CN117343374B - PE film with heat-resistant coating and preparation method thereof - Google Patents
PE film with heat-resistant coating and preparation method thereof Download PDFInfo
- Publication number
- CN117343374B CN117343374B CN202311616781.2A CN202311616781A CN117343374B CN 117343374 B CN117343374 B CN 117343374B CN 202311616781 A CN202311616781 A CN 202311616781A CN 117343374 B CN117343374 B CN 117343374B
- Authority
- CN
- China
- Prior art keywords
- heat
- resistant coating
- film
- polyethylene
- glycol
- 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.)
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- 239000011248 coating agent Substances 0.000 title claims abstract description 85
- 238000000576 coating method Methods 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000004698 Polyethylene Substances 0.000 claims description 110
- 229920000573 polyethylene Polymers 0.000 claims description 96
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 22
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 claims description 17
- 239000011256 inorganic filler Substances 0.000 claims description 16
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 16
- 239000003431 cross linking reagent Substances 0.000 claims description 14
- 239000004814 polyurethane Substances 0.000 claims description 13
- 229920002635 polyurethane Polymers 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 229920001684 low density polyethylene Polymers 0.000 claims description 12
- 239000004702 low-density polyethylene Substances 0.000 claims description 12
- -1 polyoxypropylene Polymers 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 11
- 229920001903 high density polyethylene Polymers 0.000 claims description 10
- 239000004700 high-density polyethylene Substances 0.000 claims description 10
- 239000005056 polyisocyanate Substances 0.000 claims description 10
- 229920001228 polyisocyanate Polymers 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- 229920005862 polyol Polymers 0.000 claims description 9
- 150000003077 polyols Chemical class 0.000 claims description 9
- 229920001451 polypropylene glycol Polymers 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 239000011203 carbon fibre reinforced carbon Chemical group 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 6
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims description 4
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 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 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 3
- 230000002902 bimodal effect Effects 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 229920001002 functional polymer Polymers 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 30
- 238000000034 method Methods 0.000 description 18
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 238000007789 sealing Methods 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000003973 paint Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000011247 coating layer Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000004806 packaging method and process Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 229920006262 high density polyethylene film Polymers 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 2
- 229940011051 isopropyl acetate Drugs 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- RDLGTRBJUAWSAF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-2-one Chemical compound CC(=O)CC1C=CC=CC1(C)O RDLGTRBJUAWSAF-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004595 color masterbatch Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 239000012775 heat-sealing material Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920006284 nylon film Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BFYJDHRWCNNYJQ-UHFFFAOYSA-N oxo-(3-oxo-3-phenylpropoxy)-(2,4,6-trimethylphenyl)phosphanium Chemical compound CC1=CC(C)=CC(C)=C1[P+](=O)OCCC(=O)C1=CC=CC=C1 BFYJDHRWCNNYJQ-UHFFFAOYSA-N 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- ZUFQCVZBBNZMKD-UHFFFAOYSA-M potassium 2-ethylhexanoate Chemical compound [K+].CCCCC(CC)C([O-])=O ZUFQCVZBBNZMKD-UHFFFAOYSA-M 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 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 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention discloses a PE film with a heat-resistant coating and a preparation method thereof, belonging to the field of preparation of functional polymer materials.
Description
Technical Field
The invention relates to the field of preparation of functional polymer materials, in particular to a PE film with a heat-resistant coating and a preparation method thereof.
Background
Polyethylene (PE) is a very important general plastic, has stable chemical property, is nontoxic and tasteless, and is an important material for manufacturing plastic flexible packages. Because of high strength, good toughness and moderate melting point, the plastic soft bag is often used as an inner layer heat sealing material for packaging edge sealing and bonding. However, in the actual heat sealing production process, the outer layer of the PE film needs to bear the heat of a hot pressing cutter, if the temperature of the cutter is too low, the heat sealing strength is insufficient, and the package is easy to open; if the temperature of the cutter is too high, the PE film is easy to melt and adhere to the cutter. The heat sealing temperature window of the common PE film is too narrow, which is not beneficial to continuous production.
