TW201922988A - 膠帶之電漿邊緣密封 - Google Patents
膠帶之電漿邊緣密封 Download PDFInfo
- Publication number
- TW201922988A TW201922988A TW107135042A TW107135042A TW201922988A TW 201922988 A TW201922988 A TW 201922988A TW 107135042 A TW107135042 A TW 107135042A TW 107135042 A TW107135042 A TW 107135042A TW 201922988 A TW201922988 A TW 201922988A
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- TW
- Taiwan
- Prior art keywords
- derivatives
- methacrylate
- ether
- tape
- acrylate
- Prior art date
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- 239000002390 adhesive tape Substances 0.000 title claims abstract description 21
- 238000005538 encapsulation Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 17
- 238000002161 passivation Methods 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims description 73
- 239000010410 layer Substances 0.000 claims description 65
- -1 3-ethyl-3-oxetanol methanol Chemical compound 0.000 claims description 42
- 239000000178 monomer Substances 0.000 claims description 42
- 229920000058 polyacrylate Polymers 0.000 claims description 40
- 239000002243 precursor Substances 0.000 claims description 37
- 239000012790 adhesive layer Substances 0.000 claims description 34
- 239000006260 foam Substances 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 28
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 27
- 229920005989 resin Polymers 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 239000004593 Epoxy Substances 0.000 claims description 18
- 125000003700 epoxy group Chemical group 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 13
- 125000000524 functional group Chemical group 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 12
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 11
- 229920003986 novolac Polymers 0.000 claims description 11
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 229920001971 elastomer Polymers 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 239000000806 elastomer Substances 0.000 claims description 9
- 150000004702 methyl esters Chemical class 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 claims description 6
- 229930003836 cresol Natural products 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 4
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical class C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000005062 Polybutadiene Substances 0.000 claims description 4
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 4
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920002857 polybutadiene Polymers 0.000 claims description 4
- 229920001195 polyisoprene Polymers 0.000 claims description 4
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- VLKXLWGYPOUERV-UHFFFAOYSA-N 2-[3-(oxiran-2-ylmethoxy)propoxymethyl]oxirane Chemical compound C1OC1COCCCOCC1CO1 VLKXLWGYPOUERV-UHFFFAOYSA-N 0.000 claims description 3
- ULYIFEQRRINMJQ-UHFFFAOYSA-N 3-methylbutyl 2-methylprop-2-enoate Chemical compound CC(C)CCOC(=O)C(C)=C ULYIFEQRRINMJQ-UHFFFAOYSA-N 0.000 claims description 3
- ZVYGIPWYVVJFRW-UHFFFAOYSA-N 3-methylbutyl prop-2-enoate Chemical compound CC(C)CCOC(=O)C=C ZVYGIPWYVVJFRW-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 229920002367 Polyisobutene Polymers 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 239000012080 ambient air Substances 0.000 claims description 3
- KIKYOFDZBWIHTF-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-3-ene-1,2-dicarboxylate Chemical compound C1CC=CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KIKYOFDZBWIHTF-UHFFFAOYSA-N 0.000 claims description 3
- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229920001083 polybutene Polymers 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- 125000003003 spiro group Chemical group 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- UNMJLQGKEDTEKJ-UHFFFAOYSA-N (3-ethyloxetan-3-yl)methanol Chemical compound CCC1(CO)COC1 UNMJLQGKEDTEKJ-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002619 bicyclic group Chemical group 0.000 claims description 2
