CN109721911A - Conductive polyvinyl alcohol film and combinations thereof and preparation method - Google Patents
Conductive polyvinyl alcohol film and combinations thereof and preparation method Download PDFInfo
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- CN109721911A CN109721911A CN201711052865.2A CN201711052865A CN109721911A CN 109721911 A CN109721911 A CN 109721911A CN 201711052865 A CN201711052865 A CN 201711052865A CN 109721911 A CN109721911 A CN 109721911A
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- Prior art keywords
- polyvinyl alcohol
- component
- film
- conductive
- variety
- Prior art date
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Links
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 139
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 62
- 239000000314 lubricant Substances 0.000 claims abstract description 39
- 239000004014 plasticizer Substances 0.000 claims abstract description 32
- 239000011231 conductive filler Substances 0.000 claims abstract description 22
- 238000006136 alcoholysis reaction Methods 0.000 claims abstract description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 14
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 14
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 polyethylene Polymers 0.000 claims abstract description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000004698 Polyethylene Substances 0.000 claims abstract description 7
- 239000001110 calcium chloride Substances 0.000 claims abstract description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 7
- 235000011187 glycerol Nutrition 0.000 claims abstract description 7
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229920000573 polyethylene Polymers 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 66
- 239000010410 layer Substances 0.000 claims description 59
- 210000002615 epidermis Anatomy 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 238000000137 annealing Methods 0.000 claims description 9
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000007766 curtain coating Methods 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 230000005540 biological transmission Effects 0.000 claims description 6
- 239000003974 emollient agent Substances 0.000 claims description 6
- 150000004665 fatty acids Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000004811 fluoropolymer Substances 0.000 claims description 5
- 229920002313 fluoropolymer Polymers 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 5
- 239000002356 single layer Substances 0.000 claims description 5
- 239000002250 absorbent Substances 0.000 claims description 4
- 230000002745 absorbent Effects 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical class CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000002923 metal particle Substances 0.000 claims description 3
- 239000011859 microparticle Substances 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- 150000002334 glycols Chemical class 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 230000004888 barrier function Effects 0.000 abstract description 8
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 abstract description 3
- 239000001632 sodium acetate Substances 0.000 abstract description 3
- 235000017281 sodium acetate Nutrition 0.000 abstract description 3
- 239000010408 film Substances 0.000 description 100
- 239000002994 raw material Substances 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 239000011133 lead Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000002085 enols Chemical class 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000021050 feed intake Nutrition 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000010096 film blowing Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229920006302 stretch film Polymers 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 208000032765 Device extrusion Diseases 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- UQLDLKMNUJERMK-UHFFFAOYSA-L di(octadecanoyloxy)lead Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O UQLDLKMNUJERMK-UHFFFAOYSA-L 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002313 glycerolipids Chemical class 0.000 description 1
- 229940075507 glyceryl monostearate Drugs 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention relates to polyvinyl alcohol film fields, and in particular, to conductive polyvinyl alcohol film and combinations thereof and preparation method.The conductive polyethylene alcohol composition contains polyvinyl alcohol, plasticizer, conductive filler, lubricant and optional auxiliary agent；The plasticizer contains component A, component B and component C；The component A is one of glycerine, ethylene glycol, polyethylene glycol and pentaerythrite or a variety of；The component B is one of magnesium chloride, magnesium nitrate, calcium chloride, copper sulphate and sodium acetate or a variety of；The component C is water.The present invention enables to the polyvinyl alcohol of wider alcoholysis degree range to be film-made through biaxial tension, and resulting conductive polyvinyl alcohol film mechanical property, electrical property and barrier property with higher.
Description
Technical field
The present invention relates to polyvinyl alcohol film fields, and in particular, to conductive polyvinyl alcohol film and combinations thereof and system
Preparation Method.
Background technique
Polyvinyl alcohol (PVA) is the non-petroleum base macromolecule that can be prepared from natural gas of industrialized production few in number
Material, application range spread weaving, food, medicine, building, timber processing, papermaking, printing, agricultural, steel, producing high-molecular
The fields such as work.The acid and alkali-resistance and organic solvent resistance of PVA is excellent, has splendid barrier property, and good biocompatibility can give birth to
Object degradation.But because on its strand there are polyhydroxy structure, intramolecular and it is intermolecular produce very strong hydrogen bond, lead to its fusing point
It is close with decomposition temperature, it is difficult thermoplastic processing, therefore its application is main at present or is based on solwution method technique, using solution curtain coating
The disadvantages of method prepares PVA film there is complex steps, and film strength is poor.
Fast (the highest winding of the stretching ratio of biaxial tension method big (cross directional stretch multiplying power is up to 10 times or more), shaping speed
Speed is up to hundreds of ms/min), high production efficiency, and the mechanical strength of obtained film, optical property and the thickness uniformity
More preferably, but film forming is influenced significantly by process condition fluctuations, and film stretch process difficulty is big, has for film raw material
Higher requirement.And due to the particularity of PVA processing, there are no the biaxial tension method process system researchs for PVA, so that
Biaxial tension method prepares PVA film and is difficult to realize.
Polyvinyl alcohol film has certain static electricity resistance, will not cause the reduction of its plasticity or electrostatic attached because of electrostatic
Dirt can be used for the packaging of some electronic products.But since the PVA film intensity of solwution method preparation is poor, application is also limited
System.
