CN117757376A - Direct-collecting easy-unreeling polyurethane pressure-sensitive adhesive protective film and preparation method thereof - Google Patents
Direct-collecting easy-unreeling polyurethane pressure-sensitive adhesive protective film and preparation method thereof Download PDFInfo
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- CN117757376A CN117757376A CN202311752075.0A CN202311752075A CN117757376A CN 117757376 A CN117757376 A CN 117757376A CN 202311752075 A CN202311752075 A CN 202311752075A CN 117757376 A CN117757376 A CN 117757376A
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- sensitive adhesive
- parts
- polyurethane pressure
- protective film
- prepolymer
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 124
- 239000004814 polyurethane Substances 0.000 title claims abstract description 113
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 113
- 230000001681 protective effect Effects 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 31
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 31
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010410 layer Substances 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 24
- 239000002216 antistatic agent Substances 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 150000002009 diols Chemical class 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 33
- -1 neopentyl glycol-1, 6-hexanediol adipate diol Chemical class 0.000 claims description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 13
- 239000012948 isocyanate Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229920001610 polycaprolactone Polymers 0.000 claims description 9
- 239000004632 polycaprolactone Substances 0.000 claims description 9
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 230000036961 partial effect Effects 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 239000002608 ionic liquid Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- AVBJHQDHVYGQLS-AWEZNQCLSA-N (2s)-2-(dodecanoylamino)pentanedioic acid Chemical compound CCCCCCCCCCCC(=O)N[C@H](C(O)=O)CCC(O)=O AVBJHQDHVYGQLS-AWEZNQCLSA-N 0.000 claims description 5
- IKYNWXNXXHWHLL-UHFFFAOYSA-N 1,3-diisocyanatopropane Chemical compound O=C=NCCCN=C=O IKYNWXNXXHWHLL-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 239000004642 Polyimide Substances 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims 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 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 5
- NDLNTMNRNCENRZ-UHFFFAOYSA-N 2-[2-hydroxyethyl(octadecyl)amino]ethanol Chemical compound CCCCCCCCCCCCCCCCCCN(CCO)CCO NDLNTMNRNCENRZ-UHFFFAOYSA-N 0.000 claims description 4
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 claims description 4
- LPMBTLLQQJBUOO-KTKRTIGZSA-N (z)-n,n-bis(2-hydroxyethyl)octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(CCO)CCO LPMBTLLQQJBUOO-KTKRTIGZSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 claims description 3
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 3
- SAYMDKMGIAANGQ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1,3-dimethylimidazol-1-ium Chemical compound CN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F SAYMDKMGIAANGQ-UHFFFAOYSA-N 0.000 claims description 3
- ZDMWZUAOSLBMEY-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-butyl-1-methylpiperidin-1-ium Chemical compound CCCC[N+]1(C)CCCCC1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F ZDMWZUAOSLBMEY-UHFFFAOYSA-N 0.000 claims description 3
- LRESCJAINPKJTO-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-ethyl-3-methylimidazol-3-ium Chemical class CCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F LRESCJAINPKJTO-UHFFFAOYSA-N 0.000 claims description 3
- LECQXINNQGHJBM-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-methyl-3-octylimidazol-1-ium Chemical compound CCCCCCCCN1C=C[N+](C)=C1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F LECQXINNQGHJBM-UHFFFAOYSA-N 0.000 claims description 3
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 claims description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims description 3
- JJPZOIJCDNHCJP-UHFFFAOYSA-N dibutyl(sulfanylidene)tin Chemical compound CCCC[Sn](=S)CCCC JJPZOIJCDNHCJP-UHFFFAOYSA-N 0.000 claims description 3
- WCRDXYSYPCEIAK-UHFFFAOYSA-N dibutylstannane Chemical compound CCCC[SnH2]CCCC WCRDXYSYPCEIAK-UHFFFAOYSA-N 0.000 claims description 3
- QSHZUFRQHSINTB-UHFFFAOYSA-L dibutyltin(2+);dibromide Chemical compound CCCC[Sn](Br)(Br)CCCC QSHZUFRQHSINTB-UHFFFAOYSA-L 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- GLZWNFNQMJAZGY-UHFFFAOYSA-N octaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCO GLZWNFNQMJAZGY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- RIECPYZYOLVSJK-UHFFFAOYSA-N tert-butyl 2-dimethylsilyl-5-methylindole-1-carboxylate Chemical compound C[SiH](C)c1cc2cc(C)ccc2n1C(=O)OC(C)(C)C RIECPYZYOLVSJK-UHFFFAOYSA-N 0.000 claims description 3
- NXFZDTAAMQLJEC-UHFFFAOYSA-M tributyl-(2,2,2-trichloroacetyl)oxytin(1-) Chemical compound CCCC[Sn-](CCCC)(CCCC)OC(=O)C(Cl)(Cl)Cl NXFZDTAAMQLJEC-UHFFFAOYSA-M 0.000 claims description 3
- PWBHRVGYSMBMIO-UHFFFAOYSA-M tributylstannanylium;acetate Chemical compound CCCC[Sn](CCCC)(CCCC)OC(C)=O PWBHRVGYSMBMIO-UHFFFAOYSA-M 0.000 claims description 3
- XMHKTINRBAKEDS-UHFFFAOYSA-N trioctyltin Chemical compound CCCCCCCC[Sn](CCCCCCCC)CCCCCCCC XMHKTINRBAKEDS-UHFFFAOYSA-N 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- KIQKWYUGPPFMBV-UHFFFAOYSA-N diisocyanatomethane Chemical compound O=C=NCN=C=O KIQKWYUGPPFMBV-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 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 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000011127 biaxially oriented polypropylene Substances 0.000 description 3
- 229920006378 biaxially oriented polypropylene Polymers 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- GFNDFCFPJQPVQL-UHFFFAOYSA-N 1,12-diisocyanatododecane Chemical compound O=C=NCCCCCCCCCCCCN=C=O GFNDFCFPJQPVQL-UHFFFAOYSA-N 0.000 description 2
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 2
- HVVRUQBMAZRKPJ-UHFFFAOYSA-N 1,3-dimethylimidazolium Chemical compound CN1C=C[N+](C)=C1 HVVRUQBMAZRKPJ-UHFFFAOYSA-N 0.000 description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 2
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 2