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229940089951 perfluorooctyl triethoxysilane Drugs 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 claims description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims 2
- WPHGSKGZRAQSGP-UHFFFAOYSA-N norcarane Chemical compound C1CCCC2CC21 WPHGSKGZRAQSGP-UHFFFAOYSA-N 0.000 claims 2
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 claims 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 claims 1
- 230000001568 sexual effect Effects 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 23
- 239000000853 adhesive Substances 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 17
- 230000005012 migration Effects 0.000 abstract description 6
- 238000013508 migration Methods 0.000 abstract description 6
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
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- 239000004698 Polyethylene Substances 0.000 description 11
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- 150000002118 epoxides Chemical class 0.000 description 8
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 239000003570 air Substances 0.000 description 7
- 239000012159 carrier gas Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
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- 238000012545 processing Methods 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
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- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- 238000009835 boiling Methods 0.000 description 6
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- 239000004814 polyurethane Substances 0.000 description 6
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- 238000007789 sealing Methods 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 230000003712 anti-aging effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 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 5
- 238000003475 lamination Methods 0.000 description 5
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
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- 150000001298 alcohols Chemical class 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000002346 layers by function Substances 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 4
- 229960003493 octyltriethoxysilane Drugs 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
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- 150000003254 radicals Chemical class 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
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- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
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- 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 2
- RSSGMIIGVQRGDS-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-phenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=CC=C1 RSSGMIIGVQRGDS-UHFFFAOYSA-N 0.000 description 2
- 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 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 1
- QRWZCJXEAOZAAW-UHFFFAOYSA-N n,n,2-trimethylprop-2-enamide Chemical compound CN(C)C(=O)C(C)=C QRWZCJXEAOZAAW-UHFFFAOYSA-N 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
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- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
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- 239000000049 pigment Substances 0.000 description 1
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
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- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
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- 239000011593 sulfur Substances 0.000 description 1
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- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- BWSZXUOMATYHHI-UHFFFAOYSA-N tert-butyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(C)(C)C BWSZXUOMATYHHI-UHFFFAOYSA-N 0.000 description 1
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- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
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Abstract
本發明係關於一種減少濕氣侵入黏合處之方法,其中將一具有一黏著劑層(20)之膠帶黏貼在一基材表面上,並沿著該黏著劑層(20)的側面邊緣外面藉由一電漿流施加上一疏水性鈍化層。
Description
本發明係關於一種減少濕氣侵入黏合處之方法。本發明還關於一種具有一黏著劑層之膠帶,該黏著劑層具有一長度伸度與至少一沿著長度伸度延展的側面邊緣。