Summary of the invention
The purpose of the present invention is to provide a kind of novel conductive polyvinyl alcohol film and combinations thereof and preparation methods, should
Conductive polyvinyl alcohol film tensile strength with higher, electrical property and barrier property can be used for antistatic or electromagnetic shielding and use
Electric conductivity packaging material.
To achieve the goals above, one aspect of the present invention provides a kind of conductive polyethylene alcohol composition, and the composition contains
Polyvinyl alcohol, plasticizer, conductive filler, lubricant and optional auxiliary agent；The plasticizer contains component A, component B and component C；
The component A is one of glycerine, ethylene glycol, polyethylene glycol and pentaerythrite or a variety of；The component B be magnesium chloride,
One of magnesium nitrate, calcium chloride, copper sulphate and sodium acetate are a variety of；The component C is water.
Second aspect of the present invention provides a kind of conductive polyvinyl alcohol film containing above-mentioned composition.
Third aspect present invention provides a kind of preparation method of biaxial tension conductive polyvinyl alcohol film, this method comprises:
(1) mixture of above-mentioned composition ingredient is provided；
(2) mixture is subjected to melting extrusion and is cast slab, obtain polyvinyl alcohol slab；
(3) polyvinyl alcohol slab is subjected to biaxial tension to form a film.
Fourth aspect present invention provides conductive polyvinyl alcohol film prepared by the above method.
The present invention enables to the polyvinyl alcohol of wider alcoholysis degree range to be film-made through biaxial tension, and the resulting poly- second of conduction
Enol film mechanical property with higher, electrical property and barrier property.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of conductive polyethylene alcohol composition, and the composition contains polyvinyl alcohol, plasticizer, leads
Electric filler, lubricant and optional auxiliary agent；The plasticizer contains component A, component B and component C；The component A be glycerine,
One of ethylene glycol, polyethylene glycol and pentaerythrite are a variety of；The component B is magnesium chloride, magnesium nitrate, calcium chloride, sulfuric acid
One of copper and sodium acetate are a variety of；The component C is water.
According to the present invention, the content of the component A, component B and component C can change in a wider range, in order to obtain
It is more conducive to the mechanical property of raising polyvinyl alcohol film, the plasticizer of electrical property and barrier property, it is preferable that the component A,
The weight ratio of component B and component C are 20-500:100:80-500, preferably 30-300:100:100-300, for example, 50-
200:100:120-250,80-150:100:150-200.
According to the present invention, the average molecular weight that the polyethylene glycol in the component A has is preferably 200-400.Described group
Dividing A is preferably one of glycerine, the polyethylene glycol that average molecular weight is 200-400 and pentaerythrite or a variety of.
Preferably, the component B is one of magnesium chloride, magnesium nitrate and calcium chloride or a variety of.
In a preferred embodiment of the invention, the component A is glycerine and/or number-average molecular weight is 200-
400 polyethylene glycol, the component B are magnesium chloride and/or magnesium nitrate；Alternatively, the component A is pentaerythrite, the component B
For calcium chloride.
According to the present invention, in order to obtain mechanical property, electrical property and the higher polyvinyl alcohol film of barrier property, preferably
The weight ratio of ground, the polyvinyl alcohol and plasticizer is 100:5-40, preferably 100:10-30, more preferably 100:15-25.
Preferably, the weight ratio of the polyvinyl alcohol and conductive filler is 100:1-10, preferably 100:3-8.Preferably, the poly- second
The weight ratio of enol and lubricant is 100:0.5-5, preferably 100:1-3.
Wherein, composition of the invention is suitable for the polyvinyl alcohol of wider range alcoholysis degree, the degree of polymerization and partial size, preferably
Ground, the alcoholysis degree of the polyvinyl alcohol are 80-99mol%, and the degree of polymerization is 1500 or more (preferably 1500-2500), and partial size is
90-500μm.The polyvinyl alcohol of low alcoholysis level is also suitable, such as the alcoholysis degree of the polyvinyl alcohol is 80-90mol%, is gathered
Right is 1600-1800, and partial size is 100-300 μm.The polyvinyl alcohol of high alcoholysis degree is also suitable, such as the polyvinyl alcohol
Alcoholysis degree be 95-99mol%, degree of polymerization 1700-2500, partial size be 320-400 μm.
According to the present invention, the conductive filler can have multiple choices, such as the conductive filler can be carbonaceous class
One of conductive filler, conductive metal particles, conductive fiber and metal oxide are a variety of.Wherein, the carbonaceous class is conductive
Filler for example can be one of carbon black class conductive filler, graphite-like conductive filler and carbon nanotube class conductive filler or more
Kind；The carbon black class conductive filler is preferably that acetylene carbon black, superconduction carbon black and spy lead one of carbon black or a variety of, the graphite
Class conductive filler is preferably one of natural graphite, expansible graphite, expanded graphite and graphene or a variety of, the carbon nanometer
Tubing conductive filler be preferably unmodified or single-walled carbon nanotube and multi-walled carbon nanotube Jing Guo surface modification treatment in one
Kind is a variety of.The particle that the conductive metal particles can be formed for metals such as silver, aluminium, copper, iron, nickel, stainless steels, or be coated with
One of the glass marble of one of silver, aluminium, copper, iron, nickel, lead etc. or various metals, mica sheet etc. are a variety of.The conduction
Fiber can for carbon fiber and one of be coated with silver, aluminium, copper, iron, nickel, lead etc. or the glass fibre of various metals etc. in
It is one or more.The metal oxide be preferably one of titanium oxide, zinc oxide, tin oxide, indium oxide and cadmium oxide or
It is a variety of.Preferably, the conductive filler is one of carbonaceous class conductive filler or a variety of.
