TWI498406B - Adhesive and adhesive method - Google Patents
Adhesive and adhesive method Download PDFInfo
- Publication number
- TWI498406B TWI498406B TW102120112A TW102120112A TWI498406B TW I498406 B TWI498406 B TW I498406B TW 102120112 A TW102120112 A TW 102120112A TW 102120112 A TW102120112 A TW 102120112A TW I498406 B TWI498406 B TW I498406B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- adhesive
- rubber
- adhesive layer
- polyurethane
- Prior art date
Links
- 239000000853 adhesive Substances 0.000 title claims description 59
- 230000001070 adhesive effect Effects 0.000 title claims description 59
- 238000000034 method Methods 0.000 title claims description 29
- 229920001971 elastomer Polymers 0.000 claims description 117
- 239000005060 rubber Substances 0.000 claims description 117
- 239000012790 adhesive layer Substances 0.000 claims description 84
- 239000004814 polyurethane Substances 0.000 claims description 53
- 229920002635 polyurethane Polymers 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 51
- 239000000463 material Substances 0.000 claims description 50
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 239000004848 polyfunctional curative Substances 0.000 claims description 24
- -1 aliphatic unsaturated urethane amide Chemical class 0.000 claims description 23
- 238000011282 treatment Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002313 adhesive film Substances 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 5
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 4
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical group NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims description 4
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical group C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 3
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical group O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 claims description 3
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 claims description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical group NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 3
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 3
- FYRWKWGEFZTOQI-UHFFFAOYSA-N 3-prop-2-enoxy-2,2-bis(prop-2-enoxymethyl)propan-1-ol Chemical compound C=CCOCC(CO)(COCC=C)COCC=C FYRWKWGEFZTOQI-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002560 nitrile group Chemical group 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- BMFMTNROJASFBW-UHFFFAOYSA-N 2-(furan-2-ylmethylsulfinyl)acetic acid Chemical compound OC(=O)CS(=O)CC1=CC=CO1 BMFMTNROJASFBW-UHFFFAOYSA-N 0.000 claims 1
- BGQAZAHWMRSYGG-UHFFFAOYSA-N CCCCO.CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O Chemical compound CCCCO.CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O BGQAZAHWMRSYGG-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims 1
- 125000005587 carbonate group Chemical group 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- SSGGNFYQMRDXFH-UHFFFAOYSA-N sulfanylurea Chemical compound NC(=O)NS SSGGNFYQMRDXFH-UHFFFAOYSA-N 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000010410 layer Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000005038 ethylene vinyl acetate Substances 0.000 description 11
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 11
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 244000043261 Hevea brasiliensis Species 0.000 description 8
- 238000007731 hot pressing Methods 0.000 description 8
- 229920003052 natural elastomer Polymers 0.000 description 8
- 229920001194 natural rubber Polymers 0.000 description 8
- 239000012190 activator Substances 0.000 description 7
- 238000004073 vulcanization Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 229920001084 poly(chloroprene) Polymers 0.000 description 6
- 229920000459 Nitrile rubber Polymers 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 239000012948 isocyanate Substances 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- 238000004381 surface treatment Methods 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 229920001778 nylon Polymers 0.000 description 4
- 239000005056 polyisocyanate Substances 0.000 description 4
- 229920001228 polyisocyanate Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- WNYHOOQHJMHHQW-UHFFFAOYSA-N 1-chloropyrene Chemical compound C1=C2C(Cl)=CC=C(C=C3)C2=C2C3=CC=CC2=C1 WNYHOOQHJMHHQW-UHFFFAOYSA-N 0.000 description 2
- ZCHGODLGROULLT-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;propane-1,2-diol Chemical compound CC(O)CO.OCC(CO)(CO)CO ZCHGODLGROULLT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 description 1
- OTCWVYFQGYOYJO-UHFFFAOYSA-N 1-o-methyl 10-o-(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound COC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 OTCWVYFQGYOYJO-UHFFFAOYSA-N 0.000 description 1
- RJKPEKIHHFNMGS-UHFFFAOYSA-N 2,4-ditert-butyl-3-methylphenol Chemical compound CC1=C(C(C)(C)C)C=CC(O)=C1C(C)(C)C RJKPEKIHHFNMGS-UHFFFAOYSA-N 0.000 description 1
- JGBAASVQPMTVHO-UHFFFAOYSA-N 2,5-dihydroperoxy-2,5-dimethylhexane Chemical compound OOC(C)(C)CCC(C)(C)OO JGBAASVQPMTVHO-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JMWGZSWSTCGVLX-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O.CCC(CO)(CO)CO JMWGZSWSTCGVLX-UHFFFAOYSA-N 0.000 description 1
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- ZVYPNSGWLVPWSF-UHFFFAOYSA-N 4,6-dichloro-1-benzofuran Chemical compound ClC1=CC(Cl)=C2C=COC2=C1 ZVYPNSGWLVPWSF-UHFFFAOYSA-N 0.000 description 1
- PJMDLNIAGSYXLA-UHFFFAOYSA-N 6-iminooxadiazine-4,5-dione Chemical group N=C1ON=NC(=O)C1=O PJMDLNIAGSYXLA-UHFFFAOYSA-N 0.000 description 1
- UCZBGHXSCZDEJI-UHFFFAOYSA-N C=CC=C.C=CC1=CC=CC=C1.C(CCC)C1=CC=CC=C1 Chemical compound C=CC=C.C=CC1=CC=CC=C1.C(CCC)C1=CC=CC=C1 UCZBGHXSCZDEJI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- BDJRBEYXGGNYIS-UHFFFAOYSA-N Nonanedioid acid Natural products OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 1
- 229920000562 Poly(ethylene adipate) Polymers 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical group OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- UUORTJUPDJJXST-UHFFFAOYSA-N n-(2-hydroxyethyl)prop-2-enamide Chemical compound OCCNC(=O)C=C UUORTJUPDJJXST-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- VPRUMANMDWQMNF-UHFFFAOYSA-N phenylethane boronic acid Chemical compound OB(O)CCC1=CC=CC=C1 VPRUMANMDWQMNF-UHFFFAOYSA-N 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000582 polyisocyanurate Polymers 0.000 description 1
- 239000011495 polyisocyanurate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- DIFCZTZSUFXWEJ-UHFFFAOYSA-N s-(4-butyl-1,3-benzothiazol-2-yl)thiohydroxylamine Chemical compound CCCCC1=CC=CC2=C1N=C(SN)S2 DIFCZTZSUFXWEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000001508 sulfur Nutrition 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- GSECCTDWEGTEBD-UHFFFAOYSA-N tert-butylperoxycyclohexane Chemical compound CC(C)(C)OOC1CCCCC1 GSECCTDWEGTEBD-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000012936 vulcanization activator Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- PIMBTRGLTHJJRV-UHFFFAOYSA-L zinc;2-methylprop-2-enoate Chemical compound [Zn+2].CC(=C)C([O-])=O.CC(=C)C([O-])=O PIMBTRGLTHJJRV-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本發明是有關於一種黏合件及黏合法，特別是指一種用於使未硫化橡膠與具有極性表面的異種材料相黏合的黏合件，及運用該黏合件的黏合法。The present invention relates to an adhesive member and a bonding method, and more particularly to an adhesive member for bonding an unvulcanized rubber to a dissimilar material having a polar surface, and a bonding method using the bonding member.
在工業上往往需要繁複的處理步驟，才能有效地將異種材料(dissimilar material)緊密的貼合在一起。舉例來說，橡膠(非極性材料)與其他異種材料貼合時，由於橡膠的表面易被氧化，或是加工助劑(例如：加工油、加工蠟等)遷移至橡膠表面等情況，會使橡膠表面的性質不穩定，進而對後續與異種材料進行貼合時造成不良的影響。因此為了減少橡膠表面性質的不穩定，同時避免影響後續貼合效果，橡膠在進行貼合前會先進行一連串的表面處理。以傳統橡膠表面處理流程為例：利用機械方式將已硫化橡膠的表面粗糙化，以增加貼合時的接觸面積並同時露出未被氧化的部分，接著再利用處理劑對已硫化橡膠的表面做進一步的處理，再塗上接著劑，而後貼合至一具有極性表面的異種材料上。In the industry, complicated processing steps are often required to effectively closely bond dissimilar materials together. For example, when rubber (non-polar material) is bonded to other dissimilar materials, the surface of the rubber is easily oxidized, or the processing aid (for example, processing oil, processing wax, etc.) migrates to the rubber surface. The nature of the rubber surface is unstable, which in turn adversely affects subsequent bonding to dissimilar materials. Therefore, in order to reduce the instability of the surface properties of the rubber, and to avoid affecting the subsequent bonding effect, the rubber will first perform a series of surface treatments before the bonding. Taking the conventional rubber surface treatment process as an example: the surface of the vulcanized rubber is roughened by mechanical means to increase the contact area at the time of bonding and simultaneously expose the unoxidized portion, and then the surface of the vulcanized rubber is further treated with a treating agent. The treatment is followed by an adhesive and then applied to a dissimilar material having a polar surface.