US 2016/0028041 A1中揭示一種具有一密封層之有機電子元件。該密封層包圍該有機電子元件例如OLED,其係完全施加在一基材表面上。為了密封有機電子元件,係在外面施加一包含矽成分之液體塗層;然後在塗層中植入電漿離子。如此形成的密封層具有極佳的氣體阻隔性質。此外,其對於可見光來說為透明的。藉由電漿使這些以液態施加的矽化合物反應並形成一固態薄膜。但該方法的缺點為必須先施加一液態層,其接下來在一第二程序步驟中被一電漿處理。其中層厚不利地無法精確控制,且該方法相對地昂貴。
本發明之課題為簡化開頭提過的減少濕氣侵入黏合處之方法。
於第二態樣中本發明之課題係提供開頭提過 的膠帶,其能簡單地製造且防止或至少減少濕氣侵入黏合處。
該課題係藉由具有請求項1之特徵的減少濕氣侵入黏合處之方法而解消。
1‧‧‧電漿噴嘴
2‧‧‧前驅物單元
3‧‧‧電漿單元
4‧‧‧前驅物
6‧‧‧載送氣體
7‧‧‧電漿
8‧‧‧噴頭
9‧‧‧入口
11‧‧‧製程氣體
12‧‧‧板子
13‧‧‧放電區
14‧‧‧電極端
16‧‧‧接地的不鏽鋼殼體
17‧‧‧側面入口
18‧‧‧蒸發器
19‧‧‧前驅物氣體
20‧‧‧黏著劑層
圖1顯示一使用的電漿噴嘴之主要結構。
圖2顯示一用於評估電漿邊緣密封的效果之條狀圖。
膠帶有各式各樣的實施形態。膠帶通常係以長膠帶的切段的形式來提供;膠帶能例如以卷的切片或切段的形式或是方便上以沖壓件的形式或是以捲筒上不斷的產品(阿基米德螺旋)的形式來提供。膠帶可以是簡單連續地形成,或者也可以在膠帶中設計孔洞或開口。藉此膠帶除了能完全覆蓋其外周所包圍的面以外,或是當其具有開口時,也能僅部分覆蓋其外周所包圍的面或是留空。膠帶係成形為在兩個維度上明顯大於第三個維度。明顯較大的維度係長度伸度與寬度伸度,第三個明顯較小的維度係膠帶的厚度或高度。但兩個第一維度也可以是形成為完全等大的,並藉此具有圓形、方形或其他類型的面。膠帶可以形成為單層或多層的,其通常具有約1μm至5mm的厚度。
於單層結構的情形膠帶較佳係由一黏著劑層所構成;於多層結構的情形膠帶也可包含一配備在載體 層中的載體材料。載體材料可在一側與另一側上配備一黏著劑層,或是也可以僅在一側上配備一黏著劑層。載體材料包含所有平面結構體,例如在二維上延伸的薄膜或薄膜切片、具延伸長度與有限寬度的帶子、帶子切段、沖壓件(例如以(光)電子組件的邊緣或邊界的形狀)、多層組件等等。其中對於各種應用可將各式各樣的載體(例如薄膜、織物、非織物與紙張)與各種塑料組合。
作為膠帶的載體層之材料,較佳使用聚合物膜、薄膜複合材料、或配備了有機層及/或無機層之薄膜或薄膜複合材料。此種薄膜/薄膜複合材料可由所有常見使用於薄膜製造之塑料構成,舉例但不限於有: 聚乙烯、聚丙烯(特別是藉由單軸或雙軸拉伸產生的定向聚丙烯(OPP))、環烯烴共聚物(COC)、聚氯乙烯(PVC)、聚酯(特別是聚對苯二甲酸乙二酯(PET)與聚萘二甲酸乙二酯(PEN))、乙烯/乙烯醇(EVOH)、聚偏二氯乙烯(PVDC)、聚偏二氟乙烯(PVDF)、聚丙烯腈(PAN)、聚碳酸酯(PC)、聚醯胺(PA)、聚醚碸(PES)或聚醯亞胺(PI)。
此外,載體層能與有機或無機的塗層或層組合。其能藉由一般方法產生,例如塗漆、印刷、蒸鍍、濺鍍、共擠或積層。這裡舉例但不限於如有:矽的氧化物或氮化物及鋁的氧化物或氮化物、氧化銦錫(ITO)或溶膠-凝膠塗層。
黏著劑層依據本發明也可為所有常見黏著劑層。
術語「黏合」通常敘述一種用於牢固接合基 材之製造方法。於黏合時,黏著劑藉由所謂附著力之物理交互作用(偶爾也會藉由化學交互作用)附著在基材上,並大多將它們永久結合。由於黏合一方面允許接合件之大面積的接合與由摩擦力產生的接合,另一方面基於其節省材料的性質,其係適合將幾乎所有材料彼此接合,黏合法被廣泛使用於家庭需求以及工業應用。其他結合方法,例如熔接或焊接還有螺栓固定,越來越常被黏合法取代。
較佳為使用壓敏黏著劑層來作為黏著劑層。壓敏黏著劑係指一種黏著劑,其在相對弱的接觸壓力下就已經能與黏附基底永久黏結,其具有大於1N/cm之黏著力,並在使用後能實質上無殘膠地自黏附基底再移除。壓敏黏著劑於室溫下發揮永久壓敏黏著性,也就是具有夠低的黏度與高接觸黏著性,使其在低接觸壓力下就已經潤濕任意黏著基底的表面。相關黏著劑的可黏性係基於其黏附性質,而可再拆性係基於其內聚性質。
壓敏黏著劑包含一基質與一可交聯組分,也稱為反應性樹脂。
作為用於壓敏黏著劑之基質可為各種材料,特別是非極性彈性體。
非極性彈性體(例如乙烯基芳烴嵌段共聚物)的特徵為其可溶於非極性溶劑中,也就是可溶於極性相當於乙酸乙酯或是更為非極性之溶劑及/或溶劑混合液中。其特別為具有小於6.1之介電常數的溶劑及/或溶劑混合液[2017年10月11日之http://en.wikipedia.org/ wiki/Solvent]及/或具有韓森參數(Hansen Parameter)δP極性5.3;δH氫鍵7.2的溶劑及/或溶劑混合液[Abbott,Steven and Hansen,Charles M.(2008)Hansen Solubility Parameters in Practice,ISBN 0-9551220-2-3或Hansen,Charles M.(2007)Hansen solubility parameters:a user's handbook CRC Press,ISBN 0-8493-7248-8]。
若使用嵌段共聚物作為彈性體,在此情形此嵌段共聚物包含至少一個具有大於40℃的軟化溫度之嵌段物種,例如乙烯基芳烴(還有部分氫化或完全氫化之變體)、甲基丙烯酸甲酯、甲基丙烯酸環己酯、甲基丙烯酸異莰酯與丙烯酸異莰酯。
更佳為嵌段共聚物包含一具有小於-20℃之軟化溫度的嵌段物種。
具有低軟化溫度之聚合物嵌段(「軟質嵌段」)的範例為聚醚(例如聚乙二醇、聚丙二醇、或聚四氫呋喃)、聚二烯(例如聚丁二烯或聚異戊二烯)、(部分)氫化的聚二烯(例如乙烯-丁烯共聚物、乙烯-丙烯共聚物或丁烯-丁二烯共聚物)、聚丁烯、聚異丁烯、聚烷基乙烯基醚、α,β-不飽和酯(特別是如丙烯酸酯)的聚合物嵌段之共聚物。
其中軟質嵌段在一設計中係建構為非極性的,在此情形較佳包含丁烯或異丁烯或氫化聚二烯作為均聚物嵌段或共聚物嵌段,在後者的情形較佳係與自身共聚或是與彼此共聚或是與其他特佳為非極性的共聚單體共聚。作為非極性的共聚單體舉例來說(部分)氫化聚 丁二烯、(部分)氫化聚異戊二烯及/或聚烯烴為適合的。
可交聯的組分(也稱為反應性樹脂)係由一環醚組成,適用於輻射化學交聯及視需要的熱交聯,具有低於40℃,較佳為低於20℃之軟化溫度。
基於環醚之反應性樹脂特別為環氧化物,也就是帶有至少一個環氧乙烷基之化合物或1,3-環氧丙烷。其可為芳香族或特別為脂肪族或環脂族性質。
可使用的反應性樹脂可為單官能、雙官能、三官能、四官能或更高官能乃至多官能的,其中官能度係參照環醚基。
例如但無意限於:3,4-環氧環己甲酸-3‘,4‘-環氧環己基甲酯(EEC)及衍生物、二氧化雙環戊二烯及衍生物、3-乙基-3-氧雜環丁烷甲醇及衍生物、四氫酞酸二環氧丙酯及衍生物、六氫酞酸二環氧丙酯及衍生物、1,2-乙二醇二環氧丙基醚及衍生物、1,3-丙二醇二環氧丙基醚及衍生物、1,4-丁二醇二環氧丙基醚及衍生物、更高級的1,n-烷二醇二環氧丙基醚及衍生物、己二酸雙[(3,4-環氧環己基)甲酯]及衍生物、二氧化乙烯基環己烯及衍生物、1,4-環己二甲醇雙(3,4-環氧環己甲酸酯)及衍生物、4,5-環氧四氫酞酸二環氧丙酯及衍生物、雙[1-乙基(3-氧雜環丁基)甲基)醚及衍生物、新戊四醇四環氧丙基醚及衍生物、雙酚A二環氧丙基醚(DGEBA)、氫化雙酚A二環氧丙基醚、雙酚F二環氧丙基醚、氫化雙酚F二環氧丙基醚、環氧苯酚酚醛樹脂、氫化環氧苯酚酚醛樹脂、環氧甲酚酚醛樹脂、氫化環氧甲酚酚醛樹脂、2-(7- 氧雙環)螺[1,3-二噁烷-5,3'-[7]-氧雙環[4.1.0]-庚烷]、1,4-雙((2,3-環氧丙氧基)甲基)環己烷。
反應性樹脂能以其單體形態、或是二聚物、三聚物等等乃至其寡聚物形態來使用。
反應性樹脂彼此的混合物,或是與其他共反應的化合物如醇類(單官能或多官能)或是乙烯基醚(單官能或多官能)之混合物也是可能的。
特佳為膠帶係出自tesa公司的ACXplus系列之膠帶卷。
此種膠帶有利地包含一載體層,其也被稱為硬質相。硬質相的聚合物基質較佳係自包含下列之群組中所選出:聚氯乙烯(PVC)、聚對苯二甲酸乙二酯(PET)、聚胺甲酸酯、聚烯烴、聚對苯二甲酸丁二酯(PBT)、聚碳酸酯、聚甲基丙烯酸甲酯(PMMA)、聚乙烯醇縮丁醛(PVB)、與由兩種以上前列聚合物所構成的離子聚合物與混合物。特佳為硬質相的聚合物基質係自包含下列的群組中所選出:聚氯乙烯、聚對苯二甲酸乙二酯、聚胺甲酸酯、聚烯烴、與由兩種以上前列聚合物所構成的混合物。硬質相實質上為一聚合物膜,其聚合物基質係自上述材料所選出。「聚合物膜」係理解為一種薄的、平面的、可撓的、可捲繞的帶材,其材料基質實質上係由一種以上的聚合物所形成。
「聚胺甲酸酯」係理解為一種廣義的聚合物質,其中重複單元係藉由胺甲酸酯基-NH-CO-O-彼此連結。
「聚烯烴」係理解為一種聚合物,其基於物質總量包含至少50%之通式-[-CH2-CR1R2-]n-的重複單元,其中R1係表示氫原子,而R2係表示氫原子或線形或分枝的飽和脂肪基或脂環基。若硬質相的聚合物基質中包含聚烯烴,則其特佳為聚乙烯,特別是具有超高分子量之聚乙烯(UHMWPE)。
「聚合物基質」係理解為一種聚合物或多種聚合物,其在相關層或相中所包含的所有聚合物中佔最大的重量比。