According to the present invention, the lubricant can be selected from a variety of lubricants, it is preferable that the lubricant is poly-
Glycols lubricant, fluoropolymer series lubricant agent, organic silicon lubricant, fatty alcohol type emollients, fatty acid lubrication
Agent, fatty acid ester type emollients, stearic amide series lubricant agent, fatty acid metal soaps lubricant, alkane and oxidation of alkanes class
One of lubricant and micro-and nano-particles series lubricant agent are a variety of.
Wherein, the polyethylene glycol series lubricant agent for example can be the PEG molecule that average molecular weight is 500-50000,
It can also pass through other chemical modifications or physical modification by sealing end, grafting, crosslinking Treatment.
Wherein, the fluoropolymer series lubricant agent for example can be polytetrafluoroethylene (PTFE), Kynoar, polyhexafluoropropylene
At least one of Deng, or other unimodal or multimodal fluoropolymers and crystallization or hemicrystalline fluoropolymer
Object.
Wherein, the organo-silicic oil can be existing various using carbon, silicon atom as molecular backbone, with methyl, benzene
The oligomer or oligomer of the organic groups such as base, alkoxy, vinyl are the compound of side chain.
Wherein, the fatty alcohol type emollients for example can in soft fat alcohol, tallow alcohol, tallow fatty alcohol etc. extremely
Few one kind.
Wherein, the fatty acid lubricant for example can be with stearic acid and/or 12- hydroxy stearic acid.
Wherein, the fatty acid ester type emollients for example can be butyl stearate, stearic acid list glycerolipid, palmitinic acid ten
At least one of six Arrcostabs, tearyl base ester etc..
Wherein, the stearic amide series lubricant agent for example can be stearic amide, oleamide, erucyl amide, n,
At least one of n- ethylene bis stearic acid amide (EBS) etc..
Wherein, the fatty acid metal soaps lubricant for example can be lead stearate, calcium stearate, magnesium stearate, conjunction
At at least one of calcium acetate etc..
Wherein, the alkane and oxidation of alkanes series lubricant agent for example can for atoleine, solid paraffin, polyethylene wax,
At least one of polypropylene wax, ethylene oxide wax etc..
Wherein, the micro-and nano-particles series lubricant agent for example can be powdered rubber and/or aerosil particles.
According to the present invention, the composition can also contain auxiliary agent, and the auxiliary agent can be other to polyvinyl alcohol film
Performance has a gain effect, and will not stretching film forming to polyvinyl alcohol film, mechanical property, electric conductivity and barrier property produce
The additive of raw detrimental effect.The auxiliary agent for example can be one of antioxidant, acid absorbent and antitack agent or a variety of.
Wherein, the antioxidant for example can be antioxidant 1010, antioxidant 1076, antioxidant 164, irgasfos 168, resist
At least one of oxygen agent 264 etc..The content of the antioxidant can change in a wider range, the institute relative to 100 parts by weight
Polyvinyl alcohol is stated, the content of the antioxidant is preferably 0.1-1 parts by weight.
Wherein, the acid absorbent can be for example at least one of hydrotalcite, calcium stearate, zinc stearate etc..The suction
The content of sour agent can change in a wider range, relative to the polyvinyl alcohol of 100 parts by weight, the content of the acid absorbent
Preferably 0.1-1 parts by weight.
Wherein, the antitack agent for example can be in silica, calcium carbonate, diatomite, talcum powder, glass microballoon etc.
It is at least one.The content of the antitack agent can change in a wider range, relative to the polyvinyl alcohol of 100 parts by weight, institute
The content for stating antitack agent is preferably 0.1-1 parts by weight.
Second aspect of the present invention provides a kind of conductive polyvinyl alcohol film containing above-mentioned composition.
As long as the conductive polyvinyl alcohol film that the second aspect of the invention provides is containing above-mentioned polyvinyl alcohol compositions
Can, content for example can be 80-100 weight %.
Third aspect present invention provides a kind of preparation method of biaxial tension conductive polyvinyl alcohol film, this method packet
It includes:
(1) mixture of above-mentioned composition ingredient is provided；
(2) mixture is subjected to melting extrusion and is cast slab, obtain polyvinyl alcohol slab；
(3) polyvinyl alcohol slab is subjected to biaxial tension to form a film.
According to the present invention, step (1) is mainly to provide the mixture of above-mentioned composition ingredient, in order to subsequent place
Reason forms polyvinyl alcohol film.Preferably, step (1) includes: first to mix polyvinyl alcohol and plasticizer, is then re-introduced into and leads
Electric filler, lubricant and optional auxiliary agent.It is highly preferred that including: temperature by the condition that polyvinyl alcohol and plasticizer mix
For 50-90 DEG C (preferably 60-80 DEG C), the time is 0.5-4h (preferably 1-2h).