專利案EP1323800A2揭示一種運用在鞋材組裝 的黏合膜，該黏合膜包括一由熱塑性聚胺酯類形成的極性貼合層，及一由乙烯共聚物形成的非極性貼合層，該極性貼合層能與一極性材質的待貼物貼合，該非極性貼合層能與一非極性材質的待貼物貼合，因此藉由該黏合膜能將該極性材質的待貼物與非極性材質的待貼物相互黏合。然而，上述黏合膜存在非極性貼合層與極性貼合層彼此相容性不佳的問題，除可能導致兩貼合層彼此無法緊密貼合外，在運用此黏合膜進行貼合時，也可能會讓該極性材質的待貼物與非極性材質的待貼物無法良好地接著。此外，形成該非極性貼合層的乙烯共聚物(如乙烯-醋酸乙烯酯共聚物)更存在耐熱性不足的問題。Patent EP1323800A2 discloses an application in shoe assembly The adhesive film comprises a polar bonding layer formed of thermoplastic polyurethanes and a non-polar bonding layer formed of an ethylene copolymer, and the polar bonding layer can be adhered to a material to be attached The non-polar bonding layer can be adhered to a non-polar material to be attached, so that the adhesive material can adhere the non-polar material to be attached to the non-polar material to be attached. However, the above-mentioned adhesive film has a problem that the non-polar bonding layer and the polar bonding layer have poor compatibility with each other, and the two bonding layers may not be closely adhered to each other, and when the bonding film is used for bonding, It may cause the object to be attached to the polar material to be attached to the non-polar material to be attached. Further, the ethylene copolymer (e.g., ethylene-vinyl acetate copolymer) forming the nonpolar bonding layer has a problem of insufficient heat resistance.
因此，本發明之第一目的，即在提供一種黏合件，該黏合件能改善上述極性貼合層與非極性貼合層相容性不佳的問題。Accordingly, a first object of the present invention is to provide an adhesive member which can improve the problem of poor compatibility of the above-mentioned polar bonding layer with a non-polar bonding layer.
於是本發明黏合件，包含一黏合膜。該黏合膜包括一第一黏著層，及一設置於該第一黏著層上的第二黏著層，其中，該第一黏著層是由一聚胺酯組成物經硬化所形成，該聚胺酯組成物含有聚胺酯、硬化劑，及界面相容劑，及該第二黏著層是由一橡膠組成物所形成，該橡膠組成物含有橡膠組份，及界面相容劑，該聚胺酯組成物的界面相容劑與該橡膠組成物的界面相容劑為相同或不同，且該界面相容劑具有至少一雙鍵及至少一極性基團。Thus, the adhesive of the present invention comprises an adhesive film. The adhesive film comprises a first adhesive layer and a second adhesive layer disposed on the first adhesive layer, wherein the first adhesive layer is formed by hardening a polyurethane composition, and the polyurethane composition contains polyurethane a hardener, an interfacial compatibilizer, and the second adhesive layer are formed of a rubber composition comprising a rubber component, and an interfacial compatibilizer, the interface compatibilizer of the polyurethane composition and The interface compatibilizer of the rubber composition is the same or different, and the interface compatibilizer has at least one double bond and at least one polar group.
本發明之第二目的，即在提供一種黏合法，該 黏合法運用上述黏合件使一未硫化的橡膠與一具有極性表面的異種材料相黏合。A second object of the present invention is to provide a viscous method, Adhesive The adhesive is used to bond an unvulcanized rubber to a dissimilar material having a polar surface.
於是本發明黏合法，包含：提供一上述的黏合 件；將該黏合件的第二黏著層貼合至該未硫化的橡膠並進行一熱壓處理，以使該第二黏著層與該未硫化橡膠間發生架橋反應；及將該黏合件中的第一黏著層貼合至該具有極性表面的異種材料並進行一壓合處理。Thus, the adhesive method of the present invention comprises: providing a bond as described above a second adhesive layer of the adhesive member is attached to the unvulcanized rubber and subjected to a heat pressing treatment to cause a bridging reaction between the second adhesive layer and the unvulcanized rubber; and the first in the adhesive member An adhesive layer is attached to the heterogeneous material having a polar surface and subjected to a press-bonding treatment.
本發明之功效在於：本發明黏合件是用於使一 具有極性表面的異種材料與一未硫化橡膠黏合，該第一黏著層能與該具有極性表面的異種材料黏合，該第二黏著層能與該未硫化橡膠黏合，並因為該界面相容劑，使得該第一黏著層與第二黏著層間具有很好的相容性，且透過本發明黏合件，使該具有極性表面的異種材料與未硫化橡膠能良好地貼合，同時提昇兩者貼合後的接著強度。The effect of the invention is that the adhesive of the invention is used for making one a dissimilar material having a polar surface bonded to an unvulcanized rubber, the first adhesive layer being capable of bonding to the dissimilar material having a polar surface, the second adhesive layer being capable of bonding with the unvulcanized rubber, and because of the interface compatibilizing agent The first adhesive layer and the second adhesive layer have good compatibility, and through the adhesive member of the present invention, the heterogeneous material having the polar surface can be well adhered to the unvulcanized rubber, and the adhesion between the two is improved. strength.
本發明黏合法運用該黏合件使一未硫化的橡膠 與一具有極性表面的異種材料黏合時，不只使得該未硫化的橡膠與該具有極性表面的異種材料能良好地相黏合，更能縮短貼合的操作流程。The adhesive method of the invention uses the adhesive member to make an unvulcanized rubber When it is bonded to a dissimilar material having a polar surface, not only the unvulcanized rubber but also the dissimilar material having a polar surface can be well bonded, and the laminating operation flow can be shortened.
在本文中，該未硫化橡膠指的是含有架橋劑但未經架橋反應產生硫化交聯的橡膠。橡膠的種類例如但不限於：天然橡膠、氯平橡膠、丁苯橡膠、丁腈橡膠、聚異 戊二烯橡膠、順丁橡膠、三元乙丙橡膠(Ethylene Propylene Diene Monomer，簡稱EPDM)或上述的一組合，且硫化劑是視橡膠種類調整。該具有極性表面的異種材料，「異種材料」指的是橡膠類以外的材料，且並不限於是極性材料或非極性材料，只要經表面處理後形成一極性表面即可，較佳為於該極性表面塗上一層聚胺酯膠。該具有極性表面的異種材料例如但不限於：具有極性表面的聚胺酯。As used herein, the unvulcanized rubber refers to a rubber that contains a bridging agent but which does not undergo a bridging reaction to produce a sulfurized crosslink. The types of rubber are, for example but not limited to: natural rubber, chloroprene rubber, styrene butadiene rubber, nitrile rubber, polyiso Ethylene rubber, butadiene rubber, EPDM or a combination thereof, and the vulcanizing agent is adjusted depending on the rubber type. The dissimilar material having a polar surface, the "heterologous material" refers to a material other than the rubber, and is not limited to a polar material or a non-polar material, and may be formed into a polar surface after surface treatment, preferably The polar surface is coated with a layer of polyurethane glue. The heterogeneous material having a polar surface such as, but not limited to, a polyurethane having a polar surface.
本發明黏合件包含：一黏合膜及一與該黏合膜 相疊合的離型膜。The adhesive member of the invention comprises: an adhesive film and a bonding film A superposed release film.
該黏合膜包括一第一黏著層，及一設置於該第 一黏著層上的第二黏著層，其中，該第一黏著層是由一聚胺酯組成物經硬化所形成，該聚胺酯組成物含有聚胺酯、硬化劑，及界面相容劑，及該第二黏著層是由一橡膠組成物所形成，該橡膠組成物含有橡膠組份，及界面相容劑，該聚胺酯組成物的界面相容劑與該橡膠組成物的界面相容劑為相同或不同，且該界面相容劑具有至少一雙鍵及至少一極性基團。The adhesive film includes a first adhesive layer, and one is disposed on the first a second adhesive layer on the adhesive layer, wherein the first adhesive layer is formed by hardening a polyurethane composition comprising a polyurethane, a hardener, an interfacial compatibilizer, and the second adhesive layer Formed by a rubber composition comprising a rubber component and an interfacial compatibilizer, the interface compatibilizer of the polyurethane composition being the same or different from the interfacial compatibilizer of the rubber composition, and The interfacial compatibilizer has at least one double bond and at least one polar group.