硬質相的厚度特別為150μm。硬質相的厚度較佳為10至150μm,特佳為30至120μm,特別是50至100μm,例如70至85μm。「厚度」係理解為相關層或相沿著想像的座標系統中的z軸之伸度,於該座標系統係由機械方向及相對於機械方向之橫向延展開的平面形成x-y平面。厚度係藉由測量相關層或相的至少5處不同位置,然後由所得到之測量結果計算算數平均來獲得。其中,硬質相之厚度測量係依據DIN EN ISO 4593進行。
此種膠帶能進一步具有一黏著劑層或軟質相,其包含一聚合物發泡體、一黏彈性體及/或一彈性體。軟質相的聚合物基質較佳係選自:聚烯烴、聚丙烯酸酯、聚胺甲酸酯及兩種以上前列聚合物之混合物。
於最簡單的變體中,膠帶僅包含一軟質相。
「聚合物發泡體」係理解為由填充了氣體的球狀或多面體狀單元所構成之成形體,其係被液態、半 液態、高黏度或固態之單元壁所限制住;此外,單元壁之主要組成成分係一種聚合物或多種聚合物之混合物。
「黏彈性體」係理解為一種材料,其除了純粹的彈性特徵(在受到外來機械性影響後,回復為初始狀態)以外,還顯示出黏性液體特徵,例如變形時出現的內部摩擦力。基於聚合物基質之壓敏黏著劑特別被視為黏彈性體。
「彈性體」係理解為一種材料,其具有橡膠彈性行為,並在20℃能被重複拉伸到其長度的至少2倍,及並在拉伸所需的強制力消失後,立即再次回到其大概的初始尺寸。
關於術語「聚合物基質」、「聚胺甲酸酯」及「聚烯烴」之意涵係適用於上述說明。「聚丙烯酸酯」係理解為一種聚合物,其單體基質基於物質總量有至少50%係由丙烯酸、甲基丙烯酸、丙烯酸酯及/或甲基丙烯酸酯構成,其中通常至少包含部分的丙烯酸酯及/或甲基丙烯酸酯,較佳為包含至少50%。「聚丙烯酸酯」特別被理解為一種聚合產物,其係藉由丙烯酸單體及/或甲基丙烯酸單體以及視需要的其他可共聚的單體之自由基聚合而得。
特佳為軟質相的聚合物基質係選自:聚烯烴、聚丙烯酸酯及兩種以上前列聚合物之混合物。若軟質相的聚合物基質中含有聚烯烴,則其較佳係選自:聚乙烯、乙烯-乙酸乙烯酯共聚物(EVA)、及由聚乙烯與乙烯-乙酸乙烯酯共聚物所形成的混合物(PE/EVA摻合 物)。其中聚乙烯可以是各種聚乙烯類型,例如:HDPE、LDPE、LLDPE、這些聚乙烯類型的摻合物及/或其混合物。
於一實施形態中,軟質相係包含一發泡體及分別設置在該發泡層的上面及下面之壓敏黏著層,其中發泡體的聚合物基質係包含一種以上聚烯烴,而壓敏黏著層的聚合物基質係包含一種以上聚丙烯酸酯。其中發泡體的聚合物基質特佳包含一種以上聚乙烯、乙烯-乙酸乙烯酯共聚物、及由一種以上聚乙烯及/或乙烯-乙酸乙烯酯共聚物所構成之混合物。發泡體的聚合物基質更特佳係包含一種以上聚乙烯。
聚烯烴系發泡體本身沒有或只有極些微的壓敏黏著性。因此,與硬質相或基材的接合較佳係藉由壓敏黏著層達成。發泡體的聚烯烴系起始材料之發泡較佳係藉由添加的推進氣體以物理概念發泡及/或藉由化學發泡劑(例如藉由偶氮二甲醯胺)產生。
於另一實施形態中,軟質相係一壓敏黏著性聚合物發泡體,其聚合物基質包含一種以上聚丙烯酸酯。「壓敏黏著性發泡體」意指發泡體本身為壓敏黏著劑,因此不需要施用額外的壓敏黏著層。這是較佳的,因為製程中必需合併的層較少,且降低剝離現象及其它在層邊界不期望的現象之風險。
「壓敏黏著劑」被理解為一種材料,其固化薄膜於室溫在乾燥狀態下具永久黏性且保有黏著能力,其中係藉由輕微的按壓力立即在各種不同基材上產生黏合。
聚丙烯酸酯較佳係藉由至少部分共聚合能與環氧基交聯之功能性單體而得。在此情形特佳為具酸基(特別是羧酸基、磺酸基或磷酸基)及/或羥基及/或酸酐基及/或環氧基及/或胺基之單體;特佳為含羧酸基之單體。當聚丙烯酸酯具有共聚的丙烯酸及/或甲基丙烯酸時為更佳的。這些基全都有與環氧基交聯的能力,藉此聚丙烯酸酯能較佳地與加入的環氧化物進行熱交聯。
能作為共聚單體用於聚丙烯酸酯之其它單體,除了具有至多30個C原子之丙烯酸酯及/或甲基丙烯酸酯以外,例如有:包含至多20個C原子之羧酸的乙烯酯、具有至多20個C原子之乙烯基芳烴、乙烯不飽和腈類、乙烯鹵化物、包含1至10個C原子之醇類的乙烯基醚、具2至8個C原子與1或2個雙鍵之脂族烴類、或這些單體之混合物。
相關的聚丙烯酸酯之性質,可特別透過藉由各單體不同的重量比來改變聚合物的玻璃轉移溫度來影響。聚丙烯酸酯較佳可產自以下單體組成成分:a)下式之丙烯酸酯及/或甲基丙烯酸酯CH2=C(RI)(COORII)
其中RI=H或CH3,而RII為具4至14個C原子之烷基殘基,b)具有已定義為與環氧基具反應性之類別的官能基之烯烴不飽和單體,c)任選的其它丙烯酸酯及/或甲基丙烯酸酯及/或烯烴不飽和單體,其能與組分(a)共聚合。
較佳為聚丙烯酸酯係基於一種單體組成物,其中包含比例為45至99重量%之組分(a)的單體、比例為1至15重量%之組分(b)的單體、及比例為0至40重量%之組分(c)的單體(數據係基於用於「基礎聚合物」(也就是沒有對完成的聚合物添加任何添加劑(如樹脂等))之單體混合物)。在此情形,聚合產物具有15℃(於低頻下的DMA)之玻璃轉移溫度與壓敏黏著性質。
組分(a)之單體特別為軟化及/或非極性的單體。較佳為作為單體(a)係使用具有包含4至14個C原子,特佳為4至9個C原子之烷基的丙烯酸酯與甲基丙烯酸酯。此種單體的範例為:丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸正戊酯、甲基丙烯酸正戊酯、丙烯酸正戊酯、丙烯酸正己酯、甲基丙烯酸正己酯、丙烯酸正庚酯、丙烯酸正辛酯、甲基丙烯酸正辛酯、丙烯酸正壬酯、丙烯酸異丁酯、丙烯酸異辛酯、甲基丙烯酸異辛酯,及其分支異構物,例如:丙烯酸2-乙基己酯或甲基丙烯酸2-乙基己酯。
組分(b)之單體特別為具有官能基,特別是具有能與環氧基進行反應之官能基之烯烴不飽和單體。
較佳為對於組分(b)使用具有自包含下列之群組中所選出的官能基之單體:羥基、羧基、磺酸基或亞磷酸基、酸酐、環氧基、胺基。
組分(b)之單體的特佳範例為:丙烯酸、甲基丙烯酸、伊康酸、順丁烯二酸、反丁烯二酸、巴豆酸、烏頭酸、二甲基丙烯酸、β-丙烯醯氧基丙酸、三氯丙烯 酸、3-丁烯酸、乙烯膦酸、伊康酸、順丁烯二酸酐、丙烯酸羥乙酯、丙烯酸羥丙酯、甲基丙烯酸羥乙酯、甲基丙烯酸羥丙酯、甲基丙烯酸6-羥己酯、烯丙醇、丙烯酸環氧丙酯、甲基丙烯酸環氧丙酯。
原則上作為組分(c)可使用所有能與組分(a)及/或組分(b)共聚合的乙烯官能化之化合物。組分(c)之單體能提供用來調整產生的壓敏黏著劑之性質。
組分(c)的範例單體為:丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸苄酯、甲基丙烯酸苄酯、丙烯酸二級丁酯、丙烯酸三級丁酯、丙烯酸苯酯、甲基丙烯酸苯酯、丙烯酸異莰酯、甲基丙烯酸異莰酯、丙烯酸三級丁基苯酯、甲基丙烯酸三級丁基苯酯、甲基丙烯酸十二酯、丙烯酸異癸酯、丙烯酸月桂酯、丙烯酸正十一酯、丙烯酸硬脂酯、丙烯酸十三酯、丙烯酸二十二酯、甲基丙烯酸環己酯、甲基丙烯酸環戊酯、丙烯酸苯氧基乙酯、甲基丙烯酸苯氧基乙酯、甲基丙烯酸2-丁氧基乙酯、丙烯酸2-丁氧基乙酯、丙烯酸3,3,5-三甲基環己酯、丙烯酸3,5-二甲基金剛烷酯、甲基丙烯酸4-異丙苯基苯酯、丙烯酸氰乙酯、甲基丙烯酸氰乙酯、丙烯酸4-聯苯酯、甲基丙烯酸4-聯苯酯、丙烯酸2-萘酯、甲基丙烯酸2-萘酯、丙烯酸四氫呋喃甲酯、丙烯酸二乙胺基乙酯、甲基丙烯酸二乙胺基乙酯、丙烯酸二甲胺基乙酯、甲基丙烯酸二甲胺基乙酯、丙烯酸2-丁氧基乙酯、甲基丙烯酸2-丁氧基乙酯、3-甲氧基丙烯酸甲酯、丙烯 酸3-甲氧基丁酯、丙烯酸苯氧基乙酯、甲基丙烯酸苯氧基乙酯、甲基丙烯酸2-苯氧基乙酯、二乙二醇單丁醚甲基丙烯酸酯、乙二醇丙烯酸酯、乙二醇單甲醚丙烯酸酯、聚乙二醇單甲醚甲基丙烯酸酯350、聚乙二醇單甲醚甲基丙烯酸酯500、丙二醇單甲基丙烯酸酯、二乙二醇單丁醚甲基丙烯酸酯、三伸乙二醇單乙醚甲基丙烯酸酯、丙烯酸八氟戊酯、甲基丙烯酸八氟戊酯、甲基丙烯酸2,2,2-三氟乙酯、丙烯酸1,1,1,3,3,3-六氟異丙酯、甲基丙烯酸1,1,1,3,3,3-六氟異丙酯、甲基丙烯酸2,2,3,3,3-五氟丙酯、甲基丙烯酸2,2,3,4,4,4-六氟丁酯、丙烯酸2,2,3,3,4,4,4-七氟丁酯、甲基丙烯酸2,2,3,3,4,4,4-七氟丁酯、甲基丙烯酸2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-十五氟辛酯、二甲胺丙基丙烯醯胺、二甲胺丙基甲基丙烯醯胺、N-(1-甲基十一基)丙烯醯胺、N-(正丁氧基甲基)丙烯醯胺、N-(丁氧基甲基)甲基丙烯醯胺、N-(乙氧基甲基)丙烯醯胺、N-(正十八基)丙烯醯胺,此外還有N,N-二烷基取代的胺,例如N,N-二甲基丙烯醯胺、N,N-二甲基甲基丙烯醯胺;N-苯甲基丙烯醯胺、N-異丙基丙烯醯胺、N-三級丁基丙烯醯胺、N-三級辛基丙烯醯胺、N-羥甲基丙烯醯胺、N-羥甲基甲基丙烯醯胺、丙烯腈、甲基丙烯腈;乙烯基醚,如乙烯基甲基醚、乙基乙烯基醚、乙烯基異丁基醚;乙烯基酯,如乙酸乙烯酯;氯乙烯、乙烯基鹵化物、1,1-二氯乙烯、亞乙烯鹵化物、乙烯基吡啶、4-乙烯基吡啶、N-乙烯基酞醯亞胺、N-乙烯內醯胺、N-乙烯吡咯啶酮、苯乙烯、α-與p-甲基苯乙烯、α-丁基苯乙 烯、4-正丁基苯乙烯、4-正癸基苯乙烯、3,4-二甲氧基苯乙烯。巨單體,如聚2-甲基丙烯酸苯乙烯酯(分子量Mw為4000至13000g/mol)、聚(甲基丙烯酸甲酯)甲基丙烯酸乙酯(Mw為2000至8000g/mol)。
組分(c)之單體較佳能選擇包含支持接下去的輻射化學交聯(例如藉由電子束、UV)之官能基的單體。合適的可共聚之光起始劑為例如丙烯酸安息香酯與丙烯酸酯官能化之二苯基酮衍生物。支持藉由照射電子束交聯之單體為例如丙烯酸四氫呋喃甲酯、N-三級丁基丙烯醯胺與丙烯酸烯丙酯。