The prior art is to compound a material with high melting point on the outer layer of the PE film, such as a biaxially oriented polyester film, a nylon film or a polypropylene film. However, with the development of packaging industry and the improvement of environmental protection consciousness, more and more packaging product companies tend to develop recyclable PE packages, and the composite film contains various different materials, is difficult to separate after being formed, and cannot meet the requirements of package recycling. For example, the patent of Chinese patent No. CN111267446 discloses a single transparent material barrier packaging composite film and a preparation method thereof, specifically, a heat-resistant PE film and a low-temperature-resistant PE film are respectively prepared, and then the heat-resistant PE film and the low-temperature-resistant PE film are bonded and molded by glue; wherein, the heat-resistant PE film component mainly adopts high-density polyethylene (HDPE) to improve the melting point of the PE film. The method needs to produce high-temperature and low-temperature PE films respectively and then glue the PE films, and is complex and complex in process. In another example, the heat resistance of the HDPE film is improved by performing a second unidirectional stretching treatment on the HDPE film to induce the crystallization of the HDPE, thereby improving the crystallinity and the regularity of the HDPE film. Although the heat resistance of the PE film is improved, the heat sealing temperature is correspondingly improved, and the heat sealing processing window of the PE film is not obviously improved. For example, chinese patent numbers CN114953681 and CN112571908 respectively disclose that the heat resistance of PE film is improved by using the method of silane steam crosslinking and electron irradiation crosslinking by utilizing the multilayer coextrusion technology and crosslinking technology to prepare the composite PE film. However, the method has high requirements on investment of production equipment and process control, so that the cost of the product is high.
Therefore, how to prepare a recyclable, high heat resistant PE film by a simple and controllable means remains an important research topic in the industry.
Disclosure of Invention
Based on the above, in order to solve the problem that the heat resistance, flexibility, transparency and binding force of PE are difficult to meet the use requirement on the premise of the recoverability of PE in the prior art, the invention provides a PE film with a heat-resistant coating and a preparation method thereof, and the specific technical scheme is as follows:
the PE film comprises a heat-resistant coating and a PE layer which are sequentially connected, wherein the thickness of the heat-resistant coating accounts for 1% -5% of the total thickness of the PE film;
the heat-resistant coating comprises the following raw materials in parts by weight:
100 parts of isocyanate-terminated polyurethane;
5-35 parts of a cross-linking agent;
0-30 parts of modified inorganic filler;
0.05-0.5 parts of photoinitiator;
0.05-1 part of catalyst.
Further, the isocyanate-terminated polyurethane is a polyurethane prepolymer of terminated isocyanate, and the number average molecular weight is 10000-50000.
Further, the isocyanate-terminated polyurethane is prepared by polycondensation reaction of polyol and polyisocyanate, and the molar ratio of the polyol to the polyisocyanate is 1 (1.2-1.8).
Further, the polyhydric alcohol is selected from one or more of ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, glycerol, polyethylene glycol, polypropylene glycol, polytetrahydrofuran ether glycol, polyethylene glycol adipate glycol, polyethylene glycol terephthalate glycol, polypropylene oxide glycol and polypropylene oxide triol; the polyisocyanate is selected from one or more of diphenylmethane diisocyanate, 2, 4-toluene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
Further, the crosslinking agent is a compound containing an epoxy functional group and a carbon-carbon double bond.
Further, the compound is one or more of glycidyl methacrylate, glycidyl acrylate and allyl glycidyl ether.
Further, the modified inorganic filler is lamellar inorganic filler obtained by modifying a silane coupling agent containing double bonds.
Further, the silane coupling agent containing a double bond is selected from one or more of gamma-methacryloxypropyl trimethoxysilane, gamma-methacryloxypropyl triethoxysilane, vinyl trimethoxysilane and vinyl triethoxysilane.
Further, the PE layer comprises polyethylene, and the polyethylene is one or more of low density polyethylene, linear low density polyethylene, high density polyethylene, metallocene polyethylene, bimodal polyethylene, ethylene-alpha-olefin copolymer.
In addition, the application also provides a preparation method of the PE film with the heat-resistant coating, which comprises the following steps:
preparing a PE layer with the thickness of 20-500 mu m;
after mixing the raw materials of the heat-resistant coating, dissolving the raw materials in a solvent to prepare a heat-resistant coating;
and (3) coating the heat-resistant coating on the PE layer, performing single-side or double-side UV irradiation reaction in an ultraviolet lamp box with the relative humidity of 55% -95%, and then performing drying treatment to obtain the PE film with the heat-resistant coating.