較佳地，該極性基團是選自於羥基、酯基、醚 基、三聚異氰酸酯基(isocyanurate group)、脲基甲酸酯基(allophanate group)、縮二脲基(biuret group)、N-醯基尿素基(N-acylurea group)、胺基甲酸酯基(urethane group)、脲基(urea group)、脲二酮基(uretdione group)、亞胺基一氧二氮三烯陸圜二酮基(iminooxadiazindione group)、碳二亞胺基(carbodiimide group)、異氰酸酯基、環氧基、腈基、 氯基、苯基(phenyl group)、碳酸酯基(carbonate ester group)或此等的一組合。Preferably, the polar group is selected from the group consisting of a hydroxyl group, an ester group, and an ether. , an isocyanurate group, an allophanate group, a biuret group, a N-acylurea group, a urethane group (urethane group), urea group (urea group), uretdione group, iminooxadiazindione group, carbodiimide group, Isocyanate group, epoxy group, nitrile group, A chloro group, a phenyl group, a carbonate ester group, or a combination thereof.
本發明黏合件能使一具有極性表面的異種材料 與一未硫化橡膠互相黏合，極性的聚胺酯組成物所形成的第一黏著層能與該具有極性表面的異種材料黏合，非極性的橡膠組成物所形成的第二黏著層能與該未硫化橡膠黏合。The adhesive member of the invention enables a dissimilar material having a polar surface Adhesive to an unvulcanized rubber, a first adhesive layer formed of a polar polyurethane composition can be bonded to the heterogeneous material having a polar surface, and a second adhesive layer formed of a non-polar rubber composition can be bonded to the unvulcanized rubber.
以下將對該聚胺酯組成物及橡膠組成物做進一 步的說明。The polyurethane composition and the rubber composition will be further improved below. Step description.
《聚胺酯組成物》Polyurethane Composition
較佳地，該聚胺酯組成物的結晶熔融溫度範圍 為30℃至70℃，結晶熔融熱範圍為20 J/g至55 J/g[上述性質是透過差示掃描熱分析儀(DSC)於第一次升溫所測得，升溫速率為10℃/min.]。該聚胺酯組成物包括聚胺酯、硬化劑，及界面相容劑，以下將對聚胺酯組成物中的每種組份進一步地說明。Preferably, the crystalline melting temperature range of the polyurethane composition From 30 ° C to 70 ° C, the heat of fusion of the crystal ranges from 20 J/g to 55 J/g [The above properties are measured by a differential scanning calorimeter (DSC) at the first temperature rise, and the heating rate is 10 ° C / Min.]. The polyurethane composition includes a polyurethane, a hardener, and an interfacial compatibilizer, each of which will be further described below in the polyurethane composition.
[聚胺酯][polyurethane]
該聚胺酯可為溶劑型或水分散型。較佳地，該聚胺酯的結晶熔融溫度範圍為30℃至70℃。The polyurethane may be in a solvent type or a water dispersion type. Preferably, the polyurethane has a crystalline melting temperature in the range of from 30 ° C to 70 ° C.
較佳地，該聚胺酯包含80 wt%至90 wt%的軟鏈段(soft segment)，且以該軟鏈段的總量為100 wt%計，該軟鏈段具有80 wt%至100 wt%的聚酯。該聚酯例如但不限於(1).由己二酸與一二醇化合物聚合而得，該二醇化合物例如但不限於：乙二醇、丙二醇、1,4-丁二醇、1,6-己二醇、 新戊二醇、2-甲基-1,3-丙二醇、二乙二醇或二丙二醇等，上述二醇化合物能單獨或混合使用。；(2).聚己內酯(polycaprolactone)；或(3).(1)及(2)的混合。更具體地說，該聚酯例如但不限於：聚己二酸-1,4-丁二醇酯[poly(1,4-butylene adipate)，簡稱PBA]、聚己二酸乙二醇-1,4-丁二醇酯[poly(ethylene-1,4-butylene adipate)，簡稱PEBA]、聚己二酸乙二醇酯[poly(ethylene adipate)，簡稱PEA]、或聚(己二酸六亞甲基新戊二醇酯)[poly(hexamethylene-neopentyl adipate)，簡稱PHNA]。Preferably, the polyurethane comprises 80 wt% to 90 wt% of a soft segment, and the soft segment has 80 wt% to 100 wt% based on the total amount of the soft segment of 100 wt% Polyester. The polyester is, for example but not limited to, (1). It is obtained by polymerizing adipic acid with a mono diol compound such as, but not limited to, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6- Hexanediol, Neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol or dipropylene glycol, etc., the above diol compounds can be used singly or in combination. (2). Polycaprolactone; or (3). (1) and (2). More specifically, the polyester is, for example but not limited to, poly(1,4-butylene adipate, PBA for short), polyethylene adipate-1 ,4-butylene glycol ester [poly(ethylene-1,4-butylene adipate), referred to as PEBA], poly(ethylene adipate), abbreviated as PEA, or poly(adipate) [poly(hexamethylene-neopentyl adipate), referred to as PHNA].
該聚胺酯可運用一般製法所製得，例如將二醇 與二異氰酸酯進行聚合反應所製得。較佳地，該聚胺酯可為經改質的聚胺酯，例如含有不飽和基的聚胺酯，該不飽和基例如但不限於：乙烯基、烯丙基(allyl)、丙烯酸酯基、或甲基丙烯酸酯基等。上述不飽和基可位於聚胺酯的主鏈、側鏈、主鏈的懸吊基團、或主鏈的末端基團上。當聚胺酯為含有不飽和基的聚胺酯時，該含有不飽和基的聚胺酯的不飽和基會與該橡膠組份所含的雙鍵產生反應。The polyurethane can be prepared by a general method, such as diol It is obtained by carrying out polymerization reaction with diisocyanate. Preferably, the polyurethane may be a modified polyurethane such as a polyurethane containing an unsaturated group such as, but not limited to, a vinyl group, an allyl group, an acrylate group, or a methacrylate group. Base. The above unsaturated group may be located on the main chain of the polyurethane, the side chain, the pendant group of the main chain, or the terminal group of the main chain. When the polyurethane is a polyurethane containing an unsaturated group, the unsaturated group of the unsaturated group-containing polyurethane reacts with the double bond contained in the rubber component.
[硬化劑][hardener]
該硬化劑可選用任何適合與聚胺酯併用的硬化 劑，較佳地，該硬化劑為水分散型的多元異氰酸酯(water dispersible polyisocyanate)。該硬化劑例如但不限於：六亞甲基二異氰酸酯(hexamethylene diisocyanate，HDI)、異佛酮二異氰酸酯(isophorone diisocyanate，IPDI)、甲苯二異氰酸酯(toluene diisocyanate，TDI)、二苯基甲烷二異氰 酸酯(diphenylmethane diisocyanate，MDI)、或4,4’-二環己基甲烷二異氰酸酯(4,4’-dicyclohexylmethane diisocyanate)，H12 MDI)等；上述硬化劑可選擇地另含有至少一以下的基團：三聚異氰酸酯基、脲基甲酸酯基、縮二脲基、胺酯基、脲二酮基、亞胺基一氧二氮三烯陸圜二酮基、及碳二亞胺基。更具體地說，該硬化劑例如但不限於：HDI三聚異氰酸酯、IPDI三聚異氰酸酯、HDI/IPDI三聚異氰酸酯或含有脲基甲酸酯基的HDI。上述各種硬化劑可以單獨使用或混合使用。The hardener may be selected from any hardener suitable for use with a polyurethane. Preferably, the hardener is a water dispersible polyisocyanate. The hardener is, for example but not limited to, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (diphenylmethane diisocyanate (TDI), diphenylmethane diisocyanate (TDI) Diphenylmethane diisocyanate, MDI), or 4,4'-dicyclohexylmethane diisocyanate (H 12 MDI), etc.; the above hardener optionally further contains at least one of the following groups: A polyisocyanate group, an allophanate group, a biuret group, an amine ester group, a uretdione group, an imidodiazepinene quinonedione group, and a carbodiimide group. More specifically, the hardener is, for example but not limited to, HDI trimer isocyanate, IPDI trimer isocyanate, HDI/IPDI trimer isocyanate or allophanate-containing HDI. The above various hardeners may be used singly or in combination.