聚丙烯酸酯(「聚丙烯酸酯」於本發明中理解為與「聚(甲基)丙烯酸酯」同義)之製造可依照熟習本技藝者所熟知的方法進行,特佳係藉由傳統的自由基聚合或受控自由基聚合。聚丙烯酸酯可藉由單體組分的共聚合,使用一般的聚合起始劑以及視需要的調節劑來製造,其中係在一般溫度下於本體中、於乳液(例如在水或液態烴)中、或於溶液中聚合。
較佳為聚丙烯酸酯係藉由使用一般量(基於單體的總重量,通常為0.01至5重量%,特別是0.1至2重量%)的聚合起始劑於溶劑中(特別是於沸點範圍在50至150℃,較佳為60至120℃之溶劑中)聚合單體來製造。
原則上熟習本技藝者所熟知的所有常見起始劑都適合。自由基源的範例有:過氧化物、氫過氧化物與偶氮化合物,例如過氧化二苯甲醯基、氫過氧化異丙 苯、過氧化環己酮、過氧化二(三級丁基)、乙醯環己過磺酸、過氧二碳酸二異丙酯、過辛酸三級丁酯與四苯-1,2-乙二醇。於一特佳方法中,作為自由基起始劑係使用:2,2’-偶氮雙(2-甲基丁腈)(DuPont公司的Vazo® 67TM)或2,2’-偶氮雙(2-甲基丙腈)(2,2’-偶氮雙異丁腈;AIBN;Dupont公司的Vazo® 64TM)。
作為用於聚丙烯酸酯之製造的溶劑可為:醇類,如甲醇、乙醇、正丙醇與異丙醇、正丁醇與異丁醇,較佳為異丙醇及/或異丁醇;以及烴類,如甲苯與特別是沸點範圍60至120℃之石油醚。此外,可使用酮類,如較佳為丙酮、甲乙酮、甲基異丁基酮;酯類,如乙酸乙酯,以及上述類別的溶劑的混合液,其中基於所使用的溶劑混合液,特別包含量在2至15重量%,較佳為3至10重量%之異丙醇的混合液為較佳的。
較佳為在聚丙烯酸酯之製造(聚合)後進行濃縮,且聚丙烯酸酯之進一步加工係實質上無溶劑地進行。聚合產物之濃縮可在沒有交聯劑物質與加速劑物質下完成。但也可以是這些化合物類別在濃縮前就已經加入聚合產物中,然後在這些物質存在下進行濃縮。
聚合產物能在濃縮步驟後轉送至一混練機中。視需要也可在相同的反應器中進行濃縮與混練。
聚丙烯酸酯的重量平均分子量Mw較佳在20,000至2,000,000g/mol之範圍;特佳在100,000至1,000,000g/mol之範圍,最佳在150,000至500,000g/mol之範圍(本說明中平均分子量Mw與聚合度分布性PD之 數據係參照用凝膠滲透層析之測定。作為沖提液係使用具0.1體積%的三氟乙酸之THF。測量係在25℃進行。作為保護管柱係使用PSS-SDV,5μm,103Å,ID 8.0mm x 50mm。分離係使用以下管柱:PSS-SDV,5μm,103Å、105Å與106Å,均具ID 8.0mm x 300mm。樣品濃度為4g/l,流量為每分鐘1.0ml。其係相對於PMMA標準品測量(μ=μm;1Å=10-10m)。為此,較佳可在適合的聚合調節劑,如硫醇、鹵素化合物及/或醇,的存在下進行聚合,以調整期望的平均分子量。
聚丙烯酸酯較佳具有30至90之K值,特佳為40至70,於甲苯中測量(1%溶液,21℃)。依據Fikentscher的K值為聚合產物之分子量與黏度之度量方法。
特別適合的聚丙烯酸酯係具有窄的分子量分布(聚合度分布性PD<4)。此種物質雖然在交聯後分子量相當低,但具有特佳的剪切強度。此外,較低的聚合度分布性能夠較容易地由熔體加工,因為相對於分布較廣的聚丙烯酸酯,在大體相同的應用性質下,流動黏度較低。分布窄的聚(甲基)丙烯酸酯能較佳地藉由陰離子聚合或藉由受控的自由基聚合方法來製造,其中以後者為特別適合的。此種依照RAFT法製造之聚丙烯酸酯的範例係敘述於US 6,765,078 B2與US 6,720,399 B2中。透過N-氧自由基(N-oxyl)也可製造相應的聚丙烯酸酯,例如在EP 1 311 555 B1中所述。在較佳方式中也能以原子轉移自由基聚合(ATRP)來合成分布窄的聚丙烯酸酯, 其中作為起始劑較佳使用單官能或雙官能的二級或三級之鹵化物與用於摘取鹵化物之Cu-、Ni-、Fe-、Pd-、Pt-、Ru-、Os-、Rh-、Co-、Ir-、Ag-或Au-錯合物。ATRP的不同可能性敘述於說明書US 5,945,491 A、US 5,854,364 A與US 5,789,487 A中。
用於製造聚丙烯酸酯之單體較佳部分包含適合與環氧基進行連接反應之官能基。這樣能夠藉由與環氧基反應較佳地熱交聯聚丙烯酸酯。連接反應係特別被理解為加成反應與取代反應。較佳為帶有官能基的單元與帶有環氧基的單元產生連結,特別是在帶有官能基的聚合物單元在交聯的意義上透過作為連結橋的帶有環氧基的交聯劑分子連結。其中含環氧基的物質較佳為多元環氧化物,也就是帶有至少兩個環氧基之環氧化物;相應地,整體上較佳產生帶有官能基的單元之間接連結。
聚丙烯酸酯較佳係藉由連結反應(特別是在加成或取代反應意義上的連結反應)由其所包含的官能基與熱交聯劑交聯。所有確保有足夠長的加工時間使其在加工過程不會發生凝膠化,且在比加工溫度(特別是室溫)還低的溫度下使聚合物快速後交聯至期望的交聯度之熱交聯劑都能使用。舉例來說可以是由包含羧基、胺基及/或羥基之聚合物與作為交聯劑之異氰酸酯(特別是EP 1 791 922 A1中所述的脂族異氰酸酯或以胺去活化的三聚異氰酸酯)所形成的組合。
合適的異氰酸酯特別為MDI[4,4-亞甲基二(苯基異氰酸酯)]、HDI[六亞甲基二異氰酸酯,1,6-伸己 基二異氰酸酯]及/或IPDI[異佛酮二異氰酸酯,5-異氰酸基-1-異氰酸基甲基-1,3,3-三甲基環己烷]之三聚衍生物,舉例來說有型號Desmodur® N3600與XP2410(均為BAYER AG:脂肪族聚異氰酸酯,低黏度HDI-三聚物)。同樣適合的有微粒化的三聚IPDI BUEJ 339®(現為HF9 ®(BAYER AG))之表面去活化的分散體。
基本上適用於交聯的還有其他異氰酸酯,如Desmodur VL 50(MDI系之聚異氰酸酯,Bayer AG)、Basonat F200WD(脂肪族聚異氰酸酯,BASF AG)、Basonat HW100(基於HDI系之能與水乳化之多元異氰酸酯,BASF AG)、Basonat HA 300(基於異氰脲酸酯之脲甲酸酯改性聚異氰酸酯,HDI系,BASF)或Bayhydur VPLS2150/1(親水改性IPDI,Bayer AG)。
基於待交聯之聚合物的總量,較佳係使用0.1至5重量%,特別是0.2至1重量%之熱交聯劑(例如三聚化的異氰酸酯)。
熱交聯劑較佳包含至少一種含環氧基之物質。其中含環氧基之物質特別為多元環氧化物,也就是帶有至少兩個環氧基之環氧化物;相應地,整體上產生帶有官能基的單元之間接連結。含環氧基之物質可為芳香族化合物或脂肪族化合物。
極合適的多元環氧化物有:表氯醇之寡聚物、多元醇(特別是乙二醇、丙二醇及丁二醇、聚乙二醇、二乙醇硫醚、丙三醇、新戊四醇、山梨醇、聚乙烯醇、聚烯丙醇等等)的環氧基醚;多元酚[特別是間苯二酚、 氫醌、雙(4-羥基苯基)甲烷、雙(4-羥基-3-甲基苯基)甲烷、雙(4-羥基-3,5-二溴苯基)甲烷、雙(4-羥基-3,5-二氟苯基)甲烷、1,1-雙(4-羥基苯基)乙烷、2,2-雙(4-羥基苯基)丙烷、2,2-雙(4-羥基-3-甲基苯基)丙烷、2,2-雙(4-羥基-3-氯苯基)丙烷、2,2-雙(4-羥基-3,5-二氯苯基)-丙烷、2,2-雙(4-羥基-3,5-二氯苯基)-丙烷、雙(4-羥基苯基)-苯基甲烷、雙(4-羥基苯基)-苯基甲烷、雙(4-羥基苯基)二苯基甲烷、雙(4-羥基苯基)-4'-甲基苯基甲烷、1,1-雙(4-羥基苯基)-2,2,2-三氯乙烷、雙(4-羥基苯基)-(4-氯苯基)甲烷、1,1-雙(4-羥基苯基)環己烷、雙(4-羥基苯基)環己基甲烷、4,4'-二羥基二苯基、2,2'-二羥基二苯基、4,4'-二羥基二苯基碸]的環氧基醚以及其羥乙基醚;酚-甲醛縮合產物,如酚醇與酚醛樹脂等等;含S與含N之環氧化物,例如N,N-二環氧丙基苯胺與N,N'-二甲基二環氧丙基-4,4-二胺基二苯基甲烷;以及以一般方法由多元不飽和羧酸或不飽和醇的單元不飽和羧酸酯所製成的環氧化物;環氧丙基酯;聚環氧丙基酯,其可藉由不飽和酸的環氧丙基酯之聚合或共聚合來得到,或可得自其它酸性化合物(例如三聚氰酸、二環氧丙基硫醚或環化三亞甲基三碸或是其衍生物等等)。
非常適合的醚類係例如:1,4-丁二醇二環氧丙基醚、聚丙二醇-3-環氧丙基醚、環己二甲醇二環氧丙基醚、丙三醇三環氧丙基醚、新戊二醇二環氧丙基醚、新戊四醇四環氧丙基醚、1,6-己二醇二環氧丙基醚、聚丙二醇二環氧丙基醚、三羥甲丙烷三環氧丙基醚、新戊 四醇四環氧丙基醚、雙酚A二環氧丙基醚及雙酚F二環氧丙基醚。
特佳為使用例如敘述於EP 1 978 069 A1中的交聯劑/加速劑系統(「交聯系統」),以在加工時間、交聯動力學以及交聯度上得到更好的控制。該交聯劑/加速劑系統包含至少一種含環氧基之物質作為交聯劑,與至少一種在低於用在交聯反應之待交聯的聚合物的熔化溫度下,藉由含環氧基的化合物發揮加速效果的物質作為加速劑。
作為加速劑特佳為使用胺類(形式上被理解為氨的取代產物;在下式中這些取代基係以「R」表示,特別包括:烷基殘基及/或芳基殘基及/或其他有機殘基),特佳為與待交聯之聚合物不會反應或只會些微反應之胺類。
原則上作為加速劑可選擇一級胺(NRH2)、二級胺(NR2H)以及三級胺(NR3),當然也包含具有多個一級胺基及/或二級胺基及/或三級胺基者。特佳的加速劑係三級胺,例如:三乙胺、三伸乙二胺、苄基二甲基胺、二甲胺基甲基酚、2,4,6-參(N,N-二甲胺基甲基)酚、N,N'-雙(3-(二甲胺基)丙基)脲。作為加速劑,較佳還可使用多元胺,如二胺、三胺及/或四胺。極適合的有例如:二伸乙三胺、三伸乙四胺、三甲基伸己二胺。
