CN113773770A - Double-curing pressure-sensitive adhesive and preparation method of support film protective adhesive tape thereof - Google Patents
Double-curing pressure-sensitive adhesive and preparation method of support film protective adhesive tape thereof Download PDFInfo
- Publication number
- CN113773770A CN113773770A CN202111132705.5A CN202111132705A CN113773770A CN 113773770 A CN113773770 A CN 113773770A CN 202111132705 A CN202111132705 A CN 202111132705A CN 113773770 A CN113773770 A CN 113773770A
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- CN
- China
- Prior art keywords
- sensitive adhesive
- monomer
- acrylate
- pressure
- dual
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 59
- 230000001681 protective effect Effects 0.000 title claims abstract description 36
- 239000002390 adhesive tape Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 69
- 229920006223 adhesive resin Polymers 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 14
- 239000000853 adhesive Substances 0.000 claims abstract description 13
- 230000001070 adhesive effect Effects 0.000 claims abstract description 13
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 19
- -1 alkyl (methyl) acrylate Chemical compound 0.000 claims description 17
- 239000002216 antistatic agent Substances 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 8
- 230000009977 dual effect Effects 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000005096 rolling process Methods 0.000 claims description 4
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 239000013522 chelant Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000523 sample Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 abstract description 15
- 239000003292 glue Substances 0.000 abstract description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 7
- 229920002554 vinyl polymer Polymers 0.000 abstract description 6
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 238000001723 curing Methods 0.000 description 26
- 230000008569 process Effects 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000012790 adhesive layer Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- 239000002313 adhesive film Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- RSJWKIDVVZWYTD-UHFFFAOYSA-N 1-(2-isocyanatopropan-2-yl)-2-prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1C(C)(C)N=C=O RSJWKIDVVZWYTD-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- ZEWLHMQYEZXSBH-UHFFFAOYSA-N 4-[2-(2-methylprop-2-enoyloxy)ethoxy]-4-oxobutanoic acid Chemical compound CC(=C)C(=O)OCCOC(=O)CCC(O)=O ZEWLHMQYEZXSBH-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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 2
- 238000002834 transmittance Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- JHNRZXQVBKRYKN-VQHVLOKHSA-N (ne)-n-(1-phenylethylidene)hydroxylamine Chemical compound O\N=C(/C)C1=CC=CC=C1 JHNRZXQVBKRYKN-VQHVLOKHSA-N 0.000 description 1
- JHVQWALHXJPODC-ALCCZGGFSA-N (z)-2-[2-(2-methylprop-2-enoyloxy)ethyl]but-2-enedioic acid Chemical compound CC(=C)C(=O)OCC\C(C(O)=O)=C\C(O)=O JHVQWALHXJPODC-ALCCZGGFSA-N 0.000 description 1
- HSFXEOPJXMFQHG-ARJAWSKDSA-N (z)-4-[2-(2-methylprop-2-enoyloxy)ethoxy]-4-oxobut-2-enoic acid Chemical compound CC(=C)C(=O)OCCOC(=O)\C=C/C(O)=O HSFXEOPJXMFQHG-ARJAWSKDSA-N 0.000 description 1
- JWYVGKFDLWWQJX-UHFFFAOYSA-N 1-ethenylazepan-2-one Chemical compound C=CN1CCCCCC1=O JWYVGKFDLWWQJX-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- 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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 1
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- NCAVPEPBIJTYSO-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate;2-(oxiran-2-ylmethoxymethyl)oxirane Chemical compound C1OC1COCC1CO1.OCCCCOC(=O)C=C NCAVPEPBIJTYSO-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- GDFCSMCGLZFNFY-UHFFFAOYSA-N Dimethylaminopropyl Methacrylamide Chemical compound CN(C)CCCNC(=O)C(C)=C GDFCSMCGLZFNFY-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000005518 carboxamido group Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 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 1
- 238000010030 laminating Methods 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- AWGZKFQMWZYCHF-UHFFFAOYSA-N n-octylprop-2-enamide Chemical compound CCCCCCCCNC(=O)C=C AWGZKFQMWZYCHF-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 125000006684 polyhaloalkyl group Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005463 sulfonylimide group Chemical group 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a double-curing pressure-sensitive adhesive and a preparation method of a support film protective adhesive tape thereof. The dual-curing pressure-sensitive adhesive comprises two-stage modified pressure-sensitive adhesive resin. Has the advantages that: (1) the low-Tg high-modulus glue is designed, so that the balance of the storage modulus and the initial adhesion of the glue film at normal temperature is ensured, and the adhesion of a high-surface-energy back material is optimized by using a high-content high-polarity functional monomer; meanwhile, the bonding strength is gradually increased along with the extension of the attaching time, and the bonding reliability is effectively ensured. (2) A vinyl monomer incorporating a blocked isocyanate group inhibits its mobility in the glue layer due to uniform grafting in the glue layer. Meanwhile, the adhesive can be deblocked by being heated to generate later-stage thermosetting behavior, so that internal crosslinking is increased, and the cohesive force is increased, thereby increasing the cohesiveness, forming a hot-hot dual-curing mode with early-stage thermosetting, and ensuring the stability and high-temperature viscosity of the adhesive.