- HNIBILYKBWAIPI-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid;hexane-1,6-diol Chemical compound OCC(C)(C)CO.OCCCCCCO.OC(=O)CCCCC(O)=O HNIBILYKBWAIPI-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- KCWDJXPPZHMEIK-UHFFFAOYSA-N isocyanic acid;toluene Chemical class N=C=O.N=C=O.CC1=CC=CC=C1 KCWDJXPPZHMEIK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 2
- RFJSVARKFQELLL-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole;1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound CCN1CN(C)C=C1.FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F RFJSVARKFQELLL-UHFFFAOYSA-N 0.000 description 1
- KTUWFYALZIAAGE-UHFFFAOYSA-N 1-methyl-3-octyl-2h-imidazole Chemical compound CCCCCCCCN1CN(C)C=C1 KTUWFYALZIAAGE-UHFFFAOYSA-N 0.000 description 1
- KQHZEKNQJJSVDN-KVVVOXFISA-N 2-(2-hydroxyethylamino)ethanol;(z)-octadec-9-enoic acid Chemical compound OCCNCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KQHZEKNQJJSVDN-KVVVOXFISA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RCNFOZUBFOFJKZ-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-hexyl-3-methylimidazol-3-ium Chemical compound CCCCCC[N+]=1C=CN(C)C=1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F RCNFOZUBFOFJKZ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of pressure-sensitive adhesive protective films, in particular to a direct-collecting and easy-unreeling polyurethane pressure-sensitive adhesive protective film and a preparation method thereof. The protective film comprises a substrate and a polyurethane pressure-sensitive adhesive layer; the polyurethane pressure-sensitive adhesive layer is mainly prepared from 100 parts of prepolymer, 70-200 parts of solvent, 3-15 parts of polyisocyanate and 0.01-0.02 part of catalyst; the prepolymer is mainly prepared from 10 to 40 parts of dihydric alcohol, 2 to 10 parts of trihydric alcohol, 2 to 8 parts of functional monomer, 5 to 20 parts of polyisocyanate, 0.1 to 1 part of antistatic agent, 0.001 to 0.03 part of catalyst and 20 to 50 parts of solvent; the number of moles of NCO in the polyisocyanate in the prepolymer is less than the sum of the moles of OH in the diol, triol and functional monomer. The protective film has low stripping performance and lower unwinding force, can meet the requirement of the direct-coating direct-collecting protective film on pressure-sensitive adhesive, and can save related structures and processes of release films.
Description
Technical Field
The invention relates to the technical field of pressure-sensitive adhesive protective films, in particular to a direct-collecting and easy-unreeling polyurethane pressure-sensitive adhesive protective film and a preparation method thereof.
Background
Along with the continuous expansion of market share of the China electronic industry, electronic products are layered endlessly, and in order to prevent components such as glass panels, back plates, lenses, touch screen modules and the like of the electronic products from being polluted, the demand of protective films, particularly polyurethane protective films, is gradually increased. Pressure-sensitive adhesives for protective films are mainly of three general categories: acrylic esters, organic silicon and polyurethane, wherein the stripping force of the acrylic ester pressure-sensitive adhesive is wide in controllable range, but the wettability of the acrylic ester pressure-sensitive adhesive on smooth surfaces such as glass plates is insufficient, and the adhesive coating is easy to age and has speckles; the organic silicon pressure-sensitive adhesive protective film has excellent wettability, exhaust property and high-temperature aging resistance, but has the risk of silicon residue, so the application in the electronic field is limited; the polyurethane pressure-sensitive adhesive protective film has excellent wettability and stable mechanical property, and also has good antistatic property, so that the polyurethane pressure-sensitive adhesive protective film has wide application in the field of electronic product protection, especially the protection of various glass panels.
The polyurethane pressure-sensitive adhesive protective film is prepared by uniformly coating polyurethane pressure-sensitive adhesive on a film substrate, drying and curing at high temperature, then rolling and packaging the composite release film, and stripping the release film and then attaching the release film on a protected surface when in use, so that the release film mainly plays a role in protecting the adhesive surface. If the adhesive surface of the protective film is directly rolled for standby after being dried, the cost of raw materials can be saved by nearly half, the protective film is directly unrolled for use in the later period, the release film does not need to be peeled off, the materials can be saved, the process is simplified, the use is convenient, and the production efficiency can be improved.
Aiming at the advantages of the direct-collecting protective film, the formula of the polyurethane pressure-sensitive adhesive needs to be adjusted in a targeted manner: the polyurethane pressure-sensitive adhesive is coated on a high-molecular substrate, after high-temperature drying, the adhesive layer is required to have antistatic performance, and the stripping force needs to be stabilized immediately, otherwise, the phenomena of uneven winding, difficult unwinding, too large static electricity during unwinding and use and the like can occur after direct winding, so that larger loss is caused.
In order to solve the problem of difficult direct winding and unwinding, the existing mode directly coats the polyurethane pressure-sensitive adhesive on the non-release surface of the release film, and the release film does not need to be compounded any more, but the problems of residue and long curing time still exist, and the method has no cost advantage.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a polyurethane pressure-sensitive adhesive protective film which is easy to unwind and is used for solving the technical problems of long curing time, long time required for stable stripping force, need of winding a composite release film, difficult unwinding and the like in the prior art.
The invention further aims to provide a preparation method of the direct-collecting easy-unreeling polyurethane pressure-sensitive adhesive protective film.