此外,作為加速劑較佳使用胺基醇。特佳為使用二級及/或三級的胺基醇,其中在每分子內有多個胺官能基之情形,較佳為至少一個,較佳為全部的胺官能 基為二級及/或三級的。作為較佳的胺基醇加速劑,可使用:三乙醇胺、N,N-雙(2-羥丙基)乙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、2-胺基環己醇、雙(2-羥環己基)甲胺、2-(二異丙胺基)乙醇、2-(二丁胺基)乙醇、N-丁基二乙醇胺、N-丁基乙醇胺、2-[雙(2-羥乙基)胺基]-2-(羥甲基)-1,3-丙二醇、1-[雙(2-羥乙基)胺基]-2-丙醇、三異丙醇胺、2-(二甲胺基)乙醇、2-(二乙胺基)乙醇、2-(2-二甲胺基乙氧基)乙醇、N,N,N'-三甲基-N'-羥乙基雙胺乙醚、N,N,N'-三甲基胺乙基乙醇胺及/或N,N,N'-三甲基胺丙基乙醇胺。
其他適合的加速劑有:吡啶、咪唑(例如2-甲基咪唑)、與1,8-二吖雙環[5.4.0]-十一-7-烯。也可使用環脂族多元胺作為加速劑。合適的還有基於磷酸鹽系之加速劑,如膦及/或鏻化合物,例如三苯膦或四苯硼酸四苯鏻。
此外,也可提供在頂部及/或底部塗布了壓敏黏著劑的,具有由聚丙烯酸酯形成之聚合物基質的,本身為壓敏黏著性之聚合物發泡體,其中此壓敏黏著劑的聚合物基質較佳也是由聚丙烯酸酯形成。或者可以將其它經過預處理之黏著層(也就是例如基於不同於聚(甲基)丙烯酸酯之其他聚合物的壓敏黏著層及/或可熱活化的層)積層於發泡層。適合的基礎聚合物為:天然橡膠、合成橡膠、丙烯酸酯嵌段共聚物、乙烯基芳烴嵌段共聚物(特別是苯乙烯嵌段共聚物)、EVA、聚烯烴、聚胺甲酸酯、聚乙烯醚及聚矽氧。這些層較佳不含大到可見之比例的 可遷移的組成成分,此可遷移的組成成分與發泡層的材料相容性極好,而會以顯著的量擴散在發泡層中,並因此改變性質。
膠帶的軟質相通常可包含至少一種增黏樹脂。作為增黏樹脂能使用特別是脂肪族、芳香族及/或烷基芳香族的烴樹脂、基於純單體之烴樹脂、氫化的烴樹脂、官能化的烴樹脂以及天然樹脂。較佳為增黏樹脂係自包含下列之群組中選出:蒎烯樹脂、茚樹脂及松香樹脂、其歧化、氫化、聚合化及/或酯化的衍生物與鹽、萜烯樹脂與萜烯酚醛樹脂以及C5-、C9-和其他烴樹脂。也可有利地使用這些樹脂與其他樹脂的組合,以按照期望調整產生的黏著劑之性質。特佳為增黏樹脂係自包含萜烯酚醛樹脂與松香酯之群組中所選出。
膠帶的軟質相可包含一種以上填料。填料可存在於軟質相的一或多層中。
較佳為軟質相包含一聚合物發泡體,而該聚合物發泡體包含部分膨脹或完全膨脹之微氣球,特別是當聚合物發泡體的聚合物基質包含一種以上聚丙烯酸酯時,更特佳為當聚合物發泡體的聚合物基質係由一種以上聚丙烯酸酯構成時。其中微氣球係彈性空心球,其具有一熱塑性的聚合物殼體;因此其也被稱為可膨脹的聚合物微球或被稱為微空心球。此球係填充了低沸點的液體或液化的氣體。作為殼體材料,特別使用聚丙烯腈、聚偏二氯乙烯(PVDC)、聚氯乙烯(PVC)、聚醯胺或聚丙烯酸酯。作為低沸點的液體特別以低級烷(例如異丁烷或 異戊烷)為適合的,其係在壓力下作為液化氣體封入聚合物殼體中。例如藉由對微氣球的物理作用,例如藉由熱作用,特別是藉由通過例如超音波或微波輻射產生之加熱或發熱,一方面軟化外部聚合物殼體,同時位於殼體內的液態推進氣體轉變為其氣體狀態。於一特定的壓力與溫度之配對(也稱為臨界配對)下微氣球不可逆地擴大並三維地膨脹。膨脹當內壓與外壓平衡時結束。由於聚合物殼體保持,如此得到閉孔的發泡體。
市面上可購得許多種微氣球類型,例如Akzo Nobel公司的Expancel DU型(dry unexpanded(乾燥未膨脹)),其在實質上於其大小(於未膨脹狀態下直徑6至45μm)與其膨脹所需的起始溫度(75℃至220℃)上不同。
此外,未膨脹的微氣球類型也可為具約40至45重量%之固體比例或微氣球比例的水性分散液,另外也可為結合聚合物之微氣球(母料),例如乙烯-乙酸乙烯酯中具有約65重量%之微氣球濃度。此外,可為所謂的微氣球漿液系統,其中微氣球以60至80重量%的固體比例作為水性分散液存在。微氣球分散液、微氣球漿液以及母料都與DU型一樣,適用於在膠帶的軟質相中所包含的聚合物發泡體之發泡。
特佳為聚合物發泡體包含的微氣球在未膨脹狀態下於25℃具有3μm至40μm之直徑,特別是5μm至20μm,及/或在膨脹後具有10μm至200μm之直徑,特別是15μm至90μm。
較佳為基於聚合物發泡體的總重量,聚合物 發泡體包含至多30重量%的微氣球,特別是在0.5重量%與10重量%之間。
膠帶(只要其包含聚合物發泡體)的軟質相之聚合物發泡體,較佳特徵為普遍沒有開孔的空腔。特佳為聚合物發泡體具有的沒有固有的聚合物殼體之空腔(也就是開孔的空穴)之比例係不大於2體積%,特別是不大於0.5體積%。因此聚合物發泡體較佳為閉孔的發泡體。
任選地,膠帶的軟質相,基於軟質相之總質量,還可包含高比例(即0.1至50重量%)之粉狀及/或丸粒狀的填料、染料及顏料,特別是研磨性及補強性填料,例如白堊(CaCO3)、二氧化鈦、氧化鋅及碳黑。
此外在軟質相中可包含:阻燃性填料例如多磷酸銨;導電填料例如導電碳黑、碳纖維及/或塗覆了銀的球;導熱性材料例如氮化硼、氧化鋁、碳化矽;鐵磁性添加劑例如氧化鐵(III);用於增加體積之其它添加劑,例如起泡劑、實心玻璃珠、空心玻璃球、碳化微珠、酚醛空心微球、由其他材料構成之微球;矽酸、矽酸鹽、有機再生原料例如木粉、有機及/或無機奈米粒子、纖維;抗老化劑、光穩定劑、抗臭氧劑及/或複合劑。作為抗老化劑較佳可使用一級抗老化劑(例如4-甲氧基酚或Irganox® 1076)與二級抗老化劑(例如BASF公司之Irgafos® TNPP或Irgafos® 168),視需要也能彼此組合使用。作為其它抗老化劑,在氧與氧氣本身存在下,能使用啡噻(碳自由基捕捉劑)以及氫醌甲基醚。
軟質相的厚度較佳為200至1800μm,特佳為300至1500μm,特別是400至1000μm。軟質相的厚度係依據ISO 1923測定。
將硬質相與軟質相或是還有提供於硬質相及/或軟質相中之層彼此結合成為膠帶,能例如藉由層壓、積層或共擠來進行。硬質相與軟質相可直接,也就是不中斷的彼此結合。在硬質相及軟質相之間也可配備一層以上增黏層。此外,膠帶可包含其它層。
較佳為至少一層要結合在一起之層,更佳為多層要結合在一起之層,更特佳為所有要結合在一起之層,係以電暈預處理法(以空氣或氮氣)、電漿預處理法(空氣、氮氣、或其它反應性氣體、或能以氣溶膠型態使用之反應性化合物)或火焰預處理法進行過預處理。
於背側(也就是在硬質相的背離基材側)上較佳施加上一功能層,其具有例如分離性質或UV穩定性質。此功能層較佳係由一薄膜或一清漆所構成,其中該薄膜的厚度係20μm,特佳係10μm,特別是8μm,例如5μm,而該清漆的厚度係10μm,特佳係6μm,特別是3μm,例如1.5μm。薄膜及清漆較佳都包含UV吸收劑,及/或薄膜或清漆的聚合物基質包含吸收UV的基及/或抗UV的基。
薄膜可藉由層壓、積層或共擠施加於硬質相的背側。薄膜較佳為金屬化薄膜。薄膜之聚合物基質較佳係從包含下列之群組中所選出:聚亞芳基、聚氯乙烯(PVC)、聚對苯二甲酸乙二酯(PET)、聚胺甲酸酯、聚烯 烴、聚對苯二甲酸丁二酯(PBT)、聚碳酸酯、聚甲基丙烯酸甲酯(PMMA)、聚乙烯醇縮丁醛(PVB)、及由兩種以上前列聚合物所構成之離子聚合物與混合物。「主要成分」此處係意指「基於薄膜的總重量,佔最高重量比之成分」。除了聚亞芳基以外,所有上列之薄膜材料較佳具有高含量的UV穩定劑。
於一特殊實施形態中,膠帶以朝向基材的順序包含一功能層(如前所述)、一硬質相與一軟質相,該軟質相包含一層壓敏黏著層、一聚合物發泡體(其包含由一種以上的聚烯烴所構成之聚合物基質)、與另一層壓敏黏著層。底部的壓敏黏著層能覆蓋離型裱紙,但該離型裱紙不算是膠帶。
於另一特殊實施形態中,膠帶以朝向基材的順序包含一功能層(如前所述)、一硬質相與一壓敏黏著性的軟質相,該軟質相的聚合物基質係包含一種以上聚丙烯酸酯。此實施形態中也能以一離型裱紙覆蓋軟質相的底側(也就是面對基材側),但該離型裱紙不算是膠帶。
較佳為膠帶係發泡的丙烯酸酯材料,特別是上述的類別,其可額外具有一(或多個)中間載體。
對於本發明之方法來說不可或缺的是在製造膠帶時或在膠帶黏貼於基材表面上後,藉由電漿流在膠帶的側面邊緣外施加上一疏水性鈍化層。較佳為使用大氣壓電漿法。
藉由以電漿流在黏著劑層的側面邊緣上施加上一疏水性鈍化層,防止了濕氣侵入黏合處之風險。通 常在兩基材表面(其被黏在一起)之間施加膠帶後只有圍繞膠帶側邊外是空著的,並暴露在因水與空氣濕氣造成之濕氣侵入的風險下。
該空著的側邊被配備一疏水性鈍化層。為此依據本發明使用電漿法。黏著劑層的側面邊緣之處理係在大氣壓下或是接近大氣壓下進行。
為了實施電漿法係使用具一電漿噴嘴之結構,該電漿噴嘴係被供給待離子化的製程氣體(較佳以環境空氣的形態)。此外,電漿噴嘴的出口被供給一前驅物。該前驅物較佳為矽烷或矽氧烷,其被蒸發並藉由載送氣體(例如氮氣或惰氣)引導至電漿流中。該前驅物更佳為胺丙基三乙氧基矽烷、全氟辛基三乙氧基矽烷或六甲基二矽氧烷。純氧化矽層在聚合時(也就是電漿流施加到基材表面上時)是不期望的。來自前驅物分子的未反應烴鏈的碳之比例(在六甲基二矽氧烷的情形也就是六甲基鏈)至高可為塗層的12%重量比。藉由此在氧化矽層中額外的重量比達成疏水效果。厭水層藉由水滴滴落讓膠帶側面與黏合處的邊界層無水。藉此液態媒體,也就是冷凝水,被從黏合處的影響區域帶開,而不會因水的極性在黏合處中發生水的遷移。
於一第二態樣中,本發明之課題係藉由具有請求項12之特徵的膠帶而得到滿足。
依據本發明之膠帶係具有一黏著劑層,該黏著劑層具有一長度伸度與至少一沿著該長度伸度延展之側面邊緣。沿著黏著劑層的側面邊緣施加有一疏水性鈍 化層。該疏水性鈍化層係依據上述方法之一施加。
於膠帶一較佳實施形式中,該疏水性鈍化層係以具有烴的重量比至高為12%之SiOx層形成。