According to the scheme, the reactive coating is introduced into the PE layer, and the heat-resistant coating with a three-dimensional structure is formed through the moisture and photoinitiated crosslinking/grafting reaction, so that the heat resistance of the PE film is improved, the coating proportion is lower than 5%, and the subsequent recoverability, softness and transparency of the PE film are not affected. Compared with the prior art, the scheme of the invention has the following advantages:
(1) The isocyanate end-capped polyurethane in the heat-resistant coating reacts with the epoxy functional groups in the crosslinking agent to be chain-extended and crosslinked, and simultaneously, the carbon-carbon double bonds in the crosslinking agent are grafted to the PE surface through free radical reaction under the action of UV light and a photoinitiator, so that the heat-resistant coating with high crosslinking density and good bonding force with the PE film is formed, and the heat-resistant coating after crosslinking has the characteristic of being insoluble and insoluble, so that the heat resistance of the heat-resistant coating can be remarkably improved.
(2) The invention adopts the modified inorganic lamellar filler with high diameter-thickness ratio to improve the heat shrinkage performance of the composite film, and the lamellar filler can reduce the filler consumption so as to reduce the influence on the transparency of the film; the adhesive force to the PE layer can be improved through grafting after the silane coupling agent is modified.
(3) The scheme of the invention can be produced in batches by conventional equipment, does not need to additionally input expensive mechanical equipment, and has the characteristics of high efficiency, low cost and easy popularization.
Drawings
FIG. 1 is a schematic cross-sectional view under an optical microscope of a PE film prepared in the example;
FIG. 2 is a schematic view of the curing of the heat-resistant coating of example 1 of the present invention.
Reference numerals illustrate:
1. a UV irradiation box; 2. and a drying box.
Detailed Description
The present invention will be described in further detail with reference to the following examples thereof in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
According to the PE film with the heat-resistant coating, the PE film comprises the heat-resistant coating and the PE layer which are sequentially connected, and the thickness of the heat-resistant coating is 1% -5% of the total thickness of the PE film;
the heat-resistant coating comprises the following raw materials in parts by weight:
100 parts of isocyanate-terminated polyurethane;
5-35 parts of a cross-linking agent;
0-30 parts of modified inorganic filler;
0.05-0.5 parts of photoinitiator;
0.05-1 part of catalyst.
In one embodiment, the isocyanate-terminated polyurethane is a polyurethane prepolymer of terminated isocyanate, and the number average molecular weight is 10000-50000.
In one embodiment, the isocyanate-terminated polyurethane is prepared by polycondensation reaction of polyol and polyisocyanate, and the molar ratio of the polyol to the polyisocyanate is 1 (1.2-1.8).
In one embodiment, the polyol is selected from one or more of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, glycerol, polyethylene glycol, polypropylene glycol, polytetrahydrofuran ether glycol, polyethylene glycol adipate glycol, polyethylene glycol terephthalate glycol, polypropylene oxide glycol, and polypropylene oxide triol; the polyisocyanate is selected from one or more of diphenylmethane diisocyanate, 2, 4-toluene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
In one embodiment, the method of preparing the isocyanate-terminated polyurethane comprises the steps of: and placing the polyol in a reaction vessel, heating at 110-140 ℃ for 2-5 hours to remove water, cooling to 80-95 ℃, adding the metered polyisocyanate while stirring under the protection of nitrogen, and continuing stirring and reacting for 3-5 hours in the nitrogen atmosphere after the addition is finished to obtain the isocyanate-terminated polyurethane.
In one embodiment, the crosslinking agent is a compound containing an epoxy functional group and a carbon-carbon double bond.
In one embodiment, the compound is a mixture of one or more of glycidyl methacrylate, glycidyl acrylate, and allyl glycidyl ether.
In one embodiment, the modified inorganic filler is a lamellar inorganic filler obtained by modifying a silane coupling agent containing double bonds.
In one embodiment, the lamellar inorganic filler is a mixture of one or more of kaolin, mica, talc and graphite.
In one embodiment, the silane coupling agent containing a double bond may be selected from one or more of γ -methacryloxypropyl trimethoxysilane, γ -methacryloxypropyl triethoxysilane, vinyl trimethoxysilane, and vinyl triethoxysilane. Preferably one or both of gamma-methacryloxypropyl trimethoxysilane and vinyl trimethoxysilane.
In one embodiment, the method for preparing the modified inorganic filler comprises the steps of: and placing the lamellar inorganic filler in a mixing stirrer, stirring and heating at 100-120 ℃ for 2-5 hours to remove water, then cooling to 70-95 ℃, spraying the silane coupling agent containing double bonds on the lamellar inorganic filler in a stirring state, and continuing stirring and reacting at 70-95 ℃ for 3-5 hours to obtain the modified inorganic filler.