In order to achieve the above object of the present invention, an aspect of the present invention provides a direct-receiving and easy-unwinding polyurethane pressure-sensitive adhesive protective film comprising a substrate and a polyurethane pressure-sensitive adhesive layer disposed on a surface of the substrate;
the polyurethane pressure-sensitive adhesive layer is mainly prepared from the following components in parts by weight:
100 parts of prepolymer, 70-200 parts of solvent, 3-15 parts of polyisocyanate and 0.01-0.02 part of catalyst;
the prepolymer is mainly prepared from the following components in parts by weight:
10-40 parts of dihydric alcohol, 2-10 parts of trihydric alcohol, 2-8 parts of functional monomer, 5-20 parts of polyisocyanate, 0.1-1 part of antistatic agent, 0.001-0.03 part of catalyst and 20-50 parts of solvent;
the functional monomer comprises at least one of oleic acid diethanolamine, octadecyl diethanolamine, lauroyl glutamic acid and octaethylene glycol;
in the prepolymer, the number of moles of NCO in the polyisocyanate is less than the sum of the number of moles of OH in the diol, the triol, and the functional monomer;
in the polyurethane pressure-sensitive adhesive layer, the mole number of OH in the prepolymer is smaller than the mole number of NCO in the polyisocyanate.
In a specific embodiment of the present invention, the mass ratio of the triol to the diol is 1: (1 to 5).
In a specific embodiment of the present invention, the glycol comprises at least one of polyethylene glycol, polypropylene glycol, polytetrahydrofuran, and poly (neopentyl glycol-1, 6-hexanediol adipate) glycol.
In a specific embodiment of the present invention, the triol includes at least one of trimethylolpropane, polypropylene triol and polycaprolactone triol.
In a specific embodiment of the invention, the polyisocyanate in the prepolymer is selected from aromatic isocyanates and/or aliphatic isocyanates. Further, the aromatic isocyanate includes at least one of 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 4' -diphenyl diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4' -toluidine diisocyanate, 4' -diphenyl ether diisocyanate, 1, 4-tetramethylxylylene diisocyanate, 1, 3-tetramethylxylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated phenyl methane diisocyanate; the aliphatic isocyanate includes at least one of trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 1, 2-methylene diisocyanate, 2, 3-methylene diisocyanate, 1, 3-methylene diisocyanate, dodecamethylene diisocyanate, and 2, 4-trimethylene diisocyanate.
In a specific embodiment of the present invention, the polyisocyanate in the polyurethane pressure sensitive adhesive includes at least one of hexamethylene diisocyanate, isophorone diisocyanate, and trimethylene diisocyanate.
In a specific embodiment of the present invention, the catalyst in the polyurethane pressure-sensitive adhesive and the catalyst in the prepolymer are each independently selected from at least one of dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxy, tributyltin ethoxy, stannous octoate, trioctyltin oxide, trioctyltin chloride, tributyltin trichloroacetate and tin 2-ethylhexanoate.
In a specific embodiment of the present invention, the solvent in the polyurethane pressure-sensitive adhesive and the solvent in the prepolymer are each independently selected from at least one of ethyl acetate, butyl acetate, toluene, xylene, butanone, cyclohexanone, cyclohexane, acetone, and acetylacetone.
In a specific embodiment of the invention, the antistatic agent is selected from ionic liquids. Further, the ionic liquid includes at least one of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, 1, 3-dimethylimidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-1-methylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide, and 1-hexyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide.
In a specific embodiment of the present invention, the method for preparing the prepolymer comprises:
(a) Under the protection of nitrogen, dihydric alcohol, functional monomer, polyisocyanate and solvent are uniformly mixed, heated to 50-60 ℃, added with partial catalyst and reacted for 2-3 hours at 80-90 ℃;
(b) Cooling to 50-60 deg.c, adding ternary alcohol and catalyst, reaction at 80-90 deg.c for 2-8 hr, adding antistatic agent, stirring and discharging.
In a specific embodiment of the present invention, the mass ratio of the partial catalyst in step (a) to the residual catalyst in step (b) is 1: (1.5 to 2.5).
In a specific embodiment of the present invention, the substrate includes at least one of Polyethylene (PE), polyethylene terephthalate (PET), polyimide (PI), polypropylene (BOPP), and Polyolefin (PO).
In a specific embodiment of the present invention, the thickness of the polyurethane pressure-sensitive adhesive layer is 1 to 15 μm.
The invention also provides a preparation method of any one of the direct-collecting and easy-unreeling polyurethane pressure-sensitive adhesive protective film, which comprises the following steps:
uniformly coating polyurethane pressure-sensitive adhesive on the surface of a substrate, and baking at a high temperature;
the preparation method of the polyurethane pressure-sensitive adhesive comprises the following steps: and mixing the prepolymer with a solvent, adding polyisocyanate and a catalyst, and uniformly stirring to obtain the polyurethane pressure-sensitive adhesive.
In a specific embodiment of the invention, the high-temperature baking temperature is 80-130 ℃, and the high-temperature baking time is 3-8 min.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the polyurethane pressure-sensitive adhesive protective film, the hardness, polymer and crosslinking density of a prepolymer molecular chain can be reasonably adjusted through a certain amount of dihydric alcohol, trihydric alcohol and specific functional monomers; and NCO in the prepolymer is controlled to be less than OH, so that the residual NCO in the prepolymer is prevented from reacting with water in the environment or solvent, and the glue performance is uncontrollable; when the pressure-sensitive adhesive is prepared, the NCO excess OH is controlled, so that the functional groups of the polymer are fully reacted, and after the pressure-sensitive adhesive is baked at a high temperature, the protective film product can quickly reach a low stripping stable state;
(2) The functional monomer is matched with the rest components, so that the polymerization degree of a molecular chain can be effectively improved, the flexibility and the exhaust property of the molecular chain are improved, and the electrostatic derivation effect of the protective film is further improved; meanwhile, antistatic agents are added in the preparation of the prepolymer, so that the antistatic and low film tearing voltage of the prepared polyurethane pressure-sensitive adhesive protective film are further improved;
(3) The protective film disclosed by the invention can quickly reach low stripping performance after being coated and dried, and the adhesive surface is in a solidification stable state after being coated and dried, so that the protective film has lower unwinding force, can meet the requirement of a direct-coating direct-collecting protective film on a pressure-sensitive adhesive, and can save related structures and processes of a release film;
(4) The polyurethane pressure-sensitive adhesive has good wettability, is suitable for being directly coated on the surfaces of low-surface-energy materials such as PE, BOPP, PO and the like, and widens the application range of products.
