＰ－１１５（日本精蝋社製、商品名：パラフィンワックス１１５）を配合した。
次いで、フラスコ内温を６０℃まで昇温して、２時間撹拌し、均一な乳白色分散液を得た。その後、フラスコ内を３０℃以下となるまで冷却した。冷却したフラスコ内に（１）（メタ）アクリロイル基を有する重合性単量体としてとして、ＰＭ－２１（日本化薬社製、商品名：ＫＡＹＡＭＥＲ ＰＭ―２１）５質量部、（３）還元剤として、バナジルアセチルアセトネート（新興化学工業社製、商品名：バナジルアセチルアセトネート）を加え、室温で１時間撹拌して均一化した接着剤組成物を得た。
Preparation of Part 2 In a 1 L flask equipped with a stirrer, a thermometer, and a cooling tube, (1) 65 masses of methyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester M) as a polymerizable monomer having a (meth)acryloyl group parts, 20 parts by mass of 2-hydroxyethyl methacrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Acryester HO), (4) 5 parts by mass of Dianal LP-4200 as a polymer containing polyorganosiloxane and polyalkyl methacrylate, ( 5) 10 parts by mass of acrylonitrile-butadiene rubber (trade name: DN401LL, manufactured by Nippon Zeon Co., Ltd.) containing 18% by weight of acrylonitrile as an elastomer soluble in a polymerizable monomer having a (meth)acryloyl group, and polymerized. 0.05 parts of BHT as an inhibitor, 0.2 parts by mass of P-150 (manufactured by Nippon Seiro Co., Ltd., trade name: paraffin wax 150) as paraffin wax and P-130 (manufactured by Nippon Seiro Co., Ltd., trade name: paraffin 0.2 part by mass of Wax 130) and P-115 (manufactured by Nippon Seiro Co., Ltd., trade name: Paraffin Wax 115) were blended.
Then, the temperature inside the flask was raised to 60° C. and the mixture was stirred for 2 hours to obtain a uniform milky white dispersion. After that, the inside of the flask was cooled to 30° C. or lower. In a cooled flask (1) as a polymerizable monomer having a (meth) acryloyl group, PM-21 (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAMER PM-21) 5 parts by mass, (3) a reducing agent As a solution, vanadyl acetylacetonate (manufactured by Shinko Kagaku Kogyo Co., Ltd., trade name: vanadyl acetylacetonate) was added and stirred at room temperature for 1 hour to obtain a homogenized adhesive composition.
[実施例２]
表１に示すように各成分の組成比を変更した以外は、実施例１と同様にして接着剤組成物を得た。
[Example 2]
An adhesive composition was obtained in the same manner as in Example 1, except that the composition ratio of each component was changed as shown in Table 1.
[比較例１]
（４）ポリオルガノシロキサンおよびポリアルキルメタアクリレートを含む重合体を含まないこと以外は、実施例１と同様にして接着剤組成物を得た。
[Comparative Example 1]
(4) An adhesive composition was obtained in the same manner as in Example 1, except that the polymer containing polyorganosiloxane and polyalkyl methacrylate was not included.
[比較例２]
（５）（メタ）アクリロイル基を有する重合性単量体に可溶なエラストマーを含まないこと以外は、実施例１と同様にして接着剤組成物を得た。
[Comparative Example 2]
(5) An adhesive composition was obtained in the same manner as in Example 1, except that an elastomer soluble in a polymerizable monomer having a (meth)acryloyl group was not included.
評価結果を表２に示した。 Table 2 shows the evaluation results.
表２の結果から、（４）及び（５）の両方を含有する本接着剤組成物を用いた実施例１及び２では、Ｔ型剥離接着強度及び引張せん断接着強度が高く良好であった。しかしながら、（５）成分のみを含有する比較例１と、（４）成分のみ含有する比較例２は引張せん断接着強度もしくはＴ型剥離接着強度のいずれかが不良であった。 From the results in Table 2, in Examples 1 and 2 using the present adhesive composition containing both (4) and (5), the T-peel adhesive strength and tensile shear adhesive strength were high and favorable. However, Comparative Example 1 containing only the component (5) and Comparative Example 2 containing only the component (4) were inferior in either tensile shear adhesive strength or T-peel adhesive strength.