In one embodiment, the amount of the silane coupling agent containing double bonds is 5% -30% of the mass of the inorganic filler.
In one embodiment, the photoinitiator is one or more of benzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 2,4, 6-trimethylbenzophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylphenyl acetone, benzoin, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, and 2,4, 6-trimethylbenzoyl ethoxy phenyl phosphine oxide. The photoinitiator can generate active free radicals under the irradiation of ultraviolet light with specific wavelength and intensity and trigger the polymer to generate chain reaction.
In one embodiment, the catalyst is one or more of triethylamine, triethylenediamine, pentamethyldiethylenetriamine, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethylalkylenediamine, stannous octoate, dibutyltin dilaurate, potassium acetate, and potassium octoate. The catalyst is used for catalyzing the reaction of isocyanate-terminated polyurethane and a crosslinking agent.
In one embodiment, the material of the PE layer comprises polyethylene, and the polyethylene is one or more of low density polyethylene, linear low density polyethylene, high density polyethylene, metallocene polyethylene, bimodal polyethylene, ethylene-alpha-olefin copolymer.
In one embodiment, the PE layer further comprises a secondary additive.
In one embodiment, the auxiliary additive is one or more of a toughening agent, a color masterbatch, an antioxidant, an antistatic agent, an opening agent, a slipping agent, an anti-aging agent, an anti-fog agent, an anti-cracking agent and a filler.
In one embodiment, the melting point of the PE layer is 100-132 ℃, and in the application, the melting point of the PE layer is too low, so that the overall heat resistance is reduced; too high a melting point, the heat seal strength declines.
According to the scheme, the isocyanate group end-capped polyurethane prepolymer is used as a reaction precursor, and the compound containing the epoxy functional group and the carbon-carbon double bond is used as a crosslinking agent, so that the chain extension reaction is initiated under the action of water vapor and a catalyst after the compound is coated on the surface of the PE film, and the reactive secondary polymer with the side chain carbon-carbon double bond is obtained, and the heat resistance of the PE film is obviously improved on the premise of ensuring the softness and the transparency of the PE film and the good binding force with a PE substrate. The specific reaction formula is as follows:
。
in addition, the application also provides a preparation method of the PE film with the heat-resistant coating, which comprises the following steps:
preparing a PE layer with the thickness of 20-500 mu m;
after mixing the raw materials of the heat-resistant coating, dissolving the raw materials in a solvent to prepare a heat-resistant coating;
and (3) coating the heat-resistant coating on the PE layer, performing single-side or double-side UV irradiation reaction in an ultraviolet lamp box with the relative humidity of 55% -95%, and then performing drying treatment to obtain the PE film with the heat-resistant coating.
In one embodiment, the solvent is a mixture of one or more from ethyl acetate, isopropyl acetate, n-butyl formate, n-butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
In one embodiment, the solid content of the heat-resistant coating is 20% -60%. The solid content is too low, the heat-resistant coating is too thin, and the pollution of the solvent is large; the solid content is too high, the viscosity of the paint is high, and the paint is unevenly coated.
In one embodiment, the UV irradiation light source is a high-pressure mercury lamp with the intensity of 100W/cm 2 ~200W/cm 2 Energy density 400mJ/cm 2 ~1500mJ/cm 2 。
In one embodiment, the temperature of the drying treatment is 60-80 ℃.
The preparation method of the scheme adopts the steps of coating and then chain extension reaction, firstly, the molecular weight of the prepolymer can be reduced, so that the viscosity of the coating liquid is reduced, the materials are more uniformly mixed, the solid content is favorably improved, the use of an organic solvent is reduced, and meanwhile, a thinner coating is also favorably obtained; secondly, reaction steps can be reduced, and procedures can be reduced; thirdly, the surface in-situ chain extension reaction can lead the surface coverage to be more uniform. The heat-resistant coating and the PE substrate are subjected to photoinitiated grafting. The secondary polymer with carbon-carbon double bonds can react with PE base material and be grafted to PE surface through UV irradiation under the action of photoinitiator. The specific reaction formula is as follows:
PE is activated by the action of initiator radicals:
；
b. the double bond compound is activated under the action of an initiator free radical:
；
c. double bond compound and PE reaction:
；
since the secondary polymer has a plurality of double bonds in the molecular chain, reactions also occur in the process between the molecules, thereby forming a crosslinked structure. The heat-resistant coating and the PE layer have stronger binding force because the polymer molecules in the heat-resistant coating and the PE layer are combined through chemical bonds. The inorganic filler used in the heat-resistant coating layer is also previously modified with a silane coupling agent containing a double bond, and also participates in the above reaction in the process. After the whole scheme is optimized, the heat-resistant polymer with a high cross-linking structure is obtained, and good combination with the PE layer is realized.