較佳地，該硬化劑的平均官能基數範圍為2.5至4.5，更佳為3.0至4.2。Preferably, the hardener has an average functional group number ranging from 2.5 to 4.5, more preferably from 3.0 to 4.2.
製備聚胺酯組成物時，該硬化劑能直接與其他組份混合，或先溶於一般有機溶劑中再與其他組份混和。When the polyurethane composition is prepared, the hardener can be directly mixed with other components, or dissolved in a common organic solvent and then mixed with other components.
硬化劑能增加該第一黏著層與該具有極性表面的異種材料間的貼合度，進而增加該具有極性表面的異種材料與未硫化橡膠貼合後的接著強度。較佳地，以該聚胺酯的總重為100重量份，該硬化劑的用量範圍為0.5至9.0重量份。該硬化劑的用量小於0.5重量份，會使該第一黏著層的機械強度不足，而可能致使該第一黏著層與該具有極性表面的異種材料產生剝離現象。若硬化劑的用量大於9.0重量份時，會不利於該第一黏著層與具有極性表面的異種材料的貼合。更佳地，該硬化劑的用量範圍為1至7.5重量份。The hardener can increase the adhesion between the first adhesive layer and the dissimilar material having the polar surface, thereby increasing the bonding strength of the dissimilar material having the polar surface after bonding with the unvulcanized rubber. Preferably, the hardener is used in an amount ranging from 0.5 to 9.0 parts by weight based on 100 parts by weight of the total of the polyurethane. The amount of the hardener used is less than 0.5 parts by weight, which may cause insufficient mechanical strength of the first adhesive layer, and may cause peeling of the first adhesive layer and the dissimilar material having the polar surface. If the amount of the hardener is more than 9.0 parts by weight, the adhesion of the first adhesive layer to the dissimilar material having a polar surface is disadvantageous. More preferably, the hardener is used in an amount ranging from 1 to 7.5 parts by weight.
[界面相容劑][Interface compatibilizer]
較佳地，該界面相容劑是選自於三烯丙基三聚 異氰酸酯(triallyl isocyanurate)、參(羥甲基)丙烷三甲基丙烯酸酯[tris(hydroxymethyl)propane trimethacrylate]、季戊四醇三烯丙基醚(pentaerythritol triallyl ether)、二甲基丙烯酸鋅、季戊四醇三丙烯酸酯(pentaerythritol triacrylate)、丙氧基化季戊四醇三丙烯酸酯(pentaerythritol propoxylate triacrylate)、脂肪族不飽和丙烯酸胺酯[unsaturated aliphatic urethane acrylate，市售商品如Bayer公司所製造的Desmolux® U 100]、含有異氰酸酯基的脂肪族丙烯酸胺酯[Isocyanate-bearing aliphatic urethane acrylate，市售商品如Bayer公司所製造的Desmolux® XP 2510]、羥基封端的聚丁二烯[hydroxyl-terminated polybutadiene，市售商品如Cray Valley公司所製造的Krasol® 系列]或此等的一組合。值得一提的是，該界面相容劑是透過以下方式來提昇第一黏著層與第二黏著層間的相容性：(1).該界面相容劑所含的雙鍵會與該橡膠組份的雙鍵產生架橋反應；(2).界面相容劑的極性基團與聚胺酯的極性基團會形成鍵結或凡得瓦引力。Preferably, the interfacial compatibilizer is selected from the group consisting of triallyl isocyanurate, tris (hydroxymethyl) propane trimethacrylate, and pentaerythritol triene. Pentaerythritol triallyl ether, zinc dimethacrylate, pentaerythritol triacrylate, pentaerythritol propoxylate triacrylate, unsaturated aliphatic urethane acrylate Commercially available products such as Desmolux ® U 100 manufactured by Bayer Co., Ltd., Isocyanate-bearing aliphatic urethane acrylate (commercially available as Desmolux ® XP 2510 manufactured by Bayer Co., Ltd.), hydroxyl terminated polybutadiene [hydroxyl-terminated polybutadiene, commercially available as manufactured by the company Cray Valley Krasol ® series] or a combination of these. It is worth mentioning that the interface compatibilizer improves the compatibility between the first adhesive layer and the second adhesive layer by: (1) the double bond contained in the interface compatibilizer and the rubber group The double bond produces a bridging reaction; (2) the polar group of the interfacial compatibilizer and the polar group of the polyurethane form a bond or van der Waals.
較佳地，以該聚胺酯的總重為100重量份，該 界面相容劑的用量範圍為0.5至4重量份。當界面相容劑的用量超過4重量份，會使得第一黏著層的交聯程度下降，使得第一黏著層的強度不足。更佳地，該界面相容劑的用量範圍為0.5至3重量份。Preferably, the total weight of the polyurethane is 100 parts by weight, The amount of interfacial compatibilizer is in the range of 0.5 to 4 parts by weight. When the amount of the interface compatibilizer exceeds 4 parts by weight, the degree of crosslinking of the first adhesive layer is lowered, so that the strength of the first adhesive layer is insufficient. More preferably, the interface compatibilizer is used in an amount ranging from 0.5 to 3 parts by weight.
[起始劑][starting agent]
該聚胺酯組成物中還可選擇性地添加起始劑， 該起始劑能單獨或混合使用，例如但不限於：三級丁基過氧化碳酸-2-乙基己酯(t-butyl peroxy-2-ethylhexyl monocarbonate)、1,1-二(三級丁基)過氧化環十二烷[1,1-di(t-butylperoxy)cyclohexane]、過氧化二異丙苯(dicumyl peroxide)、2,5-二甲基正己烷-2,5-二氫過氧化物(2,5-dimethylhexane 2,5-dihydroperoxide)。An initiator may also be optionally added to the polyurethane composition. The initiator can be used singly or in combination, such as, but not limited to, t-butyl peroxy-2-ethylhexyl monocarbonate, 1,1-di (tertiary) 1,1,1-di(t-butylperoxycyclohexane), dicumyl peroxide, 2,5-dimethyl-n-hexane-2,5-dihydroperoxide 2,5-dimethylhexane 2,5-dihydroperoxide.
該起始劑能使具有極性表面的異種材料與未硫 化橡膠，兩者貼合後經水洗具有較佳的接著強度。較佳地，以該聚胺酯的總重為100重量份，該起始劑的用量範圍為0至5重量份。更佳地，該起始劑的用量範圍為0.1至3重量份。The initiator can enable dissimilar materials with polar surfaces and unsulfurized The rubber has a good adhesion strength after being applied to the water and washed. Preferably, the initiator is used in an amount ranging from 0 to 5 parts by weight based on 100 parts by weight of the total of the polyurethane. More preferably, the initiator is used in an amount ranging from 0.1 to 3 parts by weight.
該聚胺酯組成物的製備並無特別限制，例如採The preparation of the polyurethane composition is not particularly limited, for example,
用將上述各組份置於攪拌器中攪拌均勻混合即可。The components described above are placed in a stirrer and stirred uniformly.
《橡膠組成物》Rubber Composition
該橡膠組成物包括橡膠組份及界面相容劑。以 下將對橡膠組成物中的每種組份進一步地說明。The rubber composition includes a rubber component and an interface compatibilizer. Take Each component in the rubber composition will be further described below.
[橡膠組份][Rubber component]
該橡膠組份的選用是配合該未硫化橡膠，目的 是使該第二黏著層與該未硫化橡膠間產生優異的接著性，該橡膠組份例如但不限於以下種類：天然橡膠(natural rubber，NR)、氯平橡膠(chloroprene rubber，CR)、丁苯橡膠(styrene-butadiene rubber，SBR)、丁腈橡膠 (nitrile-butadiene rubber，NBR)、聚異戊二烯橡膠(polyisoprene，IR)或順丁橡膠(polybutadiene，BR)等。除了上述種類的橡膠外，該橡膠組份亦可選自於經極性化合物接枝或改質的橡膠，及經氯基改質而得的氯化橡膠(Chlorinated rubber)。該經極性化合物接枝或改質的橡膠例如為：經極性化合物接枝或改質的氯平橡膠，或經極性化合物接枝的天然橡膠，上述極性化合物例如但不限於：甲基丙烯酸甲酯(methyl methacrylate，MMA)、馬來酸酐(maleic anhydride，MAH)、甲基丙烯酸羥乙酯[(hydroxyethyl)methacrylate，HEMA]、或N-羥乙基丙烯醯胺(N-hydroxyethyl acrylamide)、羧酸基等。更具體的說，該經極性化合物接枝或改質的橡膠例如但不限於：甲基丙烯酸甲酯接枝的天然橡膠、甲基丙烯酸甲酯接枝的氯平橡膠等。上述種類的橡膠可單獨或混合使用。The rubber component is selected to match the unvulcanized rubber. It is to provide excellent adhesion between the second adhesive layer and the unvulcanized rubber. The rubber component is, for example but not limited to, the following types: natural rubber (NR), chloroprene rubber (CR), butylbenzene Styrene-butadiene rubber (SBR), nitrile rubber (nitrile-butadiene rubber, NBR), polyisoprene (IR) or polybutadiene (BR). In addition to the rubber of the above kind, the rubber component may be selected from a rubber grafted or modified with a polar compound, and a Chlorinated rubber obtained by a chlorine-based modification. The rubber grafted or modified with the polar compound is, for example, a chloroprene rubber grafted or modified with a polar compound or a natural rubber grafted with a polar compound such as, but not limited to, methyl methacrylate (methyl methacrylate, MMA), maleic anhydride (MAH), hydroxyethyl methacrylate (HEMA), or N-hydroxyethyl acrylamide, carboxylic acid Base. More specifically, the rubber grafted or modified with the polar compound is, for example but not limited to, methyl methacrylate-grafted natural rubber, methyl methacrylate-grafted chloropyrene rubber, and the like. The above types of rubber may be used singly or in combination.