Detailed Description
The technical solution of the present invention will be clearly and completely described in conjunction with the specific embodiments, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The invention provides a direct-collecting easy-unreeling polyurethane pressure-sensitive adhesive protective film, which comprises a base material and a polyurethane pressure-sensitive adhesive layer arranged on the surface of the base material;
the polyurethane pressure-sensitive adhesive layer is mainly prepared from the following components in parts by weight:
100 parts of prepolymer, 70-200 parts of solvent, 3-15 parts of polyisocyanate and 0.01-0.02 part of catalyst;
the prepolymer is mainly prepared from the following components in parts by weight:
10-40 parts of dihydric alcohol, 2-10 parts of trihydric alcohol, 2-8 parts of functional monomer, 5-20 parts of polyisocyanate, 0.1-1 part of antistatic agent, 0.001-0.03 part of catalyst and 20-50 parts of solvent;
the functional monomer comprises at least one of oleic acid diethanolamine, octadecyl diethanolamine, lauroyl glutamic acid and octaethylene glycol;
in the prepolymer, the number of moles of NCO in the polyisocyanate is less than the sum of the number of moles of OH in the diol, triol and functional monomer;
in the polyurethane pressure-sensitive adhesive layer, the mole number of OH in the prepolymer is smaller than the mole number of NCO in the polyisocyanate.
According to the polyurethane pressure-sensitive adhesive protective film, the hardness, polymer and crosslinking density of a prepolymer molecular chain can be reasonably adjusted through a certain amount of dihydric alcohol, trihydric alcohol and specific functional monomers; and NCO in the prepolymer is controlled to be less than OH, so that the residual NCO in the prepolymer is prevented from reacting with water in the environment or solvent, and the glue performance is uncontrollable; when the pressure-sensitive adhesive is prepared, the NCO excess OH is controlled, so that the functional groups of the polymer are fully reacted, and after the pressure-sensitive adhesive is baked at a high temperature, the protective film product can quickly reach a low stripping stable state.
And through the structural compounding of the functional monomer, the dihydric alcohol and the trihydric alcohol, the molecular weight of the obtained prepolymer is ensured to have certain polymerization degree, meanwhile, the flexibility and the exhaust property are taken into consideration, so that the static electricity leading-out effect of the protective film is improved, the antistatic property of the protective film is improved, and the film tearing voltage is reduced, so that the use requirement of the polyurethane pressure-sensitive adhesive protective film is met.
As in the various embodiments, the components used in the preparation of the polyurethane pressure-sensitive adhesive layer may be used in the following amounts, in parts by weight, compared to 100 parts of prepolymer:
the solvent may be used in an amount ranging from 70 parts, 80 parts, 100 parts, 120 parts, 150 parts, 180 parts, 200 parts, or any two thereof;
the amount of polyisocyanate may be in the range of 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts or any two thereof;
the catalyst may be used in an amount ranging from 0.01 parts, 0.012 parts, 0.015 parts, 0.018 parts, 0.02 parts, or any two thereof.
The dosage of the solvent can be adjusted according to actual demands, and the solvent is preferably adopted to dilute the prepolymer so that the solid content after dilution reaches 15-35%.
In various embodiments, the prepolymer may be prepared from the following components in parts by weight:
the amount of the glycol may be 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts or any two thereof;
the amount of the triol may be 2 parts, 4 parts, 5 parts, 8 parts, 10 parts or any two of these;
the amount of the functional monomer may be 2 parts, 4 parts, 5 parts, 6 parts, 8 parts or a range composed of any two of them;
the amount of polyisocyanate may be in the range of 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, or any two thereof;
the antistatic agent may be used in an amount ranging from 0.1 parts, 0.2 parts, 0.5 parts, 0.8 parts, 1 part, or any two thereof;
the catalyst may be used in an amount ranging from 0.001 parts, 0.005 parts, 0.01 parts, 0.02 parts, 0.03 parts, or any two thereof;
the solvent may be used in an amount ranging from 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, or any two thereof.
In practice, the number of moles of NCO in the polyisocyanate in the prepolymer may be 95%, 90%, 80%, 70% or the like of the sum of the number of moles of OH in the diol, triol and functional monomer or a range of any two thereof. Note that OH here includes an alcoholic hydroxyl group and a carboxyl hydroxyl group.
In the polyurethane pressure-sensitive adhesive layer, the molar number of OH in the prepolymer may be in the range of 98%, 95%, 90%, 85%, 80%, etc. or any two of the molar numbers of NCO in the polyisocyanate used for producing the polyurethane pressure-sensitive adhesive layer. Note that OH here includes an alcoholic hydroxyl group and a carboxyl hydroxyl group.
In a specific embodiment of the present invention, the mass ratio of the triol to the diol is 1: (1 to 5).
As in the various embodiments, the mass ratio of triol to diol may be in the range of 1:1, 1:2, 1:3, 1:4, 1:5, or any two thereof. By further limiting the mass ratio of the triol to the diol, the hardness and the crosslinking density of the molecular chain of the prepolymer can be reasonably adjusted.
In a specific embodiment of the present invention, the glycol comprises at least one of polyethylene glycol, polypropylene glycol, polytetrahydrofuran, and poly (neopentyl glycol-1, 6-hexanediol adipate) glycol.
In a specific embodiment of the present invention, the triol comprises at least one of trimethylolpropane, polypropylene triol and polycaprolactone triol.
In practical operation, if the dihydric alcohol and the trihydric alcohol adopt polymeric polyols, the molecular weight is not limited, and the corresponding purpose can be achieved, and the number average molecular weight can be in the range of 400-4000, such as 400, 1000, 2000, 3000, 4000 or any two of the ranges.