Embodiments of the present invention will be described in detail below with reference to specific examples.
It should be noted that abbreviations in the following examples are: low Density Polyethylene (LDPE), linear Low Density Polyethylene (LLDPE), high Density Polyethylene (HDPE), metallocene polyethylene (mLLDPE).
Example 1:
a method for preparing a PE film with a heat resistant coating, comprising the steps of:
preparing an HDPE layer;
after mixing the raw materials (table 1) of the heat-resistant coating, dissolving the raw materials in n-butyl acetate to prepare a heat-resistant coating with the solid content of 35%;
the heat-resistant coating paint is coated on an HDPE layer with the melting point of 128 ℃, and is subjected to single-side UV irradiation reaction in an ultraviolet lamp box with the relative humidity of 70%, wherein a UV irradiation light source is a high-pressure mercury lamp, and the intensity is that150W/cm 2 Energy density 600mJ/cm 2 And then drying at 80 ℃ to obtain the PE film with the heat-resistant coating.
The PE film prepared in example 1 had a PE layer thickness of 150. Mu.m, and a heat-resistant coating layer thickness of 3. Mu.m. As shown in fig. 1, fig. 1 is a schematic cross-sectional view of a PE film prepared in the embodiment under an optical microscope, and examples 2 to 5 are similar structures with different thicknesses, and are not repeated.
Table 1: example 1 preparation of Heat-resistant coating
Example 2:
a method for preparing a PE film with a heat resistant coating, comprising the steps of:
preparing a mLLDPE layer;
after mixing the raw materials (table 2) of the heat-resistant coating, dissolving the raw materials in ethyl acetate to prepare a heat-resistant coating paint with the solid content of 43%;
the heat-resistant coating paint is coated on an mLLDPE layer with the melting point of 115 ℃, and is subjected to single-side UV irradiation reaction in an ultraviolet lamp box with the relative humidity of 60 percent, and the UV irradiation light source is a high-pressure mercury lamp with the intensity of 120W/cm 2 Energy density 1200mJ/cm 2 And then drying at 60 ℃ to obtain the PE film with the heat-resistant coating.
The PE film prepared in example 2 had a thickness of 100 μm in the LDPE layer and a thickness of 1.5. Mu.m in the heat-resistant coating layer.
Table 2: example 2 preparation of Heat-resistant coating
Example 3:
a method for preparing a PE film with a heat resistant coating, comprising the steps of:
preparing an LDPE layer;
after mixing the raw materials (table 3) of the heat-resistant coating, the raw materials were dissolved in a mixed solvent (8:2 vol.%) of isopropyl acetate and methyl ethyl ketone to prepare a heat-resistant coating material having a solid content of 28%;
the heat-resistant coating paint is coated on an LDPE layer with the melting point of 124 ℃, and is subjected to double-side UV irradiation reaction in an ultraviolet lamp box with the relative humidity of 95%, and the UV irradiation light source is a high-pressure mercury lamp with the intensity of 180W/cm 2 Energy density 1500mJ/cm 2 And then drying at 70 ℃ to obtain the PE film with the heat-resistant coating.
The PE film prepared in example 3 had a thickness of 350 μm in the LDPE layer and 18 μm in the heat-resistant coating.
Table 3: example 3 preparation of Heat-resistant coating
Example 4:
a method for preparing a PE film with a heat resistant coating, comprising the steps of:
preparing an LDPE layer;
after mixing the raw materials (table 4) of the heat-resistant coating, dissolving the raw materials in ethyl acetate to prepare a heat-resistant coating paint with the solid content of 20%;
the heat-resistant coating paint is coated on an LDPE layer with the melting point of 108 ℃, and is subjected to unilateral UV irradiation reaction in an ultraviolet lamp box with the relative humidity of 55 percent, and the UV irradiation light source is a high-pressure mercury lamp with the intensity of 200W/cm 2 Energy density 1400mJ/cm 2 And then drying at 65 ℃ to obtain the PE film with the heat-resistant coating.