[界面相容劑][Interface compatibilizer]
橡膠組成物中的界面相容劑是同上所述，故不再贅述。The interfacial compatibilizer in the rubber composition is the same as described above and will not be described again.
以該橡膠組份的總重為100重量份，該界面相容劑的用量範圍為1至15重量份。該界面相容劑的用量高於15重量份，則會使該第二黏著層的耐熱性變差，且該第二黏著層也容易帶有色澤。The interface compatibilizer is used in an amount ranging from 1 to 15 parts by weight based on 100 parts by weight of the total of the rubber component. When the amount of the interface compatibilizer is more than 15 parts by weight, the heat resistance of the second adhesive layer is deteriorated, and the second adhesive layer is also liable to have a color.
該橡膠組成物中還可選擇性地添加：架橋劑、活化劑、加硫促進劑、增黏劑，或抗氧化劑等添加劑。各添加劑詳細說明如下： [架橋劑]Additives such as a bridging agent, an activator, a vulcanization accelerator, a tackifier, or an antioxidant may be optionally added to the rubber composition. The details of each additive are as follows: [Bridge agent]
於後續貼合的製程中，該架橋劑能使第二黏著層與未硫化橡膠發生架橋反應，而使第二黏著層與未硫化橡膠間產生鍵結，藉此增加該第二黏著層與未硫化橡膠間的黏著程度。該架橋劑是視橡膠組份的性質來選擇，且能單獨或混合使用。該架橋劑較佳為使用十小時後，半衰期溫度高於90℃的化合物。較佳地，該架橋劑是選自於硫磺類或過氧化物類。In the subsequent bonding process, the bridging agent can bridge the second adhesive layer with the unvulcanized rubber, and bond between the second adhesive layer and the unvulcanized rubber, thereby increasing the gap between the second adhesive layer and the unvulcanized rubber. The degree of adhesion. The bridging agent is selected depending on the nature of the rubber component and can be used singly or in combination. The bridging agent is preferably a compound having a half-life temperature higher than 90 ° C after ten hours of use. Preferably, the bridging agent is selected from the group consisting of sulfurs or peroxides.
較佳地，以該橡膠組份的總重為100重量份，該架橋劑的用量範圍為0至6重量份。更佳地，該架橋劑的用量範圍為1至3重量份。Preferably, the bridging agent is used in an amount ranging from 0 to 6 parts by weight based on 100 parts by weight of the total of the rubber component. More preferably, the bridging agent is used in an amount ranging from 1 to 3 parts by weight.
在此要特別說明的是，因為貼合的過程中，該未硫化橡膠含有的架橋劑會遷移至未硫化橡膠的表面，所以即使當該橡膠組成物未包含架橋劑時，該第二黏著層與該未硫化橡膠間仍會發生架橋反應，使該第二黏著層與該未硫化橡膠間良好的黏著。It should be particularly noted here that since the bridging agent contained in the unvulcanized rubber migrates to the surface of the unvulcanized rubber during the bonding, even when the rubber composition does not contain a bridging agent, the second adhesive layer and the The bridging reaction still occurs between the unvulcanized rubber, so that the second adhesive layer and the unvulcanized rubber adhere well.
[活化劑][activator]
可依據橡膠組成物的性質及後續需求選擇性地添加活化劑(vulcanization activator)。該活性劑為能促進架橋反應進行的試劑，該活性劑的選用及用量是視橡膠組成物或未硫化橡膠的種類及用量，及架橋劑的種類及用量而調整。於本發明黏合件一具體例中，該活化劑例如但不限於：ZnO、MgO或聚乙二醇，上述活化劑能單獨或混合使用。較佳地，以該橡膠組份的總重為100重量份，該活 化劑的用量範圍為2至10重量份。An activator (vulcanization activator) can be selectively added depending on the nature of the rubber composition and subsequent requirements. The active agent is a reagent capable of promoting the bridging reaction. The selection and dosage of the active agent are adjusted depending on the type and amount of the rubber composition or the unvulcanized rubber, and the type and amount of the bridging agent. In a specific example of the adhesive of the present invention, the activator is, for example but not limited to, ZnO, MgO or polyethylene glycol, and the above activators can be used singly or in combination. Preferably, the total weight of the rubber component is 100 parts by weight, the activity The amount of the agent used is in the range of 2 to 10 parts by weight.
[加硫促進劑][Sulfurization accelerator]
該加硫促進劑(vulcanization accelerator)用以提高該第二黏著層與未硫化橡膠間架橋反應的程度。該加硫促進劑的選用及用量是視橡膠組成物或未硫化橡膠的種類及用量，及架橋劑的種類及用量而調整。該加硫促進劑能單獨或混合使用，例如但不限於：胍類(guanidines)、醛胺類(aldehyde-amines)、醛氨類(aldehyde-ammonias)、硫脲類(thioureas)、秋蘭姆類(thiurams)、黃原酸鹽類(xanthates)、次磺醯胺類(sulphenamides)、二硫代胺基甲酸類(dithiocarbamates)，或噻唑類(thiazoles)。較佳地，加硫促進劑為混用兩種以上時，能獲得較佳的接著強度。The vulcanization accelerator is used to increase the degree of bridging reaction between the second adhesive layer and the unvulcanized rubber. The selection and dosage of the vulcanization accelerator are adjusted depending on the type and amount of the rubber composition or the unvulcanized rubber, and the type and amount of the bridging agent. The vulcanization accelerator can be used singly or in combination, such as, but not limited to, guanidines, aldehyde-amines, aldehyde-ammonias, thioureas, thiurams. Thiurams, xanthates, sulphenamides, dithiocarbamates, or thiazoles. Preferably, when the vulcanization accelerator is used in combination of two or more kinds, a preferable bonding strength can be obtained.
較佳地，以該橡膠組份的總重為100重量份，該加硫促進劑的用量範圍為0.1至3重量份。Preferably, the vulcanization accelerator is used in an amount ranging from 0.1 to 3 parts by weight based on 100 parts by weight of the total of the rubber component.
[增黏劑][tackifier]
該增黏劑能提高該第二黏著層與未硫化橡膠間的接觸黏性，進而提昇該第二黏著層與未硫化橡膠間的黏著度。該增黏劑能單獨或混合使用，例如但不限於：松香(rosin)、松香衍生物、改質或未經改質的萜烯類(terpene)樹脂、脂肪族石油樹脂、環脂肪族石油樹脂，或芳香族石油樹脂。以上述改質或未經改質的萜烯類(terpene)樹脂、脂肪族石油樹脂、環脂肪族石油樹脂，及芳香族石油樹脂中具有極性官能基者為較佳。The tackifier can improve the contact viscosity between the second adhesive layer and the unvulcanized rubber, thereby improving the adhesion between the second adhesive layer and the unvulcanized rubber. The tackifier can be used singly or in combination, such as but not limited to: rosin, rosin derivatives, modified or unmodified terpene resins, aliphatic petroleum resins, cycloaliphatic petroleum resins. , or aromatic petroleum resin. It is preferred that the above-mentioned modified or unmodified terpene resin, aliphatic petroleum resin, cycloaliphatic petroleum resin, and aromatic petroleum resin have a polar functional group.