Claims (9)
剤、（４）ポリオルガノシロキサンおよびポリアルキル（メタ）アクリレートを含む重合
体、（５）（メタ）アクリル酸エステル単量体に可溶なエラストマー及び、複数種類のパ
ラフィンワックスを含有してなる第一剤と第二剤との二剤型アクリル系接着剤組成物であ
って、第二剤の（１）（メタ）アクリロイル基を有する重合性単量体が、メチル（メタ）
アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、ｉ－
プロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、ｉ－ブチル（メタ）
アクリレート、ｔ－ブチル（メタ）アクリレートのうちの１種又は２種以上のアルキル（
メタ）アクリレートと、水酸基含有（メタ）アクリレートと、リン酸エステル系重合性単
量体のみからなり、前記ポリオルガノシロキサンおよびポリアルキル（メタ）アクリレー
トを含む重合体が前記（メタ）アクリロイル基を有する重合性単量体に膨潤可能であるこ
とを特徴とする二剤型アクリル系接着剤組成物。 (1) a polymerizable monomer having a (meth)acryloyl group, (2) a polymerization initiator, (3) a reducing agent, (4) a polymer containing a polyorganosiloxane and a polyalkyl (meth)acrylate, (5) A two-component acrylic adhesive composition comprising an elastomer soluble in a (meth)acrylic acid ester monomer and a plurality of types of paraffin waxes, comprising a first component and a second component, (1) the polymerizable monomer having a (meth)acryloyl group of the agent is methyl (meth)
Acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-
Propyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)
One or more of acrylates and t-butyl (meth)acrylates (
meth)acrylates, hydroxyl group-containing (meth)acrylates, and phosphoric acid ester-based polymerizable monomers
A two-component acrylic system comprising only a monomer, wherein the polymer containing the polyorganosiloxane and the polyalkyl (meth)acrylate is swellable with the polymerizable monomer having the (meth)acryloyl group. adhesive composition.
求項１記載の二剤型アクリル系接着剤組成物。 (1) The two-component acrylic adhesive composition according to claim 1, wherein the polymerizable monomer having a (meth)acryloyl group is methyl methacrylate.
レートである請求項１に記載の二剤型アクリル系接着剤組成物。 (1) The two-component acrylic adhesive composition according to claim 1, wherein the polymerizable monomer having a (meth)acryloyl group is 2-hydroxyethyl methacrylate.
レートの６－ヘキサノリド付加重合物と無水リン酸との反応生成物である請求項１に記載
の二剤型アクリル系接着剤組成物。 (1) The two-component acrylic system according to claim 1, wherein the polymerizable monomer having a (meth)acryloyl group is a reaction product of a 6-hexanolide addition polymer of 2-hydroxyethyl methacrylate and phosphoric anhydride. adhesive composition.
に記載の二剤型アクリル系接着剤組成物。 (2) The two-component acrylic adhesive composition according to any one of items 1 to 4, wherein the polymerization initiator is cumene hydroperoxide.
載の二剤型アクリル系接着剤組成物。 (3) The two-component acrylic adhesive composition according to any one of claims 1 to 5, wherein the reducing agent is vanadyl acetylacetonate.
を（１）～（５）の合計１００質量部に対し１～１４質量部含む請求項１～６のいずれか
一項に記載の二剤型アクリル系接着剤組成物。 (4) The polymer containing polyorganosiloxane and polyalkyl (meth)acrylate according to any one of claims 1 to 6, which contains 1 to 14 parts by mass with respect to a total of 100 parts by mass of (1) to (5). A two-component acrylic adhesive composition.
ニトリル－ブタジエンゴムであり、前記アクリロニトリル－ブタジエンゴムは、アクリロ
ニトリルの含有量が１５重量％以上である請求項１～７のいずれか一項に記載の二剤型ア
クリル系接着剤組成物。 (5) The elastomer soluble in a polymerizable monomer having a (meth)acryloyl group is an acrylonitrile-butadiene rubber, and the acrylonitrile-butadiene rubber has an acrylonitrile content of 15% by weight or more. 8. The two-component acrylic adhesive composition according to any one of 7.
り二つの被着体を接合してなることを特徴とする接合体。 A joined body comprising two adherends joined with the two-component acrylic adhesive composition according to any one of claims 1 to 8.
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|---|---|---|---|---|
| US20030045609A1 (en) | 1996-12-24 | 2003-03-06 | University Of Southern Mississippi | Process for forming latex polymers |
| JP2005179548A (en) | 2003-12-22 | 2005-07-07 | Denki Kagaku Kogyo Kk | Two-component acrylic adhesive composition and joined body using the same |
| JP2015030748A (en) | 2013-07-31 | 2015-02-16 | 三菱レイヨン株式会社 | Adhesive composition, cured product thereof and conjugate |
| WO2017170957A1 (en) | 2016-03-31 | 2017-10-05 | デンカ株式会社 | Composition |
| WO2018066619A1 (en) | 2016-10-06 | 2018-04-12 | デンカ株式会社 | Composition |
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| JP2769747B2 (en) * | 1990-12-28 | 1998-06-25 | 電気化学工業株式会社 | Adhesive composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030045609A1 (en) | 1996-12-24 | 2003-03-06 | University Of Southern Mississippi | Process for forming latex polymers |
| JP2005179548A (en) | 2003-12-22 | 2005-07-07 | Denki Kagaku Kogyo Kk | Two-component acrylic adhesive composition and joined body using the same |
| JP2015030748A (en) | 2013-07-31 | 2015-02-16 | 三菱レイヨン株式会社 | Adhesive composition, cured product thereof and conjugate |
| WO2017170957A1 (en) | 2016-03-31 | 2017-10-05 | デンカ株式会社 | Composition |
| WO2018066619A1 (en) | 2016-10-06 | 2018-04-12 | デンカ株式会社 | Composition |
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