The PE film prepared in example 4 had a LDPE layer thickness of 480. Mu.m, and a heat-resistant coating layer thickness of 12. Mu.m.
Table 4: example 4 preparation of Heat-resistant coating
Example 5:
a method for preparing a PE film with a heat resistant coating, comprising the steps of:
preparing an LLDPE layer;
after mixing the raw materials (table 5) of the heat-resistant coating, dissolving the raw materials in a mixed solvent (1:9 vol%) of methyl isobutyl ketone and cyclohexanone to prepare a heat-resistant coating with a solid content of 45%;
the heat-resistant coating paint is coated on LLDPE layer with melting point of 112 ℃, and is subjected to double-side UV irradiation reaction in an ultraviolet lamp box with relative humidity of 83%, and the UV irradiation light source is a high-pressure mercury lamp with intensity of 200W/cm 2 Energy density 1500mJ/cm 2 And then drying at 80 ℃ to obtain the PE film with the heat-resistant coating.
The PE film prepared in example 5 had a LLDPE layer thickness of 260 μm and a heat resistant coating thickness of 8. Mu.m.
Table 5: example 5 preparation of Heat-resistant coating
Comparative example 1:
comparative example 1 was different from example 1 in that the raw material of the heat-resistant coating layer of comparative example 1 did not contain a crosslinking agent, and comparative sample 1 was obtained in the same manner as in example 1.
Comparative example 2:
comparative example 2 is different from example 1 in that the raw material of the heat-resistant coating layer of comparative example 2 does not contain a photoinitiator, and otherwise the same as example 1, comparative sample 2 is obtained.
Comparative example 3:
comparative example 3 is different from example 1 in that the inorganic platelet filler in the raw material of the heat-resistant coating layer in comparative example 3 is not modified by the silane coupling agent, and otherwise the same as example 1, comparative sample 3 is obtained.
Comparative example 4:
comparative sample 4 was obtained by using the packaging composite film obtained by the method of example 1 described in the prior art with the patent number CN111267446 as comparative example 4.
Comparative example 5:
the HDPE film (melting point: 128 ℃) of the same thickness as that of example 1 described in the prior art in CN113388180 was subjected to a secondary stretching treatment to obtain a comparative sample 5.
Comparative examples 6 to 10:
to verify the effect of relative humidity on the present application, comparative examples 6 to 10 were designed, and comparative examples 6 to 10 differ from example 1 in the relative humidity, and comparative examples 6 to 10 were obtained, respectively, in the same manner as in example 1, with specific relative humidities shown in the following table 6.
Table 6: relative humidity of
Performance tests were conducted on the PE films obtained in examples 1 to 5 and the comparative samples 1 to 10 obtained in comparative examples 1 to 10, respectively, according to the following methods.
Heat sealing performance: heat sealing temperature 160 ℃, pressure: 0.2MPa, time 0.4s. And (5) observing the heat sealing fastness and knife sticking condition of the sample to be tested.
Heat shrinkage rate: the samples were cut into 50X 50 mm pieces, placed in an oven at 120℃for 30min, taken out for measurement and the longitudinal and transverse shrinkage was calculated.
Coating binding force: the sample was cut into 50X 50 mm pieces and placed under a friction tester for reciprocating friction experiments. The experimental conditions were as follows: the friction head is a 30X 30 mm sponge friction head, the load is 50g, the friction length is 1cm, the friction times are 100 times, and the friction mode is as follows: and (5) dry grinding. The sample sheet friction area was then cut to size 30X 30 mm, placed in an oven at 120℃for 30min, and the measurement was taken out and the longitudinal and transverse shrinkage after friction was calculated. The results are shown in Table 7 below.
Table 7: performance comparison
From the data analysis of table 6, the PE films prepared in examples 1 to 5 in the present application have more excellent heat resistance, and are shown to have better heat sealing performance, firm heat sealing, no knife adhesion, and lower heat shrinkage, which indicates that the examples have better heat stability. Moreover, the PE films obtained in examples 1 to 5 of the present invention can be recovered and have excellent flexibility and transparency.