較佳地，以該橡膠組份的總重為100重量份， 該增黏劑的用量範圍為1至40重量份。若該增黏劑的用量高於40重量份，則會使該第二黏著層的耐曲折性下降，且易帶有色澤。Preferably, the total weight of the rubber component is 100 parts by weight, The tackifier is used in an amount ranging from 1 to 40 parts by weight. If the amount of the tackifier is more than 40 parts by weight, the toughness of the second adhesive layer is lowered, and the color is easily carried.
[抗氧化劑][Antioxidants]
該抗氧化劑用以提高第二黏著層的安定性。該抗氧化劑能單獨或混合使用，例如但不限於：2,6-二三級丁基對甲酚(Butylated hydroxytoluene，BHT)、、癸二酸雙(1,2,2,6,6-五甲基-4-哌啶基)酯[bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate]、或癸二酸甲基1,2,2,6,6-五甲基-4-哌啶基酯(methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate)。The antioxidant is used to improve the stability of the second adhesive layer. The antioxidant can be used singly or in combination, such as, but not limited to, 2,6-di-tert-butyl hydroxytoluene (BHT), and sebacic acid bis(1,2,2,6,6-five Methyl-4-piperidinyl) [bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate], or azelaic acid methyl 1,2,2,6,6-penta Methyl 4-piperidyl ester (methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate).
較佳地，以該橡膠組份的總重為100重量份，該抗氧化劑的用量範圍為0.05至2重量份。Preferably, the antioxidant is used in an amount ranging from 0.05 to 2 parts by weight based on 100 parts by weight of the total of the rubber component.
該橡膠組成物的製備並無特別限制，例如採用將上述各組份置於攪拌器中攪拌均勻混合即可。The preparation of the rubber composition is not particularly limited. For example, the above components may be placed in a stirrer and stirred uniformly.
《離型膜》Release film
該離型膜能與該第一黏著層接觸，或與該第二黏著層接觸，於本發明黏合件的較佳具體例中，該第一黏著層與該第二黏著層皆分別與一離型膜接觸。該離型膜的材質並無特別限制，例如但不限於：聚對苯二甲酸乙二酯(PET)、聚丙烯(PP)、聚乙烯(PE)、或聚四氟乙烯等。於本發明黏合件的一具體例中，該離型膜是聚對苯二甲酸乙二酯類。The release film can be in contact with the first adhesive layer or in contact with the second adhesive layer. In a preferred embodiment of the adhesive of the present invention, the first adhesive layer and the second adhesive layer are respectively separated from each other. Type film contact. The material of the release film is not particularly limited, and examples thereof include, but are not limited to, polyethylene terephthalate (PET), polypropylene (PP), polyethylene (PE), and polytetrafluoroethylene. In a specific example of the adhesive of the present invention, the release film is polyethylene terephthalate.
本發明黏合件的製備是將該聚胺酯組成物塗佈 在一離型膜後，經過乾燥處理，以形成該第一黏著層，接著，於第一黏著層上塗佈該橡膠組成物，經過乾燥處理，以形成該第二黏著層，再於該第二黏著層上覆蓋另一離型膜，即製得本發明黏合件。The adhesive of the present invention is prepared by coating the polyurethane composition After the release film is dried, to form the first adhesive layer, and then coating the rubber composition on the first adhesive layer, and drying to form the second adhesive layer, and then The adhesive layer of the present invention is obtained by covering the second adhesive layer with another release film.
本發明黏合件因為該界面相容劑使第一黏著層 與第二黏著層能良好地相容及彼此良好貼合，且本發明黏合件能有效地讓該具有極性表面的異種材料與未硫化橡膠得以良好地貼合，並同時提昇兩者貼合後的接著強度。同時，本發明黏合件適用的異種材料範圍較廣，並不限於一定要是極性材料，也適用於經表面處理後表面具有極性的非極性材料，因此對產業應用上有很大的幫助。The adhesive of the present invention makes the first adhesive layer because of the interface compatibilizer It is compatible with the second adhesive layer and is well adhered to each other, and the adhesive member of the present invention can effectively match the dissimilar material having the polar surface with the unvulcanized rubber, and simultaneously improve the bonding of the two. Then the intensity. At the same time, the adhesive material of the invention has a wide range of dissimilar materials, and is not limited to a polar material, and is also suitable for a non-polar material having a surface having a surface after surface treatment, and thus is of great help to industrial applications.
本發明黏合件後續的應用並無特別限制，只要 是需要貼合未硫化橡膠與具有極性表面的異種材料的相關應用(例如製鞋業、建築業、包裝業、運動器材等)皆適合使用本發明黏合件。本發明黏合件的一具體應用為鞋子組件的貼合組裝，更具體地說為大底(未硫化橡膠)與中底(具有極性表面的異種材料)的貼合。The subsequent application of the adhesive of the present invention is not particularly limited as long as It is suitable for the application of the unvulcanized rubber and the dissimilar materials having a polar surface (for example, footwear, construction, packaging, sports equipment, etc.) to use the adhesive of the present invention. A particular application of the adhesive of the present invention is the conforming assembly of the shoe assembly, more specifically the bonding of the outsole (unvulcanized rubber) to the midsole (a dissimilar material having a polar surface).
本發明黏合法，用於使一未硫化的橡膠與一具 有極性表面的異種材料相黏合。該黏合法包含：將一上述的黏合件移除第二黏著層上的離型膜後，將第二黏著層貼合至該未硫化的橡膠並進行一熱壓處理，以使該第二黏著層與該未硫化橡膠間發生架橋反應。接者移除該第一黏著層上的離型膜，將第一黏著層貼合至該具有極性表面的異種材料並進行一壓合處理。較佳地，第一黏著層貼合至該 具有極性表面的異種材料前先進行一熱活化處理，使該第一黏著層熱活化至表面溫度達60℃以上後，再將第一黏著層貼合至該具有極性表面的異種材料。The adhesive method of the invention is used for making an unvulcanized rubber and a Dissimilar materials with polar surfaces are bonded. The adhesive method comprises: after removing the above-mentioned adhesive member from the release film on the second adhesive layer, bonding the second adhesive layer to the unvulcanized rubber and performing a heat pressing treatment to make the second adhesive A bridging reaction occurs between the layer and the unvulcanized rubber. The release film is removed from the first adhesive layer, and the first adhesive layer is attached to the heterogeneous material having a polar surface and subjected to a press-bonding treatment. Preferably, the first adhesive layer is attached to the The dissimilar material having a polar surface is subjected to a heat activation treatment to thermally activate the first adhesive layer to a surface temperature of 60 ° C or higher, and then the first adhesive layer is attached to the dissimilar material having a polar surface.
較佳地，該熱壓處理的熱壓溫度範圍為120℃ 至180℃，熱壓壓力範圍為100 kg/cm2 至150 kg/cm2 ，熱壓時間範圍為4分鐘至6分鐘。Preferably, the hot pressing treatment has a hot pressing temperature ranging from 120 ° C to 180 ° C, a hot pressing pressure ranging from 100 kg/cm 2 to 150 kg/cm 2 , and a hot pressing time ranging from 4 minutes to 6 minutes.
較佳地，該壓合處理的壓合溫度範圍為25℃ 至40℃，壓合時間範圍為8秒至30秒，壓力範圍為20 kg/cm2 至40 kg/cm2 。Preferably, the press-bonding treatment has a press-fit temperature in the range of 25 ° C to 40 ° C, a press-fit time in the range of 8 seconds to 30 seconds, and a pressure in the range of 20 kg/cm 2 to 40 kg/cm 2 .
本發明黏合法因在該熱壓處理的過程中，使未 硫化橡膠與第二黏著層間發生架橋反應，於兩者間產生鍵結提昇兩者間的黏著度，因此不需像傳統一樣，對橡膠先進行繁複的表面處理，才能再進行後續的貼合流程，因此能有效簡化貼合的操作流程。The adhesive method of the present invention is made in the process of the hot pressing process The bridging reaction between the vulcanized rubber and the second adhesive layer causes a bond between the two to enhance the adhesion between the two, so that it is not necessary to perform a complicated surface treatment on the rubber as in the conventional case, and then the subsequent bonding process can be performed. Therefore, the operational flow of the fit can be effectively simplified.
本發明將就以下實施例來作進一步說明，但應 瞭解的是，該實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。The invention will be further illustrated by the following examples, but It is to be understood that the examples are for illustrative purposes only and are not to be construed as limiting.