In a specific embodiment of the invention, the polyisocyanate in the prepolymer is selected from aromatic isocyanates and/or aliphatic isocyanates. Further, the aromatic isocyanate includes at least one of 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 4' -diphenyl diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4' -toluidine diisocyanate, 4' -diphenyl ether diisocyanate, 1, 4-tetramethylxylylene diisocyanate, 1, 3-tetramethylxylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated phenyl methane diisocyanate; the aliphatic isocyanate includes at least one of trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 1, 2-methylene diisocyanate, 2, 3-methylene diisocyanate, 1, 3-methylene diisocyanate, dodecamethylene diisocyanate, and 2, 4-trimethylene diisocyanate.
In a specific embodiment of the present invention, the polyisocyanate in the polyurethane pressure sensitive adhesive includes at least one of hexamethylene diisocyanate, isophorone diisocyanate, and trimethylene diisocyanate.
In a specific embodiment of the present invention, the catalyst in the polyurethane pressure-sensitive adhesive and the catalyst in the prepolymer are each independently selected from at least one of dibutyl tin dichloride, dibutyl tin oxide, dibutyl tin dibromide, dibutyl tin dimaleate, dibutyl tin dilaurate, dioctyl tin dilaurate, dibutyl tin diacetate, dibutyl tin sulfide, tributyl tin oxide, tributyl tin acetate, triethyl tin ethoxy, tributyl tin ethoxy, stannous octoate, trioctyl tin oxide, trioctyl tin chloride, tributyl tin trichloroacetate, and tin 2-ethylhexanoate. The kind of the catalyst is not limited to this, and it is sufficient to catalyze the reaction of OH and NCO.
In a specific embodiment of the present invention, the solvent in the polyurethane pressure-sensitive adhesive and the solvent in the prepolymer are each independently selected from at least one of ethyl acetate, butyl acetate, toluene, xylene, butanone, cyclohexanone, cyclohexane, acetone, and acetylacetone.
In a specific embodiment of the invention, the antistatic agent is selected from ionic liquids. Further, the ionic liquid comprises at least one of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, 1, 3-dimethylimidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-1-methylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide and 1-hexyl-3-methylimidazoldi (trifluoromethanesulfonyl) imide.
In a specific embodiment of the present invention, the method for preparing the prepolymer comprises:
(a) Under the protection of nitrogen, dihydric alcohol, functional monomer, polyisocyanate and solvent are uniformly mixed, heated to 50-60 ℃, added with partial catalyst and reacted for 2-3 hours at 80-90 ℃;
(b) Cooling to 50-60 deg.c, adding ternary alcohol and catalyst, reaction at 80-90 deg.c for 2-8 hr, adding antistatic agent, stirring and discharging.
In the preparation of the prepolymer, dihydric alcohol and a functional monomer are added in the initial stage of the reaction, and the trihydric alcohol is added in the secondary catalysis, so that the crosslinking density of the polymer can be improved. Meanwhile, the catalyst is added in batches at different reaction times, so that raw materials are gradually reacted and crosslinked, the state of stable performance can be quickly achieved after the baking and drying in the later period, and the curing time of the protective film is greatly shortened.
In a specific embodiment of the present invention, the mass ratio of the partial catalyst in step (a) to the remaining catalyst in step (b) is 1: (1.5 to 2.5).
In various embodiments, the mass ratio of the partial catalyst in step (a) to the remaining catalyst in step (b) may be in the range of 1:1.5, 1:1.8, 1:2, 1:2.2, 1:2.5, or any two thereof.
In a specific embodiment of the present invention, the substrate includes at least one of Polyethylene (PE), polyethylene terephthalate (PET), polyimide (PI), polypropylene (BOPP), and Polyolefin (PO).
In a specific embodiment of the present invention, the thickness of the polyurethane pressure-sensitive adhesive layer is 1 to 15 μm.
In actual practice, the thickness of the polyurethane pressure-sensitive adhesive layer may be adjusted according to the requirements of the actual polyurethane pressure-sensitive adhesive protective film, for example, the thickness of the polyurethane pressure-sensitive adhesive layer may be 1 μm, 2 μm, 5 μm, 8 μm, 10 μm, 12 μm, 15 μm or a range composed of any two thereof.
The invention also provides a preparation method of any one of the directly-received and easily-unreeled polyurethane pressure-sensitive adhesive protective films, which comprises the following steps:
uniformly coating polyurethane pressure-sensitive adhesive on the surface of a substrate, and baking at a high temperature;
the preparation method of the polyurethane pressure-sensitive adhesive comprises the following steps: and mixing the prepolymer with a solvent, adding polyisocyanate and a catalyst, and uniformly stirring to obtain the polyurethane pressure-sensitive adhesive.
In actual operation, after high-temperature baking, the polyurethane pressure-sensitive adhesive layer with a certain thickness is formed by curing, and then the polyurethane pressure-sensitive adhesive layer can be directly rolled without additionally compounding a release film.
In the specific embodiment of the invention, the high-temperature baking temperature is 80-130 ℃, and the high-temperature baking time is 3-8 min.
As in the various embodiments, the temperature of the high temperature bake may be 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃ or a range consisting of any two thereof, and the time of the high temperature bake may be 3min, 4min, 5min, 6min, 7min, 8min or a range consisting of any two thereof.
The polyurethane pressure-sensitive adhesive protective film capable of being directly collected and easily unwound can quickly achieve stable stripping force after being coated and dried, can achieve the effect of being easily collected and easily unwound under the condition of not compounding release films, saves one release film, greatly shortens the time of post curing, improves the production efficiency of the polyurethane protective film, and is convenient and environment-friendly to use.