The mixed process, which can be, is first heated to 50-90 DEG C for polyvinyl alcohol, then introduces plasticizer and is 50- in temperature
90 DEG C of mixing 0.5-4h.Introducing for the plasticizer can be by the way of disposably feeding intake, can also be using the side that feed intake step by step
Formula, in order to improve the dispersion effect of plasticizer and polyvinyl alcohol, it is preferred to use the mode to feed intake step by step, it is preferable that the plasticising
Agent is added in 5-60min and is finished.
According to the present invention, after polyvinyl alcohol and plasticizer being mixed, conductive filler, lubricant is being added and optional is being helped
Before agent, the mixture of polyvinyl alcohol and plasticizer first can be down to room temperature (such as 20-30 DEG C) and add conductive filler, lubrication again
Agent and optional auxiliary agent, are then sufficiently mixed, and the mixture of above-mentioned composition ingredient is obtained.
According to the present invention, before carrying out step (2), the resulting mixture of step (1) can also be subjected to extruding pelletization and (squeezed
The temperature being granulated out is 100-200 DEG C), resulting master batch is used for the operation of step (2)；It is, of course, preferable to directly by step (1)
Resulting mixture carries out the processing of step (2), to reduce loss of material, especially reduces the loss of plasticizer.
According to the present invention, by step (2) by the mixture carry out melting extrusion and be cast slab can be in casting machine
It carries out, it is preferable that the temperature of the melting extrusion is 100-200 DEG C (preferably 110-160 DEG C)；The curtain coating of the curtain coating slab
Chilling roll temperature is 15-50 DEG C (preferably 20-40 DEG C).
According to the present invention, the structure for the film that the slab die head that the curtain coating slab uses can according to need acquisition is selected
It selects, for example, single layer die can be used when needing to obtain the film with single layer structure；There is multilayer knot when needing to obtain
When film (film with upper epidermis, sandwich layer and layer three-decker) of structure, the compound die head of multilayered structure can be used, and
And at least one layer of (sandwich layer) connects with the extruder hopper equipped with above-mentioned polyvinyl alcohol compositions in the compound die head of multilayered structure
Logical, at least one layer (sandwich layer) in the slab enabled in this way is the polyvinyl alcohol formed by above-mentioned polyvinyl alcohol compositions
Layer, naturally it is also possible to be that the compound die head of the multilayered structure all connects with the extruder hopper equipped with above-mentioned polyvinyl alcohol compositions
Logical, each layer in the slab enabled in this way is all the polyvinyl alcohol layer formed by above-mentioned polyvinyl alcohol compositions.
For this purpose, the polyvinyl alcohol slab is single layer structure or multilayered structure, preferably by upper epidermis, sandwich layer and layer
The three-decker of composition, the upper epidermis, sandwich layer and layer are all the layer that polyvinyl alcohol compositions are formed.
According to the present invention, in step (3), the biaxial tension may include that Synchronos method stretching or the method for fractional steps stretch.Wherein,
The Synchronos method stretching refers to carrying out film longitudinal (MD) simultaneously and laterally (TD) is stretched, and the method for fractional steps stretching refers to elder generation
Film longitudinal stretching is carried out, then carries out film cross directional stretch.
Preferably, it includes first preheating polyvinyl alcohol slab that the Synchronos method, which stretches, then carries out MD and TD simultaneously
It stretches.Preferably, the condition that the Synchronos method stretches includes: that draft temperature is 120-170 DEG C, and MD stretching ratio is 3 times or more
(for example, 3-6 times), TD stretching ratio be 3 times or more (for example, 3-6 times), MD rate of extension for 300%/s or more (for example,
300%/s-500%/s), TD rate of extension is 300%/s or more (for example, 300%/s-500%/s)
Preferably, the method for fractional steps stretching includes: first to preheat polyvinyl alcohol slab, then first carries out MD stretching,
Then progress TD stretching is preheated again.Preferably, the condition that the method for fractional steps stretches includes: that MD draft temperature is 80-100 DEG C, TD
Draft temperature be 120-200 DEG C, MD stretching ratio be 3 times or more (for example, 3-6 times), TD stretching ratio for 3 times or more (such as
Be 3-6 times), MD rate of extension be 100%/s or more (for example, 100%/s-200%/s), TD rate of extension be 100%/s with
Upper (for example, 100%/s-200%/s).
According to the present invention, this method can carry out annealing setting processing to the film after stretching, can also be fixed without this
Shape processing, in the case where carrying out setting processing namely this method further includes carrying out at annealing setting after step (3) to resulting film
The temperature of reason, annealing setting processing is preferably 180-200 DEG C.The time of annealing setting processing is preferably 5-60s.To stretching
Film afterwards, which carries out annealing setting processing, can play the role of improving film dimensions stability.
According to the present invention, this method can also include by resulting polyvinyl alcohol film carry out surface corona processing, cutting edge and
Winding processing, surface corona processing, cutting edge and winding processing are the operation of this field routine, and the present invention has no this particularly
It limits.
Fourth aspect present invention provides conductive polyvinyl alcohol film prepared by the above method.
The present invention resulting conductive polyvinyl alcohol film mechanical property, electric conductivity and barrier property with higher, it is described
The MD tensile strength of conductive polyvinyl alcohol film for example can be 45MPa or more, especially 60MPa or more, preferably 100MPa
More than, more preferably 100-200MPa；TD tensile strength for example can be 50MPa or more, especially 70MPa or more, preferably
100MPa or more, more preferably 110-210MPa；Oxygen transmission rate can be 1.6cc/m2It is hereinafter, preferably 1.5cc/m2It
Hereinafter, more preferably 0.1-1.4cc/m2It；Volume resistivity is 108Ω m is hereinafter, preferably 2 × 106Ω m hereinafter,
More preferably 105Ω m or less.