Description
Technical Field
The invention relates to the technical field of functional adhesives, in particular to a dual-curing pressure-sensitive adhesive and a preparation method of a support film protective adhesive tape thereof.
Background
In recent years, with the rapid development of electronic products such as display technologies, personal wear, folding screen mobile phones, 3D large arc screen mobile phones and the like, flexible OLED displays are more and more widely applied. The OLED (Organic Light-Emitting Diode) has many advantages of self-luminescence, all solid state, wide viewing angle, thin thickness, fast response and the like, and has a huge application prospect in flat panel display; this has also driven the development of functional materials such as functional tapes and the like used in electronic displays.
At present, the manufacturing process of the flexible OLED screen is that PI is used as a flexible substrate on a rigid glass plate, photoresist is coated on the PI and UV exposure is carried out, then the surface of the PI is attached and protected, and after development and etching, the rigid glass plate and the flexible substrate PI are separated. The manufactured OLED device has certain flexibility, but risks of scratches, damage, pollution, fracture and the like exist in the transportation and assembly processes. Based on this, a flexible adhesive tape with stiffness is needed to protect, fix and support the flexible adhesive tape. In the use process of the actually assembled OLED display screen, the surface temperature of the OLED display screen is often 70 ℃ or even above due to the influence of the heating of electronic elements and external heat sources, so that the supporting film protective adhesive tape for protecting, fixing and supporting needs to have higher temperature resistance; meanwhile, the existing screen repairing and disassembling process of the mobile phone generally needs to be heated to 80-100 ℃, so that the support film protective adhesive tape needs to have higher cohesive strength and viscosity at high temperature, and the damage of an OLED device in the disassembling process is avoided. Therefore, there is a need for an adhesive with a balance of heat resistance and peel force for application to a backing film (BP) to give adequate protection and support to a PI flexible substrate.
The support film for the flexible OLED screen is mainly characterized in that the appearance requirement is optical grade, each layer of structure is antistatic, the adhesive has the characteristics of high viscosity, high cohesion, heat resistance, static resistance, small deformation caused by heating pressure and the like, the protective film for protecting the surface of the support film also requires optical grade, the appearance is higher, the antistatic performance is realized, the voltage for tearing the film on the back side of the support film is less than 500V, the back material is required to have optical property, and the appearance grade is higher. However, in addition to Nitto, BP films in the market which can meet the performance requirements also meet the functional requirements of panel factories by Innox, and meanwhile, the problem that a small amount of bubbles exist in hot pressing and attaching exists, domestic tape factories are still in research and development verification stages, and adopted glue is generally produced in japan and is expensive, and the performance cannot balance the requirements of hot pressing and high peeling force.
In view of the above, it would be of great importance to provide a dual-cure pressure-sensitive adhesive and a supporting protective film thereof.
Disclosure of Invention
The invention aims to provide a dual-curing pressure-sensitive adhesive and a preparation method of a support film protective tape thereof, so as to solve the problems in the background technology.
The prepared support film protective adhesive tape has high peeling force at normal temperature, has specific viscosity at 150 ℃, has excellent infiltration filling property when being attached with a flexible PI film (the back surface of the PI film is provided with a circuit) at normal temperature, has the characteristic of small deformation under the high-temperature pressure of 150 ℃, can meet the force conduction requirement in the subsequent process of binding an IC circuit, has balanced performances in all aspects, and can meet the requirements of the electronic field.
In order to solve the technical problems, the invention provides the following technical scheme:
a dual cure pressure sensitive adhesive characterized by: comprises the following components:
(1) a two-stage modified pressure sensitive adhesive resin;
(2) 0.1 wt% -1.0 wt% of cross-linking agent is added into every 100 parts of two-stage type modified pressure-sensitive adhesive resin;
(3) 0.05 wt% -0.5 wt% of antistatic agent is added into every 100 parts of the two-stage adhesive;
(4) 50-70 wt% of organic solvent is added into each 100 parts of the two-stage adhesive.