Example 1
The embodiment provides a preparation method of a direct-collecting and easy-unreeling polyurethane pressure-sensitive adhesive protective film, which comprises the following steps:
(1) Preparing a prepolymer: respectively placing polyethylene glycol (600), trimethylolpropane, 2, 4-toluene diisocyanate and the like into a reaction bottle, and distilling under reduced pressure to remove water for later use. Under the protection of nitrogen, adding 30 parts by weight of polyethylene glycol (600), 8 parts by weight of lauroyl glutamic acid, 18 parts by weight of 2, 4-toluene diisocyanate, 20 parts by weight of toluene and 14 parts by weight of ethyl acetate into a reaction vessel, uniformly mixing, heating to 60 ℃, adding 0.005 part by weight of stannous octoate after 1h, heating to 80 ℃, reacting for 3h, cooling to 60 ℃, adding 10 parts by weight of trimethylolpropane and 0.01 part by weight of dibutyl tin dilaurate, heating to 80 ℃, reacting for 2h, cooling to 50 ℃, adding 0.3 part by weight of 1, 3-dimethyl imidazolium bis (trifluoromethyl sulfonyl) imine, uniformly stirring, filtering, and discharging to obtain a prepolymer.
(2) Preparing polyurethane pressure-sensitive adhesive: 100 parts by weight of the prepolymer prepared in the step (1) are weighed, 100 parts by weight of ethyl acetate is added, the mixture is stirred uniformly, 8 parts by weight of hexamethylene diisocyanate and 0.01 part by weight of tin 2-ethylhexanoate are added, and the mixture is stirred uniformly, so that the polyurethane pressure-sensitive adhesive is obtained.
(3) Preparing a polyurethane pressure-sensitive adhesive protective film: uniformly coating the polyurethane pressure-sensitive adhesive prepared in the step (2) on the surface of a transparent PET film with the thickness of 50 mu m, then baking at the high temperature of 120 ℃ for 5min, and curing to form a polyurethane pressure-sensitive adhesive layer with the thickness of 10 mu m, thus obtaining the polyurethane pressure-sensitive adhesive protective film.
Example 2
The embodiment provides a preparation method of a direct-collecting and easy-unreeling polyurethane pressure-sensitive adhesive protective film, which comprises the following steps:
(1) Preparing a prepolymer: respectively placing polyethylene glycol (600), 1, 2-methylene diisocyanate and polycaprolactone triol serving as raw materials into a reaction bottle, and distilling under reduced pressure to remove water for later use. Under the protection of nitrogen, 40 parts by weight of polyethylene glycol (600), 3 parts by weight of diethanolamine oleate, 20 parts by weight of 1, 2-methylene diisocyanate, 20 parts by weight of toluene and 22 parts by weight of ethyl acetate are added into a reaction vessel, uniformly mixed, heated to 50 ℃, 0.01 part by weight of dioctyl tin dilaurate is added after 1h, heated to 80 ℃, reacted for 2h, cooled to 60 ℃, 10 parts by weight of polycaprolactone triol and 0.02 part by weight of tin 2-ethylhexanoate are added, heated to 90 ℃, reacted for 6h, cooled to 50 ℃,1 part by weight of 1-octyl-3-methylimidazole bis (trifluoromethanesulfonyl) imine is added, uniformly stirred, filtered and discharged to obtain a prepolymer.
(2) Preparing polyurethane pressure-sensitive adhesive: 100 parts by weight of the prepolymer prepared in the step (1) are weighed, 70 parts by weight of ethyl acetate is added, the mixture is stirred uniformly, 7 parts by weight of hexamethylene diisocyanate and 0.015 part by weight of tin 2-ethylhexanoate are added, and the mixture is stirred uniformly, so that the polyurethane pressure-sensitive adhesive is obtained.
(3) Preparing a polyurethane pressure-sensitive adhesive protective film: uniformly coating the polyurethane pressure-sensitive adhesive prepared in the step (2) on the surface of a transparent PET film with the thickness of 75 mu m, then baking at the high temperature of 130 ℃ for 4min, and curing to form a polyurethane pressure-sensitive adhesive layer with the thickness of 15 mu m, thus obtaining the polyurethane pressure-sensitive adhesive protective film.
Example 3
The embodiment provides a preparation method of a direct-collecting and easy-unreeling polyurethane pressure-sensitive adhesive protective film, which comprises the following steps:
(1) Preparing a prepolymer: respectively placing polyethylene glycol (600), 2, 4-trimethylene diisocyanate and polycaprolactone triol serving as raw materials into a reaction bottle, and distilling under reduced pressure to remove water for later use. Under the protection of nitrogen, adding 30 parts by weight of polyethylene glycol (600), 5 parts by weight of octadecyl diethanolamine, 15 parts by weight of 2, 4-trimethylene diisocyanate, 6 parts by weight of acetylacetone and 30 parts by weight of ethyl acetate into a reaction vessel, uniformly mixing, heating to 55 ℃, adding 0.01 part by weight of tin 2-ethylhexanoate after 1h, heating to 80 ℃, reacting for 3h, cooling to 60 ℃, adding 6 parts by weight of polycaprolactone triol and 0.02 part by weight of stannous octoate, heating to 80 ℃, reacting for 2.5h, cooling to 50 ℃, adding 0.4 part by weight of 1-ethyl-3-methylimidazole bistrifluoro-sulfimide salt, stirring uniformly, filtering, and discharging to obtain a prepolymer.
(2) Preparing polyurethane pressure-sensitive adhesive: weighing 100 parts by weight of the prepolymer prepared in the step (1), adding 200 parts by weight of ethyl acetate, stirring uniformly, adding 10 parts by weight of hexamethylene diisocyanate and 0.02 part by weight of dibutyl tin dilaurate, and stirring uniformly to obtain the polyurethane pressure-sensitive adhesive.
(3) Preparing a polyurethane pressure-sensitive adhesive protective film: uniformly coating the polyurethane pressure-sensitive adhesive prepared in the step (2) on the surface of a transparent PE film with the thickness of 45 mu m, then baking at the high temperature of 90 ℃ for 8min, and curing to form a polyurethane pressure-sensitive adhesive layer with the thickness of 4 mu m, thus obtaining the polyurethane pressure-sensitive adhesive protective film.