For conductive polyvinyl alcohol film resulting for the polyvinyl alcohol of higher alcoholysis degree (for example, 95-99mol%),
The MD tensile strength of the conductive polyvinyl alcohol film is 150MPa or more, preferably 150-200MPa；TD tensile strength is
150MPa or more, preferably 170-210MPa；Oxygen transmission rate is 1.2cc/m2It is hereinafter, preferably 0.1-1.1cc/m2It；Body
Product resistivity is 108Ω m is hereinafter, preferably 106Ω m or less.
For conductive polyvinyl alcohol film resulting for the polyvinyl alcohol compared with low alcoholysis level (for example, 80-90mol%),
The MD tensile strength of the conductive polyvinyl alcohol film for example can be 45MPa or more, especially 60MPa or more, preferably
100MPa or more, more preferably 100-130MPa；TD tensile strength for example can be 50MPa or more, especially 70MPa or more,
Preferably 100MPa or more, more preferably 120-140MPa；Oxygen transmission rate is 1.6cc/m2It is hereinafter, preferably 0.5-1.4cc/
m2It；Volume resistivity is 108Ω m is hereinafter, preferably 2 × 106Ω m or less.
The present invention will be described in detail by way of examples below.
In following example:
PEG200 is to recover the polyethylene glycol that the average molecular weight of fine chemistry industry research institute is 200 purchased from Tianjin.
PEG400 is to recover the polyethylene glycol that the average molecular weight of fine chemistry industry research institute is 400 purchased from Tianjin.
Tensile strength, elongation at break and the tensile modulus of elasticity of polyvinyl alcohol film are according to GB/T1040.3-2006
Specified in method measure；
The oxygen transmission rate of polyvinyl alcohol film is that the method according to specified in ASTM D-3985 measures.
The volume resistivity of polyvinyl alcohol film is that the method according to specified in GB/T 1410-2006 measures.
Plasticizer preparation example
By according to the formula in table 1, component A, component B and component C are proportionally mixed, corresponding plasticizer is obtained.
Table 1
Note: the above component A and component B is measured with the pure material of substance listed in table.
Embodiment 1
The present embodiment is for illustrating conductive polyvinyl alcohol film of the invention and combinations thereof and preparation method.
(1) by 100 weight account polyethylene alcohol, (alcoholysis degree 88mol%, the degree of polymerization 1700, are purchased from Shanxi three by 180 μm of partial size
Dimension group company) 60 DEG C are warming up to, the plasticizer E1 (finishing in 30min) of 15 parts by weight is gradually added dropwise；After finishing, temperature is protected
It holds and is stirred 1h at 50 DEG C.After naturally cooling to 30 DEG C, the Kynoar lubricant that 1 parts by weight are added is (public purchased from 3M
Take charge of the FX5911 trade mark), the carbon nanotubes of 5 parts by weight (produces, diameter 20-30nm, length purchased from U.S. Cheaptubes company
20-30 μm) and 0.25 parts by weight antioxidant 1010 (be purchased from Switzerland's vapour bar chemistry (China) Co., Ltd, the same below), mix
Polyvinyl alcohol compositions are obtained after uniformly；
(2) polyvinyl alcohol compositions made from step (1) are added to the model LCR400's of Labtech company, Sweden
Melting extrusion is carried out in the sandwich layer extruder of multilayer extrusion casting machine and upper and lower surface layer extruder and is cast slab, and melting is squeezed
Each section of temperature is 110-160 DEG C out, and curtain coating chilling roll temperature is 25 DEG C, is thus obtained by upper epidermis, sandwich layer and layer structure
At polyvinyl alcohol slab；
(3) above-mentioned polyvinyl alcohol slab is put into the stretching clamp of film biaxial tension equipment, using two-way substep
Stretch film comprising: first polyvinyl alcohol slab is preheated, then first carries out MD stretching, then preheats then progress TD drawing
It stretches；Its condition includes: that the preceding preheating temperature of MD stretching is 90 DEG C, and MD draft temperature is 90 DEG C, and 3 times of MD stretching ratio, film MD is drawn
Stretching rate is 100%/s；Preheating temperature is 140 DEG C before TD is stretched, and TD draft temperature is 140 DEG C, and TD stretching ratio is 4 times, thin
Film TD rate of extension is 100%/s；Then the resulting film of biaxial tension is subjected to annealing setting processing 30s at 180 DEG C, obtained
The film for being 25 μm to average thickness, is made of, each layer raw material is the poly- second of the present embodiment upper epidermis, sandwich layer and layer
Enol composition.Gained biaxially oriented film performance is as shown in table 2.
Embodiment 2
The present embodiment is for illustrating conductive polyvinyl alcohol film of the invention and combinations thereof and preparation method.