Wherein the organic solvent is one or more of ethyl acetate, butyl acetate, toluene, xylene, acetone, butanone, ethanol, isopropanol, glycol alkyl ether, heptane, cyclohexanone and the like.
Preferably, the two-stage modified pressure-sensitive adhesive resin comprises the following components:
(a) 80-90 wt% of a first alkyl (meth) acrylate main monomer; 10-20 wt% of a second (methyl) acrylate functional monomer; the sum of the first alkyl (methyl) acrylate main monomer and the second functional (methyl) acrylate monomer is 100 wt%;
(b) adding 0.1 wt% -0.6 wt% of thermal initiator into every 100 parts of (a);
(c) adding 350 wt% -450 wt% of solvent into every 100 parts of (a).
Wherein the solvent is one or more of ethyl acetate, butyl acetate, toluene, xylene, acetone, butanone, ethanol, isopropanol, ethylene glycol alkyl ether, heptane, cyclohexanone and the like.
Preferably, the first alkyl (meth) acrylate main monomer is an alkyl (meth) acrylate containing 4 or more carbon atoms; the second type of (methyl) acrylate functional monomer is a mixture of isocyanate group terminated monomer containing carbon-carbon double bond and other types of (methyl) acrylate functional monomers.
Wherein the first alkyl (meth) acrylate main monomer is one or more of octadecyl (meth) acrylate, dodecyl (meth) acrylate, 2-hexyl (meth) acrylate, isooctyl (meth) acrylate, n-butyl (meth) acrylate, and the like;
wherein, the isocyanate group-terminated monomer containing carbon-carbon double bonds comprises one or more of isopropenyl dimethyl benzyl isocyanate (which can be terminated by acetophenone oxime) and 2- [ (3, 5-dimethyl-1-H-pyrazolyl) carboxyl amino ] ethyl acrylate;
preferably, the other type of (meth) acrylate functional monomer is one or more of a monomer containing a carboxyl functional group, a monomer containing a hydroxyl functional group, a monomer containing an amide functional group, and a monomer containing an epoxy functional group.
Wherein, the monomer containing carboxyl functional group comprises one or more of (methyl) acrylic acid, maleic anhydride, itaconic acid, methacryloxyethyl succinate monoester, methacryloxyethyl maleic acid monoester and the like; the monomer containing hydroxyl functional group comprises one or more of (meth) acrylic acid, maleic anhydride, itaconic acid, methacryloyloxyethyl succinate monoester, methacryloyloxyethyl maleate monoester, etc.; the monomer containing the amide functional group comprises one or more of (meth) acrylamide, N-dimethylacrylamide, N-octylacrylamide, N-methylolacrylamide, N-vinylcaprolactam, N- (3-dimethylaminopropyl) methacrylamide, acryloylmorpholine and the like; the monomer containing epoxy functional group includes one or more of glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, allyl glycidyl ether, etc.
Preferably, the thermal initiator is an organic peroxide compound or an azo compound.
Wherein, one or more of benzoyl peroxide, benzoyl peroxide tert-butyl ester, methyl ethyl ketone peroxide, dicumyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, dimethyl azobisisobutyrate and the like.
Preferably, the antistatic agent is one or more of an imide salt and a lithium salt antistatic agent.
The antistatic agent is well known in the industry and comprises one or more of (polyhaloalkyl sulfonyl imide) salt, tributyl ammonium bis (trifluoromethanesulfonyl) imide salt, lithium bistrifluoromethanesulfonimide and the like.
Preferably, the crosslinking agent is one or more of isocyanate crosslinking agent, epoxy crosslinking agent, aziridine crosslinking agent and metal salt chelate;
the crosslinking agent is well known in the industry and comprises one or more of Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), amine modified epoxy curing agent (Y202), aziridine (Sac-100), aluminum acetylacetonate, and the like.
Preferably, the preparation method of the dual-curing pressure-sensitive adhesive comprises the following steps:
s1, adding a first type of alkyl (meth) acrylate main monomer and other types of (meth) acrylate functional monomers into a reaction bottle provided with a probe temperature sensor, a nitrogen guide pipe and a stirring device, stirring in a nitrogen atmosphere and under a heat source, adding a thermal initiator diluent in batches, after reacting for 2-3 hours, beginning to dropwise add a diluent of an isocyanate-terminated monomer containing a carbon-carbon double bond, stirring for reacting for 4-6 hours, finishing the reaction, and cooling the reaction solution to normal temperature to obtain the two-stage modified pressure-sensitive adhesive resin; wherein the thermal initiator diluent is obtained by diluting the thermal initiator and the monomer in advance with a solvent.