Example 4
The embodiment provides a preparation method of a direct-collecting and easy-unreeling polyurethane pressure-sensitive adhesive protective film, which comprises the following steps:
(1) Preparing a prepolymer: respectively placing polyethylene glycol (600), trimethylolpropane, 2, 4-toluene diisocyanate and the like into a reaction bottle, and distilling under reduced pressure to remove water for later use. Under the protection of nitrogen, adding 30 parts by weight of polyethylene glycol (600), 8 parts by weight of lauroyl glutamic acid, 18 parts by weight of 2, 4-toluene diisocyanate, 20 parts by weight of toluene and 14 parts by weight of ethyl acetate into a reaction vessel, uniformly mixing, heating to 60 ℃, adding 0.025 parts by weight of stannous octoate after 1h, heating to 80 ℃, reacting for 3h, adding 10 parts by weight of trimethylolpropane, continuously reacting for 2h, cooling to 50 ℃, adding 0.3 parts by weight of 1, 3-dimethyl imidazolium bis (trifluoromethyl sulfonyl) imine, uniformly stirring, filtering, and discharging to obtain a prepolymer.
(2) Preparing polyurethane pressure-sensitive adhesive: 100 parts by weight of the prepolymer prepared in the step (1) are weighed, 100 parts by weight of ethyl acetate is added, the mixture is stirred uniformly, 8 parts by weight of hexamethylene diisocyanate is added, and the mixture is stirred uniformly, so that the polyurethane pressure-sensitive adhesive is obtained.
(3) Preparing a polyurethane pressure-sensitive adhesive protective film: uniformly coating the polyurethane pressure-sensitive adhesive prepared in the step (2) on the surface of a transparent PET film with the thickness of 50 mu m, then baking at the high temperature of 120 ℃ for 5min, and curing to form a polyurethane pressure-sensitive adhesive layer with the thickness of 10 mu m, thus obtaining the polyurethane pressure-sensitive adhesive protective film.
Example 5
In this example, the method for preparing the direct-recycling easy-unwinding polyurethane pressure-sensitive adhesive protective film according to example 3 is different only in the amounts of polyethylene glycol (600) and polycaprolactone triol used in step (1).
In this example, the amount of polyethylene glycol (600) was 31 parts by weight and the amount of polycaprolactone triol was 5 parts by weight.
Comparative example 1
Comparative example 1 the method for preparing the direct-receiving easy-unwinding polyurethane pressure-sensitive adhesive protective film of reference example 3 is different only in the amount of 2, 4-trimethylene diisocyanate, polyethylene glycol (600) used in step (1).
In this comparative example, the amount of 2, 4-trimethylene diisocyanate was 20 parts by weight and the polyethylene glycol (600) was 25 parts by weight.
Comparative example 2
Comparative example 2 reference example 3 was prepared with the difference that: in the preparation of the prepolymer in the step (1), octadecyl diethanol amine is not added.
Comparative example 3
Comparative example 3 reference example 3 preparation method, differing in: no antistatic agent 1-ethyl-3-methylimidazole bistrifluoromethanesulfonimide salt was added.
Experimental example
The relevant performance test and comparison were carried out for each example and comparative example respectively, the relevant test items and methods are referenced below, and the test results are shown in table 1:
rubber surface resistance: standing on the adhesive surface of the protective film by using a surface resistance meter, and directly measuring the resistance of the adhesive surface;
offline peel force: after the preparation of the polyurethane pressure-sensitive adhesive protective film is finished, namely the polyurethane pressure-sensitive adhesive is baked and dried on the surface of the high polymer film to form a pressure-sensitive adhesive layer, and after cooling, the 180-degree stripping force is tested according to GB/T2792-2014;
stable peel force: after the polyurethane pressure-sensitive adhesive protective film is dried and rolled, curing for 7 days at normal temperature, and testing 180-degree stripping force according to national standard GB/T2792-2014;
unreeling force: after the adhesive surface of the polyurethane pressure-sensitive adhesive protective film is dried, the adhesive surface is directly compounded with an equivalent film material (the same material as a base film coated with the polyurethane pressure-sensitive adhesive), and is cured for 7 days at normal temperature, the 180-degree stripping force of stripping the single-layer protective film from the surface of the composite film is tested by referring to the mode of national standard GB/T2792-2014, and when the stripping force is more than or equal to 100g/25mm, the stripping force is considered to be larger;
film tearing voltage: and (3) sticking a polyurethane pressure-sensitive adhesive protective film on the surface of the glass, standing for 24 hours, rapidly stripping at a speed of not less than 500m/min, and testing the static voltage of the surface of the glass by using a static voltage tester.
Table 1 data comparison of different examples and comparative examples
From the test results, the polyurethane pressure-sensitive adhesive protective film prepared by the embodiment of the invention has similar offline stripping force and stable stripping force, has small unreeling force (for example, can be less than 5g/25 mm) when being directly reeled, is easy to realize smooth unreeling, has the film tearing voltage of less than 100V, and is very friendly to protected materials; the preparation formula and the process of the polyurethane pressure-sensitive adhesive have great influence on the performance of the protective film, especially the off-line stripping force, the unwinding force and the film tearing voltage.
Comparative examples 1 and 4 show that in the preparation of the prepolymer, the catalyst is added at one time, the reaction speed of the chain extension in the early stage is too high, the crosslinking density of the molecular chains is small, the molecular weight distribution width is large, and the off-line stripping force is too large after the prepolymer is coated on the substrate, so that the unwinding force is large.
Comparative examples 3 and 5 show that when the ratio of the diol and the triol exceeds a certain range, the off-line peeling force and the unreeling force of the protective film are affected to some extent.
As is clear from comparative examples and comparative example 1, the molar number of NCO in isocyanate is larger than the sum of molar numbers of OH in diol, triol and functional monomer in the prepolymer preparation process, resulting in poor film forming property, and the off-line peeling force and the unwinding force are too large to be suitable for direct coating of direct-receiving protective film.
As is clear from comparative examples and comparative example 2, functional monomers were not added during the preparation of the prepolymer, and thus wettability and static electricity conductive properties were insufficient, so that when the surface tension of the base film was small, the phenomenon of insufficient adhesion was liable to occur, and the film tearing voltage was also large.