(1) by 100 weight account polyethylene alcohol, (alcoholysis degree 85mol%, the degree of polymerization 1500, are purchased from Shanxi three by 200 μm of partial size
Dimension group company) 70 DEG C are warming up to, the plasticizer E2 (finishing in 25min) of 20 parts by weight is gradually added dropwise；After finishing, temperature is protected
It holds and is stirred 1.5h at 60 DEG C.After naturally cooling to 30 DEG C, the polyethylene glycol lubricant that 2 parts by weight are added (is purchased from Switzerland
Clariant Corporation, average molecular weight 10000), the carbon nanotubes of 2 parts by weight (produces, diameter purchased from U.S. Cheaptubes company
20-30nm, 20-30 μm of length), the irgasfos 168s of the antioxidant 1010 of 0.15 parts by weight and 0.25 parts by weight (be purchased from Switzerland's vapour
Ba Huaxue (China) Co., Ltd), polyvinyl alcohol compositions are obtained after mixing；
(2) polyvinyl alcohol compositions made from step (1) are added to the model LCR400's of Labtech company, Sweden
Melting extrusion is carried out in the sandwich layer extruder of multilayer extrusion casting machine and upper and lower surface layer extruder and is cast slab, and melting is squeezed
Each section of temperature is 110-160 DEG C out, and curtain coating chilling roll temperature is 20 DEG C, is thus obtained by upper epidermis, sandwich layer and layer structure
At polyvinyl alcohol slab；
(3) above-mentioned polyvinyl alcohol slab is put into the stretching clamp of film biaxial tension equipment, using two-way substep
Stretch film comprising: first polyvinyl alcohol slab is preheated, then first carries out MD stretching, then preheats then progress TD drawing
It stretches；Its condition include: MD stretch before preheating temperature be 100 DEG C, MD draft temperature be 100 DEG C, 4 times of MD stretching ratio, film MD
Rate of extension is 100%/s；Preheating temperature is 135 DEG C before TD is stretched, and TD draft temperature is 135 DEG C, and TD stretching ratio is 5 times,
Film TD rate of extension is 150%/s；The resulting film of biaxial tension is then subjected to annealing setting processing 10s at 200 DEG C,
The film that average thickness is 25 μm is obtained, is made of upper epidermis, sandwich layer and layer, each layer raw material is the poly- of the present embodiment
Vinyl alcohol compositions.Gained biaxially oriented film performance is as shown in table 2.
Embodiment 3
The present embodiment is for illustrating conductive polyvinyl alcohol film of the invention and combinations thereof and preparation method.
According to method described in embodiment 1, the difference is that:
Step (1): E1 is replaced using the plasticizer E3 of 25 parts by weight, the graphene of 3 parts by weight replaces carbon nanotube, lubrication
Agent using 1 parts by weight glyceryl monostearate (be purchased from the standing grain major company Atmer163 trade mark)；
Step (3): preheating temperature is 145 DEG C before TD is stretched, and TD draft temperature is 145 DEG C；
The film that average thickness is 25 μm is finally obtained, is made of upper epidermis, sandwich layer and layer, each layer raw material is
The polyvinyl alcohol compositions of the present embodiment.Gained biaxially oriented film performance is as shown in table 2.
Embodiment 4-11
The present embodiment is for illustrating conductive polyvinyl alcohol film of the invention and combinations thereof and preparation method.
According to method described in embodiment 1, unlike, the plasticizer E4-E11 for the parts by weight such as being respectively adopted replaces E1,
The film that average thickness is 25 μm is finally respectively obtained, is made of upper epidermis, sandwich layer and layer, each layer raw material is this reality
Apply the polyvinyl alcohol compositions of example.Gained biaxially oriented film performance is as shown in table 2.
Embodiment 12
The present embodiment is for illustrating conductive polyvinyl alcohol film of the invention and combinations thereof and preparation method.
According to method described in embodiment 1, the difference is that, the dosage of the plasticizer is 5 parts by weight；
The film that average thickness is 25 μm is finally obtained, is made of upper epidermis, sandwich layer and layer, each layer raw material is
The polyvinyl alcohol compositions of the present embodiment.Gained biaxially oriented film performance is as shown in table 2.
Embodiment 13
The present embodiment is for illustrating conductive polyvinyl alcohol film of the invention and combinations thereof and preparation method.
According to method described in embodiment 1, the difference is that, the dosage of the plasticizer is 35 parts by weight；
The film that average thickness is 25 μm is finally obtained, is made of upper epidermis, sandwich layer and layer, each layer raw material is
The polyvinyl alcohol compositions of the present embodiment.Gained biaxially oriented film performance is as shown in table 2.
Embodiment 14
The present embodiment is for illustrating conductive polyvinyl alcohol film of the invention and combinations thereof and preparation method.
According to method described in embodiment 1, the difference is that:
Step (3) replaces method of fractional steps biaxial tension namely the behaviour of the Synchronos method biaxial tension using Synchronos method biaxial tension
Work includes: first to preheat polyvinyl alcohol slab, then carries out MD simultaneously and stretches and TD stretching；Its condition includes: preheating temperature
Degree is 130 DEG C, and draft temperature is 130 DEG C, and 3.5 times of MD stretching ratio, MD rate of extension is 300%/s, and TD stretching ratio is 3.5
Times, TD rate of extension is 400%/s；
The film that average thickness is 25 μm is finally obtained, is made of upper epidermis, sandwich layer and layer, each layer raw material is
The polyvinyl alcohol compositions of the present embodiment.Gained biaxially oriented film performance is as shown in table 2.
Embodiment 15
The present embodiment is for illustrating conductive polyvinyl alcohol film of the invention and combinations thereof and preparation method.