And S2, sequentially adding the two-stage modified pressure-sensitive adhesive resin, the cross-linking agent, the antistatic agent, the thermal initiator and the organic solvent into a PP bottle with a cover, uniformly rolling in a three-roller machine, and standing for defoaming to obtain the dual-curing pressure-sensitive adhesive.
Wherein the obtained two-stage type modified pressure-sensitive adhesive resin has a weight average molecular weight of 75 × 10 as measured by GPC4～90×104The distribution index D is between 1.9 and 2.1 in daltons.
Preferably, the support film protective tape comprises an antistatic protective film, a PET base material, a dual-curing pressure-sensitive adhesive and a PET release liner from top to bottom in sequence.
The antistatic protective film can be a PU system antistatic protective film or an acrylic system antistatic protective film, and can be made by self or be purchased commercially. The 180 DEG peeling force of the glass is required to be less than 3gf/inch, the 180 DEG peeling force of the back side (antistatic coating side: PET substrate) of the support film is required to be 2 to 5gf/inch, and the resistance of the base film is 105～108Omega, the impedance of the glue surface is 1012Omega below, and the dynamic tearing voltage required on the back side of the supporting film is less than 500V, which is known as above, the invention is not detailedThe description is given.
Preferably, the preparation method of the support film protective adhesive tape comprises the following steps: spraying a dual-curing pressure-sensitive adhesive on one surface of the PET base material, baking, attaching a PET release liner, and curing; and attaching an antistatic protective film to the other surface of the PET substrate to obtain the support film protective adhesive tape.
Wherein the baking temperature is 110 ℃, the baking time is 3min, and the thickness of the adhesive layer after baking is 25 μm; the curing condition is curing at 50 deg.C for 3d or at room temperature for 7 d.
In the scheme:
(1) the antistatic agent is added into the double-curing pressure-sensitive adhesive in an amount of 0.05 to 0.5 weight percent; compared with the prior art, the addition amount is lower, and the specific type of antistatic agent is selected, so that the impedance required by design can be met under the condition of less addition amount. The reason is that: the antistatic agent can migrate to the surface of the adhesive layer in the using process, the later adhesion is affected, and the antistatic agent needs to be added as little as possible.
(2) In the dual-curing pressure-sensitive adhesive, two-section type modified pressure-sensitive adhesive resin is used, and 10-20 wt% of a second (methyl) acrylate functional monomer is added into the resin; compared with 3 wt% in the prior art, the content is far more than that in the prior art. The designed resin has a low glass transition temperature Tg, and even if the resin contains a great amount of acrylic acid, the initial peeling force and initial adhesion of the resin can still meet the requirement of initial adhesion of PI and glass materials; after bonding, due to the high addition amount of acrylic acid, the bonding strength is prolonged along with time, the bonding force is firmer and firmer, and the high-temperature cohesive strength is achieved.
(3) The two-stage modified pressure-sensitive adhesive resin is introduced with isocyanate group terminated monomer containing carbon-carbon double bond. In the resin synthesis process, the modified monomer is introduced into a resin molecular chain in a later-stage dropwise adding mode, and because the polymerization rates of the monomers are different, if the modified monomer is added into the resin for reaction at the beginning, more self-polymerization tendency exists, so that the modified monomer is excessively and intensively distributed, and the distribution uniformity of the modified monomer in a resin main chain is influenced. The first type of alkyl (methyl) acrylate main monomer and the second type of (methyl) acrylate functional monomer except the isocyanate-terminated monomer containing the carbon-carbon double bond are reacted firstly, and then the modified monomer is dropwise added, so that the modified monomer can be uniformly reacted on the resin main chain better.
In the process, the curing agent is added in the early stage to ensure the primary bonding effect, and the grafted vinyl monomer containing the blocked isocyanate group is uniformly and stably distributed in the adhesive layer because the vinyl group of the grafted vinyl monomer reacts with the acrylate monomer before the later-stage use of the mobile phone is influenced by a heat source or self-heating, so that the grafted vinyl monomer cannot migrate in the adhesive layer. When the IC circuit is bound in the later stage, through high-temperature deblocking, two-stage heat curing can be performed more uniformly, isocyanate groups can be slowly crosslinked with reactive groups in the adhesive layer again, the cohesion is slightly increased, and the bonding property is gradually enhanced. Generally, the deblocking start temperature is about 130 ℃, the deblocking speed is directly accelerated at a high temperature of 140 ℃ or higher, the deblocking time can be shortened to about 10 seconds at a temperature of 150 ℃ or higher, and instantaneous deblocking can be performed at 160 ℃ or higher.
Meanwhile, compared with a thermo-optic dual-curing mode, thermo-optic dual-curing in the scheme is better in practical application, because light transmittance is needed for photo-curing crosslinking, and bonding strength is affected due to limitation in the practical use process.