The comparative examples 1-2 do not contain a cross-linking agent or a photoinitiator, and the examples 1-5 contain the cross-linking agent and the photoinitiator, so that the heat resistance of the coating and the binding force to the PE film substrate can be effectively improved, and the good retention degree can be maintained after friction test, which shows that the heat shrinkage rate after friction is not changed obviously. In comparative examples 1-2 without cross-linking agent and photoinitiator, the coating was destroyed after abrasion and the heat shrinkage yield was significantly improved. The inorganic platelet filler in comparative example 3 was not modified with the silane coupling agent, and it can be seen that the performance was inferior to that of the examples. Comparative examples 4 to 5 are technical schemes disclosed in the prior art, and it is obvious that samples in comparative example 4 and comparative example 5 are all sticky and inapplicable, and are difficult to meet the requirements of the prior art. Comparative examples 6-10 are different relative humidities, and it can be seen that the performance of the PE film prepared in the present application is also affected by the process parameters of the relative humidities.
FIG. 2 is a schematic view of curing the heat-resistant coating of example 1 according to the present invention, and as can be seen from FIG. 2, the benefits of the application of photoinitiated graft polymerization are: firstly, the photoinitiation reaction has higher reaction efficiency, and the crosslinking degree can be regulated and controlled by adjusting the light input intensity; secondly, the reaction can be carried out at room temperature or low temperature, so that the defects of shrinkage, warping or uneven surface of the PE film caused by high temperature initiation are avoided; and thirdly, the method can be used for continuous production, and meets the requirements of scale and industrialization. The in-situ chain extension reaction and the photo-grafting reaction can be completed in the UV irradiation box 1 with humidity control, and the crosslinking degree of the coating is regulated by regulating the humidity and the irradiation intensity, namely, the humidity is improved to be beneficial to chain extension; the irradiation intensity is improved, the crosslinking and grafting are facilitated, and the drying treatment is carried out in the drying box 2.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (7)
1. The PE film comprises a heat-resistant coating and a PE layer which are sequentially connected, and is characterized in that the thickness of the heat-resistant coating accounts for 1% -5% of the total thickness of the PE film;
the heat-resistant coating comprises the following raw materials in parts by weight:
100 parts of isocyanate-terminated polyurethane;
5-35 parts of a cross-linking agent;
0-30 parts of modified inorganic filler;
0.05-0.5 parts of photoinitiator;
0.05-1 part of catalyst;
wherein the cross-linking agent is a compound containing an epoxy functional group and a carbon-carbon double bond, and the compound is one or more of glycidyl methacrylate, glycidyl acrylate and allyl glycidyl ether;
the preparation method of the PE film comprises the following steps:
preparing a PE layer with the thickness of 20-500 mu m;
after mixing the raw materials of the heat-resistant coating, dissolving the raw materials in a solvent to prepare a heat-resistant coating;
and (3) coating the heat-resistant coating on the PE layer, performing single-side or double-side UV irradiation reaction in an ultraviolet lamp box with the relative humidity of 55% -95%, and then performing drying treatment to obtain the PE film with the heat-resistant coating.
2. The PE film according to claim 1, wherein the isocyanate-terminated polyurethane is an isocyanate-terminated polyurethane prepolymer having a number average molecular weight of 10000 to 50000.
3. The PE film according to claim 2, wherein the isocyanate-terminated polyurethane is prepared by polycondensation of a polyol and a polyisocyanate, and the molar ratio of the polyol to the polyisocyanate is 1 (1.2-1.8).
4. A PE film according to claim 3, characterized in that the polyol is selected from one or more of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, glycerol, polyethylene glycol, polypropylene glycol, polytetrahydrofuran ether glycol, polyethylene glycol adipate glycol, polyethylene glycol terephthalate glycol, polyoxypropylene glycol and polyoxypropylene triol; the polyisocyanate is selected from one or more of diphenylmethane diisocyanate, 2, 4-toluene diisocyanate, p-phenylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.
5. The PE film according to claim 1, wherein the modified inorganic filler is a lamellar inorganic filler modified with a silane coupling agent containing a double bond.
6. The PE film according to claim 5, wherein the silane coupling agent containing a double bond is selected from one or more of γ -methacryloxypropyl trimethoxysilane, γ -methacryloxypropyl triethoxysilane, vinyl trimethoxysilane, and vinyl triethoxysilane.
7. The PE film according to claim 1, wherein the material of the PE layer comprises polyethylene and the polyethylene is one or more of low density polyethylene, linear low density polyethylene, high density polyethylene, metallocene polyethylene, bimodal polyethylene, ethylene-alpha-olefin copolymer.
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