疏水性鈍化層較佳係在大氣壓電漿法中以上述前驅物之一(特別是HMDSO)使用環境空氣作為製程氣體來製造。
更佳為黏著劑層具有至少兩個(較佳為正好兩個)配備了疏水性鈍化層之側面邊緣。較佳為黏著劑層係捲繞於捲筒上的膠帶的一層。
黏著劑層可包含至少一彈性體與一反應性樹脂。關於彈性體與反應性樹脂的結構請參考前面說明。黏著劑層還可包含一壓敏黏著性的軟質相。關於此軟質相也請參考前面說明。
以下參照兩個圖式中的實施例來說明本發明。其中:圖1顯示所使用的一電漿噴嘴之主要結構,圖2顯示一用於評估電漿邊緣密封的效果之條狀圖。
圖1顯示噴嘴1的主要視圖,其係Plasmatreat GmbH公司之OpenAir系統。
電漿噴嘴1包含一前驅物單元2(其示於圖1中左方)與一電漿單元3。該前驅物單元2產生一富含前驅物4之載送氣體6,同時電漿單元3產生一電漿7。前驅物4與電漿7被匯流至噴頭8。
此處電漿7被理解為一高能量的製程氣體 11,特別是一激發並離子化的空氣-氮氣混合物。為了產生電漿7,首先透過一入口9將製程氣體11送至電漿單元3,這裡製程氣體11為空氣或是氮氣或是它們產生的混合物。製程氣體11通過入口9被導引至電漿單元3,並穿過一個有開孔的板子12進入放電區13,製程氣體11流動遍布該處。於放電區13中製程氣體11經過一電極端14,於該電極端上連接著具數千伏特與約10kHz的頻率之高頻交流電。在電極端14與一相對電極(其可為例如接地的不銹鋼外殼16)之間形成一強烈的交流電場,其會導致所謂的電暈放電,它會將通過電漿單元3流過電極端14的加工氣體11離子化並轉化為電漿7的氣流。該電漿7被導引通過噴頭8,其上在側面入口17連接著前驅物單元2。
該噴頭8的側面入口17與前驅物單元2接合。該前驅物單元2包含一用於前驅物4之第一供給源與一用於載送氣體6之第二供給源。此處作為載送氣體6無論是空氣或是氮氣或是空氣與氮氣的混合物均可使用。該前驅物4被霧化並以小滴狀供應給載送氣體6,該混合物到達一蒸發器18,其中溫度係高於前驅物4的沸點。作為前驅物4可使用有機的、多官能的矽烷,例如辛基三乙氧基矽烷(OCS)、(3-環氧丙氧基丙基)三甲氧基矽烷(GLYMO)與六甲基二矽氧烷(HMDSO)。
此處所使用的前驅物4為六甲基二矽氧烷(HMDSO),其以10、20、40g/h乃至150g/h的數量被供應給載送氣體6。蒸發器18中的溫度為約120℃,也就 是高於HMDSO的沸點(其約在100℃)。
在蒸發器18中產生的前驅物氣體19被供應給噴頭8並在該處與電漿7混合。前驅物4如此與電漿7一起到達黏著劑層20的側面邊緣上。
電漿噴嘴1與黏著劑層20的側面邊緣呈垂直角度並通向噴頭8。
黏著劑層20的側面邊緣之處理係發生在大氣壓下或是接近大氣壓下,其中電漿噴嘴1的電氣放電區13中的壓力也可以更高。電漿7在此實施例中被理解為大氣壓電漿,其為電氣活化的均勻反應性氣體,其不處於熱平衡,在其作用範圍內具有接近環境壓力之壓力。通常該壓力高於環境壓力0.5bar。藉由在放電區13的電場中電氣放電或是離子化過程製程氣體11被活化,並在氣體組成成分中產生高激發態。然後前驅物4以氣體形態或是作為氣溶膠通過一導氣通道通過側面入口17在噴頭8中被供應給製程氣體11,該前驅物4在黏著劑層的側面邊緣之表面上形成實際的氧化矽層。
此處作為製程氣體11係使用環境空氣。
於一實施例中對於側面邊緣密封係使用具以下條件與參數之裝置:電漿噴嘴:Generator FG 5001,固定噴嘴216028WE(Plasmatreat公司)
前驅物:六甲基二矽氧烷(HMDSO),前驅物量:10~150g/小時
處理速度:40m/min
噴嘴間隔距離:15mm
PCT(脈衝週期(Pulse-Cycle-Time)):20%與100%
蒸發器溫度:120℃
基本上奈米塗層的側面邊緣會致使黏著劑中水的吸收減少,特別是ACXplus的載體單元。這特別係以主要產生具低有機比例的玻璃質沉積之參數設定達成。舉例來說可提出ACXplus 6812,其在例如濕熱85/85測試與100%相對濕度下的40℃之負載下顯示出明顯的改善。此外,前驅物為有趣的,其可帶來明顯的疏水性。黏著接合處一般於測試條件下係被一水層永久潤濕,因為黏著製品的成分具有充足的極性基團。這促使水分子遷移進黏著製品的體內以及促使濕氣移入界面層。黏著接合處的疏水性質造成水以滴液的形式「排出」並避免形成封閉的水膜。用發揮疏水作用的前驅物之初步結果能對耐濕熱性達成顯著提升,其比起未儲存的參考例顯示出更高的強度值。使用的前驅物為辛基三乙氧基矽烷(OCS)、(3-環氧丙氧基丙基)三甲氧基矽烷(GLYMO)與六甲基二矽氧烷(HMDSO)。透過修改電漿參數(功率、間隔距離、速度與脈衝週期)可影響施加的層之有機比例。在使黏著劑去活化時,參數選擇係有意地匹配前驅物的總反應率,以藉由電漿聚合替玻璃質的層去除主要有機的比例。此處追尋相反的目標以調高疏水性。此外提高前驅物的流率。
在例如HMDSO的情形,以大氣壓電漿塗層在基材上產生玻璃質層。但在此情形能以適合的參數管 理(脈衝寬度調變)來影響HMDSO的反應率。在此聚合中不預期有純的SiOx層。來自前驅物分子的未反應烴鏈(在HMDSO的情形為六甲基鏈)的碳之比例至高可為塗層的12%重量比。這產生疏水性。此厭水層藉由水滴滴落讓膠帶側面與黏合處的邊界層無水。最後液態媒體被從影響區域(於該處對黏附產生負面影響)帶開,而不會因極性在黏合處中發生遷移(參見具疏水性纖維素且未處理的薄膜)。
圖2顯示一用於評量電漿邊緣密封的效果之條狀圖。其顯示ACXplus 6812對聚丙烯(PP)於室溫(RT)下三天後(3d)及於40℃與100%相對濕度下3天後的黏著力。其中兩個左邊的條柱沒有作側面邊緣的鈍化,而右邊有作側面邊緣的鈍化。黏著力係以90°的剝離角度測定。藉由側面邊緣的鈍化顯示出黏著力之顯著上升。此效果在高濕度時特別強烈地顯示出來。
條狀圖中顯示的虛線代表黏合處在膠合體分層時的黏著力。超出虛線上的黏著力係歸因於不同的測量裝置、測量誤差等等。無論如何,條狀圖上明顯看出電漿邊緣密封導致黏著力顯著上升,特別是導致能夠更長期的儲放。
藉由邊緣密封,對具遷移能力的物質,特別是對氣體擴散的阻隔能力下降,如下表所示:
此處HMDSO處理為示範性代表含矽氧烷的前驅物之處理。處理係以上述電漿噴嘴:Plasmatreat公司的Generator FG 5001,固定噴嘴216028WE來進行。結果顯示,藉由電漿處理能大幅下降滲透率。
Claims (20)
- 一種減少濕氣侵入黏合處之方法,其中將具有黏著劑層(20)之膠帶黏貼在基材表面上,並沿著該黏著劑層(20)的側面邊緣外面藉由電漿流施加上疏水性鈍化層。
- 如請求項1之方法,其中係將前驅物(4)供應給電漿流,而使用矽烷及/或矽氧烷作為該前驅物(4)。
- 如請求項2之方法,其中係使用出自以下群組的前驅物(4):胺丙基三乙氧基矽烷、全氟辛基三乙氧基矽烷、HMDSO。
- 如請求項1至3中任一項之方法,其中係蒸發該前驅物(4),並藉由一惰氣輸送至電漿流中。
- 如上述請求項中任一項之方法,其中係激發製程氣體(11),且使用環境空氣作為該製程氣體(11)。
- 如上述請求項中任一項之方法,其中該黏著劑層(20)至少包含一彈性體與一反應性樹脂。
- 如上述請求項中任一項之方法,其中該彈性體係選自以下群組:乙烯基芳烴(還有部分氫化或完全氫化之變體)、甲基丙烯酸甲酯、甲基丙烯酸環己酯、甲基丙烯酸異莰酯與丙烯酸異莰酯;或是選自以下群組:聚醚,特別是聚乙二醇、聚丙二醇或聚四氫呋喃;或是選自以下群組:聚二烯,特別是聚丁二烯或聚異戊二烯,(部分)氫化的聚二烯,特別是乙烯-丁烯共聚物、乙烯-丙烯共聚物或丁烯-丁二烯共聚物,聚丁烯、聚異丁烯、聚烷基乙烯基醚、α,β-不飽和酯(特別是丙烯酸酯)的聚 合物嵌段之共聚物。
- 如上述請求項中任一項之方法,其中該反應樹脂係自包含下列之群組中選出:3,4-環氧環己甲酸-3’,4’-環氧環己基甲酯(EEC)及衍生物、二氧化雙環戊二烯及衍生物、3-乙基-3-氧雜環丁烷甲醇及衍生物、四氫酞酸二環氧丙酯及衍生物、六氫酞酸二環氧丙酯及衍生物、1,2-乙二醇二環氧丙基醚及衍生物、1,3-丙二醇二環氧丙基醚及衍生物、1,4-丁二醇二環氧丙基醚及衍生物、更高級的1,n-烷二醇二環氧丙基醚及衍生物、己二酸雙[(3,4-環氧環己基)甲酯]及衍生物、二氧化乙烯基環己烯及衍生物、1,4-環己二甲醇雙(3,4-環氧環己甲酸酯)及衍生物、4,5-環氧四氫酞酸二環氧丙酯及衍生物、雙[1-乙基(3-氧雜環丁基)甲基)醚及衍生物、新戊四醇四環氧丙基醚及衍生物、雙酚A二環氧丙基醚(DGEBA)、氫化雙酚A二環氧丙基醚、雙酚F二環氧丙基醚、氫化雙酚F二環氧丙基醚、環氧苯酚酚醛樹脂、氫化環氧苯酚酚醛樹脂、環氧甲酚酚醛樹脂、氫化環氧甲酚酚醛樹脂、2-(7-氧雙環)螺[1,3-二噁烷-5,3'-[7]-氧雙環[4.1.0]-庚烷]、1,4-雙((2,3-環氧丙氧基)甲基)環己烷。
- 如上述請求項中任一項之方法,其中係使用一壓敏黏著性的軟質相作為該黏著劑層(20)。
- 如上述請求項中任一項之方法,其中係使用壓敏黏著性的聚合物發泡體作為壓敏黏著性的軟質相,其包含一種以上聚丙烯酸酯。
- 如請求項10之方法,其中該聚丙烯酸酯包含:(a)下式之丙烯酸酯及/或甲基丙烯酸酯CH 2=C(R I)(COOR II)其中R I=H或CH 3,而R II為具4至14個C原子之烷基殘基,(b)具有已定義為與環氧基具反應性之類型的官能基之烯烴不飽和單體,(c)任選的其它丙烯酸酯及/或甲基丙烯酸酯及/或烯烴不飽和單體,其能與組分(a)共聚合。
- 一種具黏著劑層(20)之膠帶,該黏著劑層(20)具有長度伸度與至少一與至少一沿著該長度伸度延展之側面邊緣與沿著該黏著劑層(20)的側面邊緣施加上的疏水性鈍化層。