(4) In the support film protective adhesive tape, a two-section type modified pressure-sensitive adhesive is coated on the surface of a PET substrate, after a solvent is dried and removed, another PET release liner is attached, and then the PET release liner is cured for standby use, a DHR-2 rheometer is used for laminating pure foam adhesive films into a thickness of 1mm, the diameter of the pure foam adhesive films is 8mm, and under the conditions of 1Hz and 0.1% torsion, the storage modulus G' of the adhesive films at 25 ℃ and 150 ℃ is 105ps, more precisely, 0.8 × 105～1.2×105pa and 0.4 × 105～0.8×105pa; if the storage modulus G 'at 25 ℃ is too high, the adhesive layer is hard and is not beneficial to bonding and filling the flexible PI at the initial stage (the back side of the PI contains a circuit), and if the storage modulus G' is too low, the concentration in the pressure-sensitive adhesive layer is small and is not beneficial to force transmission when an IC circuit is bound at the later stage; similarly, the storage modulus G' at 150 ℃ cannot be too low, otherwise the yield of the binding process is too low, and the production is not facilitated.
Similarly, the coating film is baked at 120 ℃ for 60min or at 150 ℃ for 20min, and the storage modulus is measured by the same method, wherein G' is 0.8 × 10 at 25 ℃5～1.5×105pa, G' is 0.5X 10 at 150 ℃5～0.8×105pa. And testing creep deformation (keeping for 10min under 20Kpa and recovering for 10min under no stress) by using a DHR-2 rheometer, and measuring the deformation rate to be below 50% and the deformation recovery rate to be above 90%, so that the design is favorable for the support film protective adhesive tape to be not easy to cause failure of the binding process due to overlarge stress deformation in the binding process.
The PET base material and the PET release liner adopted by the method have the thickness of 25-75 mu m, the appearance requirement is optical grade, the visible light transmittance can be more than 88%, the haze is less than 2.0%, the surface of the PET base material and the PET release liner can be coated with an antistatic coating, and the impedance is 105～108Omega is between.
Compared with the prior art, the invention has the following beneficial effects: (1) the low-Tg high-modulus glue is designed, so that the balance of the storage modulus and the initial adhesion of the glue film at normal temperature is ensured, and the adhesion of a high-surface-energy back material is optimized by using a high-content high-polarity functional monomer; meanwhile, the bonding strength is gradually increased along with the extension of the attaching time, and the bonding reliability is effectively ensured. (2) A vinyl monomer incorporating a blocked isocyanate group inhibits its mobility in the glue layer due to uniform grafting in the glue layer. Meanwhile, the adhesive can be deblocked by being heated to generate later-stage thermosetting behavior, so that internal crosslinking is increased, and the cohesive force is increased, thereby increasing the cohesiveness, forming a hot-hot dual-curing mode with early-stage thermosetting, and ensuring the stability and high-temperature viscosity of the adhesive. (3) The low-temperature polymerization and accurate temperature control are carried out, the molecular weight is designed to be about 80 ten thousand daltons, the distribution width is about 2, the content of small molecules in a glue system is low, the storage modulus G' of the glue layer is slowly reduced in a high-temperature environment, the overall temperature resistance of the glue layer is improved due to the small molecular weight, and the lasting and effective bonding of the adhesive is ensured.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a graph showing the change in peel force with time of application of a support film protective tape according to example A2;
FIG. 2 is a graph showing the peel force versus temperature for the support film protective tape of example A2;
FIG. 3 is a DMA rheology plot of the support film protective tape of example A2;
FIG. 4 is a graph of Creep of the supporting film protective tape of example A2;
FIG. 5 is a view showing a laminated structure of a support film protective tape;
in the figure: 1 antistatic protective film, 2PET base material, 3 dual-curing pressure-sensitive adhesive and 4PET release liner.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The basic preparation method comprises the following steps:
s1, adding a first type of alkyl (methyl) acrylate main monomer and a second type of (methyl) acrylate functional monomer except for a carbon-carbon double bond-containing isocyanate-terminated monomer into a 1000mL reaction bottle with a temperature sensor, a stirring device and a nitrogen atmosphere, setting the nitrogen flow to be 0.3L, stirring at the rotating speed of 300rpm, simultaneously heating the reaction liquid to 60-65 ℃, starting to dropwise heat initiator diluent in batches after introducing nitrogen for 30 minutes, dropwise adding diluent (with the concentration of 1.0%) of the carbon-carbon double bond-containing isocyanate-terminated monomer after reacting for 3 hours, continuing to react for 4-6 hours, and supplementing a solvent to dilute and finish the reaction to obtain the two-stage modified pressure-sensitive adhesive resin.