Comparative examples and comparative example 3 show that: the antistatic agent is not added, the film tearing voltage is larger, but the adhesive surface still has a certain antistatic effect, mainly because the functional monomer selected in the pressure-sensitive adhesive has a long-chain structure and has certain air exhaust property and electrostatic conduction effect.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. The direct-collecting easy-unreeling polyurethane pressure-sensitive adhesive protective film is characterized by comprising a base material and a polyurethane pressure-sensitive adhesive layer arranged on the surface of the base material;
the polyurethane pressure-sensitive adhesive layer is mainly prepared from the following components in parts by weight:
100 parts of prepolymer, 70-200 parts of solvent, 3-15 parts of polyisocyanate and 0.01-0.02 part of catalyst;
the prepolymer is mainly prepared from the following components in parts by weight:
10-40 parts of dihydric alcohol, 2-10 parts of trihydric alcohol, 2-8 parts of functional monomer, 5-20 parts of polyisocyanate, 0.1-1 part of antistatic agent, 0.001-0.03 part of catalyst and 20-50 parts of solvent;
the functional monomer comprises at least one of oleic acid diethanolamine, octadecyl diethanolamine, lauroyl glutamic acid and octaethylene glycol;
in the prepolymer, the number of moles of NCO in the polyisocyanate is less than the sum of the number of moles of OH in the diol, the triol, and the functional monomer;
in the polyurethane pressure-sensitive adhesive layer, the mole number of OH in the prepolymer is smaller than the mole number of NCO in the polyisocyanate.
2. The direct-collecting easy-unreeling polyurethane pressure-sensitive adhesive protective film of claim 1, wherein the mass ratio of the triol to the diol is 1: (1-5);
preferably, the dihydric alcohol comprises at least one of polyethylene glycol, polypropylene glycol, polytetrahydrofuran and neopentyl glycol-1, 6-hexanediol adipate diol;
preferably, the triol includes at least one of trimethylolpropane, polypropylene triol and polycaprolactone triol.
3. The direct-recycling easy-unreeling polyurethane pressure-sensitive adhesive protective film of claim 1 wherein the polyisocyanate in the prepolymer is selected from aromatic isocyanate and/or aliphatic isocyanate.
4. The direct-recycling easy-unreeling polyurethane pressure-sensitive adhesive protective film of claim 1 wherein the polyisocyanate in the polyurethane pressure-sensitive adhesive comprises at least one of hexamethylene diisocyanate, isophorone diisocyanate, and trimethylene diisocyanate.
5. The direct-recycling easy-unwind polyurethane pressure-sensitive adhesive protective film according to claim 1, characterized in that the catalyst in the polyurethane pressure-sensitive adhesive and the catalyst in the prepolymer are each independently selected from at least one of dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxy, tributyltin ethoxy, stannous octoate, trioctyltin oxide, trioctyltin chloride, tributyltin trichloroacetate and tin 2-ethylhexanoate;
and/or the solvent in the polyurethane pressure-sensitive adhesive and the solvent in the prepolymer are each independently selected from at least one of ethyl acetate, butyl acetate, toluene, xylene, butanone, cyclohexanone, cyclohexane, acetone, and acetylacetone.
6. The direct-recovery easy-unreeling polyurethane pressure-sensitive adhesive protective film of claim 1 wherein the antistatic agent is selected from ionic liquids;
preferably, the ionic liquid comprises at least one of 1-ethyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide salt, 1, 3-dimethylimidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-1-methylpiperidinium bis (trifluoromethanesulfonyl) imide, 1-octyl-3-methylimidazolium bis (trifluoromethanesulfonyl) imide and 1-hexyl-3-methylimidazoldi (trifluoromethanesulfonyl) imide.
7. The direct-recycling easy-unreeling polyurethane pressure-sensitive adhesive protective film of claim 1, wherein the preparation method of the prepolymer comprises the following steps:
(a) Under the protection of nitrogen, the dihydric alcohol, the functional monomer, the polyisocyanate and the solvent are uniformly mixed, heated to 50-60 ℃, added with partial catalyst and reacted for 2-3 hours at 80-90 ℃;
(b) Cooling to 50-60 ℃, adding the triol and the rest catalyst, reacting for 2-8 hours at 80-90 ℃, adding the antistatic agent, uniformly stirring, and discharging;
preferably, the mass ratio of the partial catalyst in step (a) to the residual catalyst in step (b) is 1: (1.5-2.5).
8. The direct-recycling easy-unreeling polyurethane pressure-sensitive adhesive protective film of claim 1 wherein the substrate comprises at least one of polyethylene, polyethylene terephthalate, polyimide, and polypropylene;
and/or the thickness of the polyurethane pressure-sensitive adhesive layer is 1-15 mu m.
9. The method for preparing the direct-collecting easy-unreeling polyurethane pressure-sensitive adhesive protective film of any one of claims 1 to 8, which is characterized by comprising the following steps:
uniformly coating polyurethane pressure-sensitive adhesive on the surface of a substrate, and baking at a high temperature;
the preparation method of the polyurethane pressure-sensitive adhesive comprises the following steps: and mixing the prepolymer with a solvent, adding polyisocyanate and a catalyst, and uniformly stirring to obtain the polyurethane pressure-sensitive adhesive.
10. The method according to claim 9, wherein the high temperature baking is performed at 80 to 130 ℃ for 3 to 8 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311752075.0A CN117757376A (en) | 2023-12-19 | 2023-12-19 | Direct-collecting easy-unreeling polyurethane pressure-sensitive adhesive protective film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311752075.0A CN117757376A (en) | 2023-12-19 | 2023-12-19 | Direct-collecting easy-unreeling polyurethane pressure-sensitive adhesive protective film and preparation method thereof |
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| Publication Number | Publication Date |
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| CN117757376A true CN117757376A (en) | 2024-03-26 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN202311752075.0A Pending CN117757376A (en) | 2023-12-19 | 2023-12-19 | Direct-collecting easy-unreeling polyurethane pressure-sensitive adhesive protective film and preparation method thereof |
Country Status (1)
| Country | Link |
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| CN (1) | CN117757376A (en) |
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2023
- 2023-12-19 CN CN202311752075.0A patent/CN117757376A/en active Pending
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