According to method as described in example 4, unlike, using the alcoholysis degree 99mol%, poly- purchased from Ningxia Neng Hua company
Right 2000 and 360 μm of partial size polyvinyl alcohol replace embodiment 4 in polyvinyl alcohol.
The film that average thickness is 25 μm is finally obtained, is made of upper epidermis, sandwich layer and layer, each layer raw material is
The polyvinyl alcohol compositions of the present embodiment.Gained biaxially oriented film performance is as shown in table 2.
Embodiment 16
The present embodiment is for illustrating conductive polyvinyl alcohol film of the invention and combinations thereof and preparation method.
According to method described in embodiment 15, the difference is that:
Step (3) replaces method of fractional steps biaxial tension namely the behaviour of the Synchronos method biaxial tension using Synchronos method biaxial tension
Work includes: first to preheat polyvinyl alcohol slab, then carries out MD simultaneously and stretches and TD stretching；Its condition includes: preheating temperature
Degree is 130 DEG C, and draft temperature is 130 DEG C, and 3.5 times of MD stretching ratio, MD rate of extension is 300%/s, and TD stretching ratio is 3.5
Times, TD rate of extension is 400%/s；
The film that average thickness is 25 μm is finally obtained, is made of upper epidermis, sandwich layer and layer, each layer raw material is
The polyvinyl alcohol compositions of the present embodiment.Gained biaxially oriented film performance is as shown in table 2.
Embodiment 17
The present embodiment is for illustrating conductive polyvinyl alcohol film of the invention and combinations thereof and preparation method.
According to method described in embodiment 16, the difference is that, using the alcoholysis degree for being purchased from middle petrochemical industry Sichuan vinylon plant
97mol%, the degree of polymerization 1800 and 360 μm of partial size of polyvinyl alcohol replace the polyvinyl alcohol in embodiment 16.
The film that average thickness is 25 μm is finally obtained, is made of upper epidermis, sandwich layer and layer, each layer raw material is
The polyvinyl alcohol compositions of the present embodiment.Gained biaxially oriented film performance is as shown in table 2.
Comparative example 1-5
According to method described in embodiment 1, unlike, the plasticizer DE1-DE5 for the parts by weight such as being respectively adopted replaces E1,
Rupture of membranes occurs in biaxial orientation process for comparative example 1-3, can not stretch, and is unable to get respective films, and comparative example 4-5 is finally respective
The film that average thickness is 25 μm is obtained, is made of upper epidermis, sandwich layer and layer, each layer raw material is the poly- of this comparative example
Vinyl alcohol compositions.Gained biaxially oriented film performance is as shown in table 2.
Comparative example 6-7
According to method described in embodiment 15, unlike, the plasticizer DE4-DE5 for the parts by weight such as being respectively adopted is replaced
E4 finally respectively obtains the film that average thickness is 25 μm, is made of upper epidermis, sandwich layer and layer, each layer raw material is
The polyvinyl alcohol compositions of this comparative example.Gained biaxially oriented film performance is as shown in table 2.
Comparative example 8
According to method described in embodiment 1, the difference is that, step (2) adds polyvinyl alcohol compositions made from step (1)
The sandwich layer extruder and upper and lower surface layer for entering the multilayer extrusion casting machine of the model LCR400 to Labtech company, Sweden squeeze
Melting extrusion and direct casting film-forming are carried out in machine out, the temperature that each section of melting extrusion is 110-160 DEG C, is cast chilling roll temperature
It is 25 DEG C, thus directly obtains the cast film that average thickness is 25 μm, gained cast film performance is as shown in table 2.
Comparative example 9
According to method described in embodiment 1, the difference is that, this comparative example uses the upper blowing method of DR.COLLIN company, Germany
Film blowing device extrusion and blow molding obtains conductive polyvinyl alcohol film, and specific method is by polyvinyl alcohol group made from step (1)
It closes object to be added in the hopper of upper blowing method film blowing device extruder, raw material is after the abundant fusion plastification of extruder, by the ring of head
Melt membrane tube is made in shape die extrusion, after through compressed air inflation (blow-up ratio be 2.5 times), and be made and blow after vane is cooling
Polyvinyl alcohol film is moulded, film is the single layer structure that average thickness is 25 μm.Gained blown films porperties are as shown in table 2.
Table 2
It can be seen that by the data of table 2 using plasticizer provided in the present invention, enable to wider alcoholysis degree range
Polyvinyl alcohol be film-made through biaxial tension, prepare resulting polyvinyl alcohol film with high-strength and high every high conductivity.Wherein, special
Be not under preferred proportion, MD and TD to tensile strength in 100MPa or more, oxygen transmission rate is 1.4cc/m2It with
Under, volume resistivity 106Ω m or less.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (16)
1. a kind of conductive polyethylene alcohol composition, which is characterized in that the composition contain polyvinyl alcohol, plasticizer, conductive filler,
Lubricant and optional auxiliary agent；The plasticizer contains component A, component B and component C；The component A be glycerine, ethylene glycol,
One of polyethylene glycol and pentaerythrite are a variety of；The component B is magnesium chloride, magnesium nitrate, calcium chloride, copper sulphate and acetic acid
One of sodium is a variety of；The component C is water.
2. composition according to claim 1, wherein the weight ratio of the component A, component B and component C are 20-500:
100:80-500, preferably 30-300:100:100-300.