S2, adding two-stage type modified pressure-sensitive adhesive resin, a cross-linking agent, an antistatic agent and a solvent into a 250mL PP bottle with a cover, rolling for 1h in a three-roller machine, and standing for defoaming to obtain a dual-curing pressure-sensitive adhesive;
s3, spraying a dual-curing pressure-sensitive adhesive on one surface of the PET substrate, baking, attaching a PET release liner to obtain a BP adhesive tape, and curing (curing condition: curing at 50 ℃ for 3d or at normal temperature for 7 d); then, a support film protective tape was obtained. And attaching an antistatic protective film of an acrylic system or a PU system to the back side (namely the other side of the PET substrate) of the cured BP adhesive tape substrate to obtain the complete flexible support film protective adhesive tape for the OLED screen.
Sources of materials in the examples:
| materials abbreviations | Name of Material | Source |
| 2-EHA | 2-ethylhexyl acrylate | Zhejiang satellite petrifaction |
| BA | Acrylic acid n-butyl ester | Zhejiang satellite petrifaction |
| AA | Acrylic acid | Zhejiang satellite petrifaction |
| HEA | Acrylic acid hydroxy ethyl ester | Zhejiang satellite petrifaction |
| AOI-BP | 2- [ (3, 5-dimethyl-1-H-pyrazolyl) carboxamido]Ethyl acrylate | Aladdin |
| AP8 | (polyhaloalkylsulfonimide salts | Japan village and honor society |
| TMI-MK | Methyl ethyl ketoxime end-capped isopropenyl dimethyl benzyl isocyanate | Aladdin |
| AIBN | Azobisisobutyronitrile | Aladdin |
| Y202 | 5% strength epoxy hardener | Chemistry of azon |
| MEK | Butanone | Satellite petrochemistry |
| ETAc | Ethyl acetate | Satellite |
| PET substrate | ||
| 1 | 50 μm single-sided antistatic polyester film | |
| PET substrate | ||
| 2 | 75 μm double-sided antistatic polyester film | Mitsubishi |
| |
25 mu mPE release liner | YANGZHOU ALVIN FILM Co.,Ltd. |
| |
50 mu m double-sided antistatic PET release substrate | Mitsubishi |
Taking example a1 as an example:
s1, adding 150g ETAc, 80g 2-EHA, 18gAA, 1.5g HEA and 0.3L nitrogen flow into a 1000mL reaction bottle with a temperature sensor, a stirring device and a nitrogen atmosphere, stirring at the rotating speed of 300rpm, simultaneously heating the reaction solution to 62 ℃, starting to dropwise add initiator diluent in batches after introducing nitrogen for 30 minutes, dropwise adding 50g AOI-BP diluent (with the concentration of 1.0%) after reacting for 3 hours, continuing to react for 5 hours, and adding 200g diluting solvent ETAc to finish the reaction to obtain the two-stage modified pressure-sensitive adhesive resin with the viscosity of about 7000 cps.
S2, adding 100g of two-stage modified pressure-sensitive adhesive resin, 0.2g of epoxy curing agent Y202, 0.1g of imine salt antistatic agent, 0.1g of organic tin catalyst TMA-218 and 30g of ethyl acetate into a 250mL PP bottle with a cover, rolling for 1h in a three-roller machine, and standing for defoaming to obtain the dual-cured pressure-sensitive adhesive;
s3, coating a dual-curing pressure-sensitive adhesive on the surface of a 75-micrometer double-sided antistatic polyester film, baking in an oven at 110 ℃ for 3min to remove the solvent, wherein the thickness of a dry adhesive layer is 25 micrometers, then attaching a 50-micrometer double-sided antistatic PET release liner on the surface of the coating to obtain a BP adhesive tape, and curing at 50 ℃ for 3d for later use; and attaching an antistatic protective film to the back side of the cured BP adhesive tape base material to obtain the support film protective adhesive tape.
Examples A1-A7, comparative examples CA1-CA 4: the specific changes of the conditions such as the compounds and the contents in example A1 are shown in tables 1 and 2.
Experiment: the two-stage modified pressure-sensitive adhesive resins prepared in examples A1-A7 and comparative examples CA1-CA4 were subjected to a series of tests, and the supporting protective film tapes were subjected to a performance test. The data obtained are shown in tables 1 and 2.