<實施例><Example>
以下實施例與比較例分別使用下列材料進行製備：The following examples and comparative examples were prepared using the following materials, respectively:
1.聚胺酯：使用由大東樹脂公司所製造的大東71(溶劑型聚胺酯，軟鏈段含量範圍為80 wt%至90 wt%)，及大東6608(水分散型聚胺酯，軟鏈段含量範圍為80 wt%至90 wt%)。1. Polyurethane: Dadong 71 (solvent type polyurethane, soft segment content ranging from 80 wt% to 90 wt%) manufactured by Dadong Resin Co., Ltd., and Dadong 6608 (water-dispersed polyurethane) with a soft segment content of 80 Wt% to 90 wt%).
2.硬化劑：使用由大東樹脂公司所製造的大東367S(聚異氰酸酯硬化劑)，及大東368(聚異氰酸酯硬化劑)。2. Hardener: Dadong 367S (polyisocyanate hardener) manufactured by Dadong Resin Co., Ltd., and Dadong 368 (polyisocyanate hardener) were used.
3.界面相容劑：使用Acros公司製造的TAIC(三烯丙基三聚異氰酸酯)，及Aldrich公司製造的PETA(季戊四醇三丙烯酸酯，pentaerythritol triacrylate)、PEPTA(丙氧基化季戊四醇三丙烯酸酯，pentaerythritol propoxylate triacrylate)，及Bayer公司製造的Desmolux® XP 2510(含有異氰酸酯基的脂肪族丙烯酸胺酯，Isocyanate-bearing aliphatic urethane acrylate)。3. Interfacial compatibilizer: TAIC (trylyl tripolyisocyanate) manufactured by Acros, PETA (pentaerythritol triacrylate) manufactured by Aldrich, PEPTA (pentoxytetramethylene triacrylate) Pentaerythritol propoxylate triacrylate), and Desmolux ® XP 2510 (isocyanate-bearing aliphatic urethane acrylate) manufactured by Bayer.
4.起始劑：使用日本油脂NOF公司製造的79C[1,1-二(三級丁基)過氧化環十二烷[1,1-di(t-butylperoxy)cyclohexane]。4. Starting agent: 79C [1,1-di(t-butylperoxy)cyclohexane] manufactured by NOF, Japan.
5.橡膠組份：使用天然橡膠(rubbertex公司製造的ADS-XL，表1及表2中以NR表示)、丁苯橡膠(LG公司製造的SBR1502，表1及表2中以SBR表示)、聚異戊二烯橡膠(Sterlitamak公司製造的SKI-3S，表1及表2中以IR表示)、氯平橡膠(TOSOH公司製造的CR570及G-40，表1及表2中以CR表示)、甲基丙烯酸甲酯接枝天然橡膠(自行合成，表1及表2中以MMA-g-NR表示)、甲基丙烯酸甲酯接枝氯平橡膠(自行合成，表1及表2中以MMA-g-CR表示)，及氯化橡膠(Bayer公司製造的S-20，表1及表2中以Chlorinated rubber表示)5. Rubber component: natural rubber (ADS-XL manufactured by Rubbertex Co., Ltd., NR in Tables 1 and 2), styrene-butadiene rubber (SBR1502 manufactured by LG Corporation, and SBR in Table 1 and Table 2), Polyisoprene rubber (SKI-3S manufactured by Sterlitamak Co., Ltd., represented by IR in Tables 1 and 2), Chloroprene rubber (CR570 and G-40 manufactured by TOSOH Co., Ltd., and CR in Tables 1 and 2) Methyl methacrylate grafted natural rubber (self-synthesized, represented by MMA-g-NR in Tables 1 and 2), methyl methacrylate-grafted chloropyrene rubber (self-synthesis, in Tables 1 and 2) MMA-g-CR), and chlorinated rubber (S-20 manufactured by Bayer, indicated by Chlorinated rubber in Tables 1 and 2)
6.活化劑：使用氧化鋅及聚乙二醇。6. Activator: Zinc oxide and polyethylene glycol are used.
7.架橋劑：使用日本油脂NOF公司製造的79C。7. Bridging agent: 79C manufactured by NOF, Japan.
8.加硫促進劑：使用Sovereign公司製造的TS(一硫化四甲基秋蘭姆，tetramethylthiuram monosulfide)，及TBBS[N-第三丁基-苯幷噻唑-次磺醯胺(N-tert-butyl-2-benzothiazole sulfenamide)]。8. Sulfurizing accelerator: TS (tetramethylthiuram monosulfide) manufactured by Sovereign, and TBBS [N-tert-butyl-benzothiazole-sulfenamide (N-tert-) Butyl-2-benzothiazole sulfenamide)].
9.增黏劑：使用Arakawa公司製造的松香樹脂及氫化樹脂。9. Tackifier: A rosin resin and a hydrogenated resin manufactured by Arakawa Co., Ltd. were used.
[實施例1]黏合件的製備及黏合法[Example 1] Preparation and adhesion of adhesive parts
依據表1的各成分種類及用量製備實施例1的聚胺酯組成物：將聚胺酯組分、硬化劑、起始劑，及界面相容劑投入120 L的批次式反應器，於25℃下攪拌15分鐘至均勻狀態，即製得實施例1的聚胺酯組成物。The polyurethane composition of Example 1 was prepared according to the types and amounts of the components of Table 1. The polyurethane component, the hardener, the initiator, and the interfacial compatibilizer were placed in a 120 L batch reactor and stirred at 25 ° C. The polyurethane composition of Example 1 was prepared in a uniform state for 15 minutes.
依據表1的各成分種類及用量製備實施例1的橡膠組成物：依以下順序將溶劑、橡膠組分、活化劑、界面相容劑、加硫促進劑，及增黏劑投入200 L的批次式反應器中，待該批次式反應器的溫度下降至30℃時再加入架橋劑，接著於60℃下攪拌分散至均勻狀態，上述進料至攪拌的過程共歷時8小時後，即製得實施例1的橡膠組成物。The rubber composition of Example 1 was prepared according to the types and amounts of the components of Table 1. The solvent, the rubber component, the activator, the interfacial compatibilizer, the vulcanization accelerator, and the tackifier were put into a batch of 200 L in the following order. In the secondary reactor, when the temperature of the batch reactor is lowered to 30 ° C, the bridging agent is further added, followed by stirring and dispersing to a uniform state at 60 ° C, and the above-mentioned feeding to stirring process lasts for 8 hours, that is, The rubber composition of Example 1 was obtained.
使用連續式comma coater塗佈機台進行聚胺酯組成物及橡膠組成物的塗佈。將實施例1的聚胺酯組成物塗佈於一離型膜上[奕普公司製造，材質：聚對苯二甲酸乙二酯(polyethylene terephthalate，PET)，膜厚：25至38微米]，進行乾燥處理以使聚胺酯組成物硬化(採階段式乾 燥，乾燥溫度：80-90-100℃)，即形成第一黏著層(膜厚：25至50微米)。接著將實施例1橡膠組成物以一混合溶劑溶解後(以該混合溶劑的總重為100 wt%，該混合溶劑包含碳氫溶劑38 wt%(碳氫溶劑為Exxonmobil公司製造的DSP80/100)、甲基環己烷23 wt%、乙酸正丙酯17 wt%，及丁酮22 wt%。且以該混合溶劑的總重為100 wt%，該橡膠組成物的用量範圍為17 wt%至22 wt%)，塗佈在第一黏著層上，進行乾燥處理(採階段式乾燥，乾燥溫度：70-80-90℃)，即形成第二黏著層(膜厚：25至50微米)，再於該第二黏著層上覆蓋另一離型膜，即製得實施例1黏合件。The coating of the polyurethane composition and the rubber composition was carried out using a continuous comma coater coating machine. The polyurethane composition of Example 1 was applied onto a release film [manufactured by Sigma, Polyethylene terephthalate (PET), film thickness: 25 to 38 μm], and dried. Treatment to harden the polyurethane composition Drying, drying temperature: 80-90-100 ° C), that is, forming a first adhesive layer (film thickness: 25 to 50 μm). Next, after the rubber composition of Example 1 was dissolved in a mixed solvent (100 wt% based on the total weight of the mixed solvent, the mixed solvent contained 38 wt% of a hydrocarbon solvent (hydrocarbon solvent was DSP80/100 manufactured by Exxonmobil Co., Ltd.) , 23 wt% of methylcyclohexane, 17 wt% of n-propyl acetate, and 22 wt% of methyl ethyl ketone, and the total weight of the mixed solvent is 100 wt%, and the amount of the rubber composition ranges from 17 wt% to 22 wt%), coated on the first adhesive layer, dried (staged drying, drying temperature: 70-80-90 ° C), that is, a second adhesive layer (film thickness: 25 to 50 μm) is formed. Then, another release film was covered on the second adhesive layer, that is, the adhesive of Example 1 was obtained.