- 如請求項12之膠帶,其中該疏水性鈍化層係形成為具有烴的重量比至高為12%之SiO x層。
- 如請求項12或13之膠帶,其中該黏著劑層(20)具有兩個側面邊緣,它們兩個都配備有疏水性鈍化層。
- 如請求項12至14中任一項之膠帶,其中該黏著劑層(20)至少包含彈性體與反應性樹脂。
- 如請求項12至15中任一項之膠帶,其中該彈性體係來自以下群組:乙烯基芳烴(還有部分氫化或完全氫化之變體)、甲基丙烯酸甲酯、甲基丙烯酸環己酯、甲基丙烯酸異莰酯與丙烯酸異莰酯;或是來自以下群組:聚醚,特別是聚乙二醇、聚丙二醇或聚四氫呋喃;或是來自以下群組:聚二烯,特別是聚丁二烯或聚異戊 二烯,(部分)氫化的聚二烯,特別是乙烯-丁烯共聚物、乙烯-丙烯共聚物或丁烯-丁二烯共聚物,聚丁烯、聚異丁烯、聚烷基乙烯基醚、α,β-不飽和酯(特別是丙烯酸酯)的聚合物嵌段之共聚物。
- 如請求項12至16中任一項之膠帶,其中反應性樹脂來自以下群組:3,4-環氧環己甲酸-3’,4’-環氧環己基甲酯(EEC)及衍生物、二氧化雙環戊二烯及衍生物、3-乙基-3-氧雜環丁烷甲醇及衍生物、四氫酞酸二環氧丙酯及衍生物、六氫酞酸二環氧丙酯及衍生物、1,2-乙二醇二環氧丙基醚及衍生物、1,3-丙二醇二環氧丙基醚及衍生物、1,4-丁二醇二環氧丙基醚及衍生物、更高級的1,n-烷二醇二環氧丙基醚及衍生物、己二酸雙[(3,4-環氧環己基)甲酯]及衍生物、二氧化乙烯基環己烯及衍生物、1,4-環己二甲醇雙(3,4-環氧環己甲酸酯)及衍生物、4,5-環氧四氫酞酸二環氧丙酯及衍生物、雙[1-乙基(3-氧雜環丁基)甲基)醚及衍生物、新戊四醇四環氧丙基醚及衍生物、雙酚A二環氧丙基醚(DGEBA)、氫化雙酚A二環氧丙基醚、雙酚F二環氧丙基醚、氫化雙酚F二環氧丙基醚、環氧苯酚酚醛樹脂、氫化環氧苯酚酚醛樹脂、環氧甲酚酚醛樹脂、氫化環氧甲酚酚醛樹脂、2-(7-氧雙環)螺[1,3-二噁烷-5,3'-[7]-氧雙環[4.1.0]-庚烷]、1,4-雙((2,3-環氧丙氧基)甲基)環己烷。
- 如請求項12至17中任一項之膠帶,其中該黏著劑層(20)包含壓敏黏著性的軟質相。
- 如請求項12至18中任一項之膠帶,其中該壓敏黏著 性的軟質相包含壓敏黏著性的聚合物發泡體,其包含一種以上聚丙烯酸酯。
- 如請求項12至19中任一項之膠帶,其中該聚丙烯酸酯包含:(a)下式之丙烯酸酯及/或甲基丙烯酸酯CH 2=C(R I)(COOR II)其中R I=H或CH 3,而R II為具4至14個C原子之烷基殘基,(b)具有已定義為與環氧基具反應性之類型的官能基之烯烴不飽和單體,(c)任選的其它丙烯酸酯及/或甲基丙烯酸酯及/或烯烴不飽和單體,其能與組分(a)共聚合。
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DE102017219311.5 | 2017-10-27 | ||
DE102017219311.5A DE102017219311A1 (de) | 2017-10-27 | 2017-10-27 | Plasmarandverkapselung von Klebebändern |
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EP (1) | EP3700993A1 (zh) |
CN (1) | CN111278941A (zh) |
DE (1) | DE102017219311A1 (zh) |
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WO (1) | WO2019081153A1 (zh) |
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JPS5364243A (en) * | 1976-11-19 | 1978-06-08 | Sekisui Chem Co Ltd | Adhesive tape rolls |
CH687614A5 (de) * | 1994-02-04 | 1997-01-15 | Tetra Pak Suisse Sa | Verfahren zum Versehen einer Verpackung mit hervorragenden Sperreigenschaften in bezug auf Gase. |
US5789487A (en) | 1996-07-10 | 1998-08-04 | Carnegie-Mellon University | Preparation of novel homo- and copolymers using atom transfer radical polymerization |
FR2757865B1 (fr) | 1996-12-26 | 1999-04-02 | Atochem Elf Sa | Procede de polymerisation ou copolymerisation radicalaire controlee de monomeres (meth)acryliques, vinyliques, vinylideniques et dieniques et (co)polymeres obtenus |
DE10030217A1 (de) | 2000-06-20 | 2002-01-03 | Beiersdorf Ag | Verfahren zur Herstellung von Polyacrylaten |
DE10036801A1 (de) | 2000-07-28 | 2002-02-07 | Tesa Ag | Acrylathaftklebemassen mit enger Molekulargewichtsverteilung |
DE10149084A1 (de) | 2001-10-05 | 2003-06-18 | Tesa Ag | UV-vernetzbare Acrylathaftschmelzhaftkleber mit enger Molekulargewichtsverteilung |
DE102004044086A1 (de) | 2004-09-09 | 2006-03-16 | Tesa Ag | Thermisch vernetzte Acrylat-Hotmelts |
DE102007006251B4 (de) * | 2007-02-08 | 2016-07-07 | Lohmann Gmbh & Co. Kg | Verfahren zur kantenseitigen Passivierung von Haftklebebändern, nach dem Verfahren hergestellte Haftklebebandrolle und deren Verwendung |
DE102007016950A1 (de) | 2007-04-05 | 2008-10-09 | Tesa Ag | Thermisch vernetzende Polyacrylate und Verfahren zu deren Herstellung |
CN101697343B (zh) * | 2009-10-27 | 2011-06-15 | 苏州纳科显示技术有限公司 | 一种薄膜封装方法 |
KR102039390B1 (ko) | 2012-02-21 | 2019-11-04 | 린텍 가부시키가이샤 | 유기 전자 소자 및 유기 전자 소자의 제조 방법 |
US20180009002A1 (en) * | 2015-02-20 | 2018-01-11 | Tesa Se | Method for reducing the winding level adhesiveness of an adhesive tape roll |
DE102016212971A1 (de) * | 2016-07-15 | 2018-01-18 | Tesa Se | Reduzierung der Seitenkantenklebrigkeit einer Klebebandrolle |
DE102017210066A1 (de) * | 2017-06-14 | 2018-12-20 | Tesa Se | Verfahren zur simultanen Plasmarandverkapselung von mindestens zwei Klebebandseiten |
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2018
- 2018-09-27 CN CN201880069082.1A patent/CN111278941A/zh active Pending
- 2018-09-27 WO PCT/EP2018/076230 patent/WO2019081153A1/de unknown
- 2018-09-27 EP EP18782363.8A patent/EP3700993A1/de active Pending
- 2018-10-04 TW TW107135042A patent/TW201922988A/zh unknown
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WO2019081153A1 (de) | 2019-05-02 |
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