TABLE 1 modified pressure sensitive adhesive resins of examples A1-A10 and comparative examples CA1-CA 3
And (4) conclusion: as can be seen from the data of Table 1, when the functional monomer exceeds 20 parts, the viscosity of the modified pressure-sensitive adhesive resin is too high and microgel phenomenon exists, so that coating is difficult; when the amount is less than 10 parts, the viscosity of the reaction liquid modified pressure-sensitive adhesive resin is small and the molecular weight is small.
TABLE 2 influence of examples A1-A10 and comparative examples CA1-CA 3 on storage modulus and peel force
Remarking: (1) the storage modulus after heating mainly simulates the storage modulus change of a flexible OLED device in the process of being subjected to 150-30 min, and the characteristic is that the OLED device is subjected to a 12S adhesive film deformation state under the high temperature of 150 ℃ when an IC circuit is bound, and only if the high temperature is subjected to pressure, enough storage modulus is kept, and a BP adhesive layer can have enough viscoelasticity to maintain the effective force transmission generated in the process of binding at the high temperature; (2) cf indicates that cohesive failure of the bondline occurred upon peeling.
And (4) conclusion: combining the data in tables 1 and 2, it can be seen that: when the functional monomer exceeds 10 parts, the polymerization of the modified pressure-sensitive adhesive resin fails to generate the microgel phenomenon,can not be coated; when the functional monomer is less than 10 parts, the molecular weight of the modified pressure-sensitive adhesive resin is smaller, and when the modified pressure-sensitive adhesive resin is in a high-temperature environment of more than 85 ℃, the storage modulus is greatly reduced, especially when the modified pressure-sensitive adhesive resin is at 150 ℃, the storage modulus G' is reduced by one order of magnitude to 0.09 multiplied by 105Pa, the adhesive layer is seriously softened at the moment and cannot effectively conduct the force conduction in the binding process, which seriously influences the yield of the IC circuit bound at 150 ℃, and meanwhile, under the modulus, the peeling force at 85 ℃ is in a half-failure state, and cohesive failure occurs during peeling.
When the total amount of the functional monomers is 10-20 parts, the normal-temperature modulus and the high-temperature modulus G' of the functional monomers are always 105Pa or so, the stripping force at room temperature and high temperature is more than 800gf/inch, the lasting and stable bonding of the support film adhesive tape to the flexible OLED device can be maintained, and the fault of the mobile phone in daily use is effectively avoided.
Meanwhile, in the comparative example CA4, no vinyl monomer containing blocked isocyanate group is added, and after the pressure-sensitive adhesive resin after polymerization is used for preparing a support film at the later stage, when the support film needs to be heated at a high temperature, the storage modulus G' is not basically improved, so that the lower modulus at the high temperature is low, the adhesive film becomes soft at the high temperature, the stripping force at 85 ℃ is small, and the hidden troubles of bonding failure and binding process failure are caused.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A dual cure pressure sensitive adhesive characterized by: comprises the following components:
(1) a two-stage modified pressure sensitive adhesive resin;
(2) 0.1 wt% -1.0 wt% of cross-linking agent is added into every 100 parts of two-stage type modified pressure-sensitive adhesive resin;
(3) 0.05 wt% -0.5 wt% of antistatic agent is added into every 100 parts of the two-stage adhesive;
(4) 50-70 wt% of organic solvent is added into each 100 parts of the two-stage adhesive.
2. The dual cure pressure sensitive adhesive of claim 1, wherein: the two-stage type modified pressure-sensitive adhesive resin comprises the following components:
(a) 80-90 wt% of a first alkyl (meth) acrylate main monomer; 10-20 wt% of a second (methyl) acrylate functional monomer; the sum of the first alkyl (methyl) acrylate main monomer and the second functional (methyl) acrylate monomer is 100 wt%;
(b) adding 0.1 wt% -0.6 wt% of thermal initiator into every 100 parts of (a);
(c) adding 350 wt% -450 wt% of solvent into every 100 parts of (a).
3. The dual cure pressure sensitive adhesive of claim 2, wherein: the first alkyl (meth) acrylate main monomer is alkyl (meth) acrylate containing more than 4C atoms; the second type of (methyl) acrylate functional monomer is a mixture of isocyanate group terminated monomer containing carbon-carbon double bond and other types of (methyl) acrylate functional monomers.
4. The dual cure pressure sensitive adhesive of claim 3, wherein: the other type of (methyl) acrylate functional monomer is one or more of a monomer containing a carboxyl functional group, a monomer containing a hydroxyl functional group, a monomer containing an amide functional group and a monomer containing an epoxy functional group.
5. The dual cure pressure sensitive adhesive of claim 2, wherein: the thermal initiator is an organic peroxide compound and an azo compound.
6. The dual cure pressure sensitive adhesive of claim 1, wherein: the antistatic agent is one or more of imide salt and lithium salt antistatic agents.