將實施例1黏合件的第二黏著層與欲貼合的未 硫化橡膠(未硫化橡膠種類：BR、IR、NBR及SBR的混合)接觸，放入熱壓機(廠牌型號：大田油壓01EA-10)中進行熱壓處理，以使第二黏著層與欲貼合的未硫化橡膠貼合及發生架橋反應，熱壓處理條件為：溫度120℃至180℃，壓力150 kg/cm2 ，時間5分鐘。熱壓處理完成後移除離型膜，使第一黏著層與一具有極性表面的EVA待貼物接觸，接著進行壓合處理，壓合處理條件為：壓力30 kg/cm2 ，時間10秒，即完成實施例1黏合法，並獲得一貼合樣品(表1中表示為：橡膠貼合EVA)。將具有極性表面的EVA待貼物置換為具有極性表面的耐綸(nylon)待貼物，重複上述黏合法，並獲得另一貼合樣品(表1中表示為：橡膠貼合Nylon)。The second adhesive layer of the adhesive of Example 1 was brought into contact with the unvulcanized rubber to be bonded (the type of unvulcanized rubber: a mixture of BR, IR, NBR and SBR), and placed in a hot press (brand type: Daejeon Oil Pressure 01EA- 10) performing a hot pressing treatment so that the second adhesive layer is bonded to the unvulcanized rubber to be bonded and a bridging reaction occurs, and the hot pressing treatment conditions are: temperature 120 ° C to 180 ° C, pressure 150 kg / cm 2 , time 5 minute. After the hot pressing process is completed, the release film is removed, and the first adhesive layer is brought into contact with an EVA to be attached with a polar surface, followed by pressing treatment, and the pressing treatment condition is: pressure 30 kg/cm 2 , time 10 seconds That is, the adhesion of Example 1 was completed, and a bonded sample (indicated in Table 1 as: rubber-bonded EVA) was obtained. The EVA-attached article having a polar surface was replaced with a nylon-attached article having a polar surface, the above-mentioned adhesion method was repeated, and another bonded sample (indicated as: rubber-bonded Nylon in Table 1) was obtained.
[實施例2至12及比較例1至4]黏合件的製備 及黏合法[Examples 2 to 12 and Comparative Examples 1 to 4] Preparation of Adhesives And sticky
實施例2至12及比較例1至4，是以與實施例1相同的方式製備黏合件，並以相同方式進行黏合法並獲得貼合樣品。In Examples 2 to 12 and Comparative Examples 1 to 4, an adhesive member was prepared in the same manner as in Example 1, and the adhesion was carried out in the same manner and a bonded sample was obtained.
實施例1至12及比較例1至4中各組份的種類及用量是由表1及表2所示。The types and amounts of the components in Examples 1 to 12 and Comparative Examples 1 to 4 are shown in Tables 1 and 2.
[評價項目][evaluation project]
1.接著強度測試1. Then the strength test
分別將上述實施例1至12及比較例1至4的貼合樣品依ASTM D-1876進行接著強度測試。The bonded samples of the above Examples 1 to 12 and Comparative Examples 1 to 4 were subjected to the adhesion strength test in accordance with ASTM D-1876.
橡膠貼合EVA：接著強度7 kg/in以上表示合格。Rubber-bonded EVA: The strength is 7 kg/in or more.
橡膠貼合Nylon：接著強度9 kg/in以上表示合格。Rubber-bonded Nylon: The subsequent strength of 9 kg/in or more indicates pass.
2.界面相容性測試2. Interface compatibility test
以目視觀察實施例1至12及比較例1至4的貼合樣品經上述接著強度測試後破壞面的位置，破壞面若是位於第一黏著層與第二黏著層相接觸的表面，界面相容性測試結果表示為×。破壞面若是位於橡膠、EVA(或Nylon)的表面，或第一黏著層與EVA(或Nylon)貼合的表面，或第二黏著層與橡膠貼合的表面，則界面相容性測試結果表示○。The position of the fracture surface of the bonded samples of Examples 1 to 12 and Comparative Examples 1 to 4 after the above-mentioned adhesion strength test was visually observed, and the fracture surface was located on the surface where the first adhesive layer and the second adhesive layer were in contact with each other, and the interface was compatible. The result of the sex test is expressed as ×. If the damage surface is on the surface of rubber, EVA (or Nylon), or the surface of the first adhesive layer that is bonded to EVA (or Nylon), or the surface of the second adhesive layer that is bonded to the rubber, the interface compatibility test results indicate ○.
3.水洗測試3. Wash test
將實施例1至12及比較例1至4的貼合樣品(橡膠貼合EVA)以Electrolux的Wascator水洗機，在水溫50℃的條件下，水洗8小時，水洗後待貼合樣品於25℃乾 燥16小時後，依ASTM D-1876進行接著強度測試。經水洗後，橡膠貼合EVA：接著強度5.2 kg/in以上表示合格。The bonded samples (rubber-bonded EVA) of Examples 1 to 12 and Comparative Examples 1 to 4 were washed with an Electrolux Wascator water washing machine at a water temperature of 50 ° C for 8 hours, and after washing with water, a sample to be laminated was set at 25 °C dry After 16 hours of drying, the strength test was performed in accordance with ASTM D-1876. After washing with water, the rubber was bonded to EVA: the strength was then 5.2 kg/in or more.
4.耐熱測試4. Heat resistance test
耐熱測試：將實施例1至12及比較例1至4的貼合樣品(橡膠貼合EVA，尺寸為2.54 cm x 10 cm)置於恆溫測試儀(廠商型號：成嘉儀器CJ-6012，測試條件：溫度70℃，荷重1 kg)中5小時，觀察5小時後貼合樣品的情況。橡膠與EVA間的裂口為0公分至1.5公分，則耐熱測試結果表示○。橡膠與EVA完全分離，則耐熱測試結果表示×。Heat resistance test: The bonded samples of Examples 1 to 12 and Comparative Examples 1 to 4 (rubber-bonded EVA, size 2.54 cm x 10 cm) were placed in a thermostatic tester (manufacturer model: Chengjia Instrument CJ-6012, tested) Conditions: temperature: 70 ° C, load 1 kg) for 5 hours, observe the sample after 5 hours. The crack between the rubber and the EVA is 0 cm to 1.5 cm, and the heat resistance test result indicates ○. The rubber is completely separated from the EVA, and the heat resistance test result indicates ×.
表1及表2的結果所示，比較例1至4的黏合件因聚胺酯組成物及橡膠組成物中未同時使用界面相容劑，使得第一黏著層與第二黏著層間發生界面分離的現象，及貼合樣品的接著強度表現較不佳。The results of Tables 1 and 2 show that the adhesive members of Comparative Examples 1 to 4 have an interface separation between the first adhesive layer and the second adhesive layer due to the absence of the use of the interface compatibilizing agent in the polyurethane composition and the rubber composition. And the adhesion strength of the bonded samples is less than good.
反觀實施例1至12的黏合件因使用界面相容劑，所以第一黏著層與第二黏著層間並沒有發生界面分離的現象，及貼合樣品的接著強度具有較優異的表現。In contrast, in the adhesive members of Examples 1 to 12, since the interface compatibilizing agent was used, the interface between the first adhesive layer and the second adhesive layer did not occur, and the adhesive strength of the bonded sample was excellent.
除此之外，實施例1、實施例3至5及實施例7至12的黏合件因使用起始劑，使得貼合樣品具有很好的耐熱性，及在水洗後仍能維持良好的接著強度。In addition, the adhesives of Example 1, Examples 3 to 5 and Examples 7 to 12 have excellent heat resistance due to the use of the initiator, and can maintain good after washing. strength.
綜上所述，本發明黏合件因使用界面相容劑，使得第一黏著層與第二黏著層間具有很好的相容性，並能提昇未硫化橡膠與具有極性表面的異種材料貼合後的接著強度。本發明黏合法配合使用上述黏合件，不只使得未硫化的橡膠與具有極性表面的異種材料能良好地相黏合，更能縮短貼合的操作流程。In summary, the adhesive of the present invention has good compatibility between the first adhesive layer and the second adhesive layer due to the use of the interface compatibilizing agent, and can improve the bonding of the unvulcanized rubber to the dissimilar material having the polar surface. Then the intensity. The adhesive method of the present invention, in combination with the above-mentioned adhesive member, not only allows the unvulcanized rubber to adhere well to the dissimilar material having a polar surface, but also shortens the laminating operation process.
惟以上所述者，僅為本發明之較佳實施例而已，當不能以此限定本發明實施之範圍，即大凡依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。The above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and patent specification content of the present invention, All remain within the scope of the invention patent.
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