3. composition according to claim 1 or 2, wherein the component A is glycerine, average molecular weight 200-400
Polyethylene glycol and one of pentaerythrite or a variety of；
The component B is one of magnesium chloride, magnesium nitrate and calcium chloride or a variety of.
4. composition described in any one of -3 according to claim 1, wherein the weight ratio of the polyvinyl alcohol and plasticizer
For 100:5-40, preferably 100:10-30, more preferably 100:15-25；
Preferably, the weight ratio of the polyvinyl alcohol and conductive filler is 100:1-10, preferably 100:3-8；
Preferably, the weight ratio of the polyvinyl alcohol and lubricant is 100:0.5-5, preferably 100:1-3.
5. composition described in any one of -4 according to claim 1, wherein the alcoholysis degree of the polyvinyl alcohol is 80-
99mol%, the degree of polymerization are 1500 or more, and partial size is 90-500 μm；
Preferably, the alcoholysis degree of the polyvinyl alcohol is 80-90mol%, and degree of polymerization 1600-1800, partial size is 100-300 μ
m；
Preferably, the alcoholysis degree of the polyvinyl alcohol is 95-99mol%, and degree of polymerization 1700-2500, partial size is 320-400 μ
m。
6. composition described in any one of -5 according to claim 1, wherein the conductive filler is that carbonaceous class conduction is filled out
One of material, conductive metal particles, conductive fiber and metal oxide are a variety of, preferably one in carbonaceous class conductive filler
Kind is a variety of；
Preferably, the lubricant is polyethylene glycol series lubricant agent, fluoropolymer series lubricant agent, organic silicon lubricant, rouge
Fat alcohol type emollients, fatty acid lubricant, fatty acid ester type emollients, stearic amide series lubricant agent, fatty acid metal soap
Series lubricant agent, alkane and one of oxidation of alkanes series lubricant agent and micro-and nano-particles series lubricant agent or a variety of.
7. composition described in any one of -6 according to claim 1, wherein the auxiliary agent is antioxidant, acid absorbent and prevents
One of stick is a variety of.
8. a kind of conductive polyvinyl alcohol film containing composition described in any one of claim 1-7.
9. a kind of preparation method of biaxial tension conductive polyvinyl alcohol film, this method comprises:
(1) mixture of composition ingredient described in any one of claim 1-7 is provided；
(2) mixture is subjected to melting extrusion and is cast slab, obtain polyvinyl alcohol slab；
(3) polyvinyl alcohol slab is subjected to biaxial tension to form a film.
10. according to the method described in claim 9, wherein, step (1) includes: first to mix polyvinyl alcohol and plasticizer,
Then it is re-introduced into conductive filler, lubricant and optional auxiliary agent；
Wherein, by the condition that polyvinyl alcohol and plasticizer mix include: temperature be 50-90 DEG C, time 0.5-4h.
11. method according to claim 9 or 10, wherein the temperature of the melting extrusion is 100-200 DEG C；The stream
The curtain coating chilling roll temperature for prolonging slab is 15-50 DEG C.
12. the method according to any one of claim 9-11, wherein the polyvinyl alcohol slab be single layer structure or
Multilayered structure, the three-decker being preferably made of upper epidermis, sandwich layer and layer.
13. the method according to any one of claim 9-12, wherein the biaxial tension include Synchronos method stretch or
The method of fractional steps stretches；
It includes first preheating polyvinyl alcohol slab that the Synchronos method, which stretches, then carries out MD and TD simultaneously and stretches；It is described same
Footwork stretch condition include: draft temperature be 120-170 DEG C, MD stretching ratio be 3 times or more, TD stretching ratio be 3 times with
On, MD rate of extension is 300%/s or more, and TD rate of extension is 300%/s or more；
Method of fractional steps stretching includes: first to preheat polyvinyl alcohol slab, then first carries out MD stretching, then is preheated and laggard
Row TD is stretched；The condition that the method for fractional steps stretches includes: that MD draft temperature is 80-100 DEG C, and TD draft temperature is 120-200 DEG C,
MD stretching ratio is 3 times or more, and TD stretching ratio is 3 times or more, and MD rate of extension is 100%/s or more, and TD rate of extension is
100%/s or more.
14. the method according to claim 9 or 13, wherein this method further includes carrying out after step (3) to resulting film
Setting of annealing is handled, and the temperature of annealing setting processing is 180-200 DEG C.
15. conductive polyvinyl alcohol film made from the method as described in any one of claim 9-14.
16. conductive polyvinyl alcohol film according to claim 15, wherein the MD of the conductive polyvinyl alcohol film is stretched
Intensity is 45MPa or more, preferably 60MPa or more, more preferably 100MPa or more；TD tensile strength is 50MPa or more, preferably
For 70MPa or more, more preferably 100MPa or more；Oxygen transmission rate is 1.6cc/m2It is hereinafter, preferably 1.5cc/m2It with
Under；Volume resistivity is 108Ω m or less.
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| CN201711052865.2A CN109721911A (en) | 2017-10-30 | 2017-10-30 | Conductive polyvinyl alcohol film and combinations thereof and preparation method |
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| CN201711052865.2A CN109721911A (en) | 2017-10-30 | 2017-10-30 | Conductive polyvinyl alcohol film and combinations thereof and preparation method |
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