7. The dual cure pressure sensitive adhesive of claim 1, wherein: the cross-linking agent is one or more of isocyanate cross-linking agent, epoxy cross-linking agent, aziridine cross-linking agent and metal salt chelate.
8. The preparation method of the dual-curing pressure-sensitive adhesive is characterized by comprising the following steps: the method comprises the following steps:
s1, adding a first type of alkyl (meth) acrylate main monomer and other types of (meth) acrylate functional monomers into a reaction bottle provided with a probe temperature sensor, a nitrogen guide pipe and a stirring device, stirring in a nitrogen atmosphere and under a heat source, adding a thermal initiator diluent in batches, after reacting for 2-3 hours, beginning to dropwise add a diluent of an isocyanate-terminated monomer containing a carbon-carbon double bond, stirring for reacting for 4-6 hours, finishing the reaction, and cooling the reaction solution to normal temperature to obtain the two-stage modified pressure-sensitive adhesive resin;
and S2, sequentially adding the two-stage modified pressure-sensitive adhesive resin, the cross-linking agent, the antistatic agent, the thermal initiator and the organic solvent into a PP bottle with a cover, uniformly rolling in a three-roller machine, and standing for defoaming to obtain the dual-curing pressure-sensitive adhesive.
9. Support membrane protection sticky tape, its characterized in that: the adhesive comprises an antistatic protective film, a PET base material, the dual-curing pressure-sensitive adhesive as claimed in any one of claims 1 to 8 and a PET release liner from top to bottom in sequence.
10. The preparation method of the support film protective adhesive tape is characterized by comprising the following steps: the method comprises the following steps: spraying the dual-curing pressure-sensitive adhesive as defined in any one of claims 1 to 8 on one side of a PET substrate, baking, attaching a PET release liner, and curing; and attaching an antistatic protective film to the other surface of the PET substrate to obtain the support film protective adhesive tape.
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| CN202111132705.5A Active CN113773770B (en) | 2021-09-27 | 2021-09-27 | Double-curing pressure-sensitive adhesive and preparation method of support film protective adhesive tape thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115109178A (en) * | 2022-06-23 | 2022-09-27 | 乐凯华光印刷科技有限公司 | Additive resin, and barrier protective layer, high barrier film and oxygen-blocking and water-blocking steam packaging material containing additive resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140295180A1 (en) * | 2013-03-28 | 2014-10-02 | Nitto Denko Corporation | Antistatic pressure-sensitive adhesive sheet and optical film |
| CN108611010A (en) * | 2018-03-30 | 2018-10-02 | 东莞市澳中电子材料有限公司 | A kind of two-sided UV Protection glues band of easy-clear and preparation method thereof |
| CN110862782A (en) * | 2019-11-26 | 2020-03-06 | 新纶科技（常州）有限公司 | Flexible OLED supports uses protection film sticky tape |
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2021
- 2021-09-27 CN CN202111132705.5A patent/CN113773770B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140295180A1 (en) * | 2013-03-28 | 2014-10-02 | Nitto Denko Corporation | Antistatic pressure-sensitive adhesive sheet and optical film |
| CN108611010A (en) * | 2018-03-30 | 2018-10-02 | 东莞市澳中电子材料有限公司 | A kind of two-sided UV Protection glues band of easy-clear and preparation method thereof |
| CN110862782A (en) * | 2019-11-26 | 2020-03-06 | 新纶科技（常州）有限公司 | Flexible OLED supports uses protection film sticky tape |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115109178A (en) * | 2022-06-23 | 2022-09-27 | 乐凯华光印刷科技有限公司 | Additive resin, and barrier protective layer, high barrier film and oxygen-blocking and water-blocking steam packaging material containing additive resin |
| CN115109178B (en) * | 2022-06-23 | 2023-12-01 | 乐凯华光印刷科技有限公司 | Resin-added barrier protection layer, high barrier film and oxygen-blocking and water-blocking steam packaging material containing resin |
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| CN113773770B (en) | 2022-11-18 |
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Effective date of registration: 20240517 Address after: No. 56 Beijing North Road, Jiangsu Yangtze River International Chemical Industry Park, Zhangjiagang City, Suzhou City, Jiangsu Province, 215600 Patentee after: Jiangsu Shituo New Materials Technology Co.,Ltd. Country or region after: China Address before: 215200 no.1099 Xinzi Road, Wujiang Economic and Technological Development Zone, Suzhou City, Jiangsu Province Patentee before: SUZHOU SHINUO NEW MATERIAL TECHNOLOGY Co.,Ltd. Country or region before: China |