CN109705424A - A kind of Biaxially-oriented polyethylene antibacterial film and preparation method thereof - Google Patents
A kind of Biaxially-oriented polyethylene antibacterial film and preparation method thereof Download PDFInfo
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- CN109705424A CN109705424A CN201711015501.7A CN201711015501A CN109705424A CN 109705424 A CN109705424 A CN 109705424A CN 201711015501 A CN201711015501 A CN 201711015501A CN 109705424 A CN109705424 A CN 109705424A
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- Prior art keywords
- polyethylene
- guanidine
- antibacterial
- weight
- salt
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- -1 polyethylene Polymers 0.000 title claims abstract description 188
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 148
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 104
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 150000002357 guanidines Chemical class 0.000 claims abstract description 79
- 239000002344 surface layer Substances 0.000 claims abstract description 70
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 230000000845 anti-microbial effect Effects 0.000 claims abstract description 29
- 150000003751 zinc Chemical class 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000013508 migration Methods 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 19
- 229920001971 elastomer Polymers 0.000 claims abstract description 19
- 239000005060 rubber Substances 0.000 claims abstract description 19
- 239000004599 antimicrobial Substances 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims abstract description 11
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- 230000005012 migration Effects 0.000 claims abstract 3
- 239000003242 anti bacterial agent Substances 0.000 claims description 56
- 239000002131 composite material Substances 0.000 claims description 45
- 239000012792 core layer Substances 0.000 claims description 40
- 239000002994 raw material Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 33
- 238000005266 casting Methods 0.000 claims description 33
- 229920000126 latex Polymers 0.000 claims description 31
- 239000004816 latex Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 28
- 238000001125 extrusion Methods 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 26
- 150000001879 copper Chemical class 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 11
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 11
- 239000000155 melt Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- 229920001228 polyisocyanate Polymers 0.000 claims description 9
- 239000005056 polyisocyanate Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 229920013716 polyethylene resin Polymers 0.000 claims description 8
- 229920002379 silicone rubber Polymers 0.000 claims description 8
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 claims description 7
- 230000003449 preventive effect Effects 0.000 claims description 7
- 239000004945 silicone rubber Substances 0.000 claims description 7
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 7
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 7
- 229960001763 zinc sulfate Drugs 0.000 claims description 7
- 238000004132 cross linking Methods 0.000 claims description 6
- 230000005855 radiation Effects 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 5
- 229960004198 guanidine Drugs 0.000 claims description 5
- 229960000789 guanidine hydrochloride Drugs 0.000 claims description 5
- VVTZNCQOVBDXRL-UHFFFAOYSA-N guanidine;propanoic acid Chemical compound NC(N)=N.CCC(O)=O VVTZNCQOVBDXRL-UHFFFAOYSA-N 0.000 claims description 5
- PJJJBBJSCAKJQF-UHFFFAOYSA-N guanidinium chloride Chemical compound [Cl-].NC(N)=[NH2+] PJJJBBJSCAKJQF-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229920000459 Nitrile rubber Polymers 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 239000011858 nanopowder Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- NDRMWPVNHDJUCA-UHFFFAOYSA-N carbamimidoylazanium;octadecanoate Chemical compound NC(N)=N.CCCCCCCCCCCCCCCCCC(O)=O NDRMWPVNHDJUCA-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- MIVUEFFMYVHTQD-UHFFFAOYSA-N buta-1,3-diene;2-ethenylpyridine Chemical compound C=CC=C.C=CC1=CC=CC=N1 MIVUEFFMYVHTQD-UHFFFAOYSA-N 0.000 claims description 2
- DNOSZYUZVCJLMM-UHFFFAOYSA-N carbamimidoylazanium;benzoate Chemical compound NC(N)=[NH2+].[O-]C(=O)C1=CC=CC=C1 DNOSZYUZVCJLMM-UHFFFAOYSA-N 0.000 claims description 2
- CEDDGDWODCGBFQ-UHFFFAOYSA-N carbamimidoylazanium;hydron;phosphate Chemical compound NC(N)=N.OP(O)(O)=O CEDDGDWODCGBFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- YTFCZSQYONEXEQ-UHFFFAOYSA-N dodecanoic acid;guanidine Chemical compound NC(N)=N.CCCCCCCCCCCC(O)=O YTFCZSQYONEXEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- DXTIKTAIYCJTII-UHFFFAOYSA-N guanidine acetate Chemical compound CC([O-])=O.NC([NH3+])=N DXTIKTAIYCJTII-UHFFFAOYSA-N 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims 2
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- 238000001035 drying Methods 0.000 description 18
- 238000012360 testing method Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- 241000588724 Escherichia coli Species 0.000 description 14
- 241000191967 Staphylococcus aureus Species 0.000 description 14
- 238000009835 boiling Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- 230000002265 prevention Effects 0.000 description 6
- 239000002174 Styrene-butadiene Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
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- 229940043810 zinc pyrithione Drugs 0.000 description 5
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 5
- 229920002413 Polyhexanide Polymers 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
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- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 230000000843 anti-fungal effect Effects 0.000 description 3
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
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- WYVVKGNFXHOCQV-UHFFFAOYSA-N 3-iodoprop-2-yn-1-yl butylcarbamate Chemical compound CCCCNC(=O)OCC#CI WYVVKGNFXHOCQV-UHFFFAOYSA-N 0.000 description 2
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- 241001136494 Talaromyces funiculosus Species 0.000 description 2
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- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 2
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- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 description 2
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- 150000002825 nitriles Chemical class 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
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- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 2
- 239000012745 toughening agent Substances 0.000 description 2
- VCRZAKVGPJFABU-UHFFFAOYSA-N 10-phenoxarsinin-10-yloxyphenoxarsinine Chemical compound C12=CC=CC=C2OC2=CC=CC=C2[As]1O[As]1C2=CC=CC=C2OC2=CC=CC=C21 VCRZAKVGPJFABU-UHFFFAOYSA-N 0.000 description 1
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- QMMKOUARLJQQNC-UHFFFAOYSA-N 4-butyl-1,2-benzothiazol-3-one Chemical compound CCCCC1=CC=CC2=C1C(=O)NS2 QMMKOUARLJQQNC-UHFFFAOYSA-N 0.000 description 1
- BYNSSDLXMDZGPJ-UHFFFAOYSA-N 4-methyl-1,2-benzothiazol-3-one Chemical compound CC1=CC=CC2=C1C(=O)NS2 BYNSSDLXMDZGPJ-UHFFFAOYSA-N 0.000 description 1
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- 229960002026 pyrithione Drugs 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention belongs to Biaxial tension polyethylene film field, it is related to a kind of Biaxially-oriented polyethylene antibacterial film and preparation method thereof.The Biaxially-oriented polyethylene antibacterial film includes polyethylene core and the antimicrobial surface layer for being attached to a polyethylene core at least side surface, and the antimicrobial surface layer is the polyethylene layer for being dispersed with guanidine salt complex antimicrobials；The guanidine salt complex antimicrobials contain guanidine salt polymer, zinc salt and/or mantoquita, migration inhibitor, nanometer grade powder rubber and dispersing agent；In the guanidine salt complex antimicrobials, by the content of guanidine salt polymer be 100 parts by weight in terms of, the content of the zinc salt and/or mantoquita is 0.01~40 parts by weight, the content of the migration inhibitor is 0.1~10 parts by weight, the content of the nanometer grade powder rubber is 0.5~100 parts by weight, and the content of the dispersing agent is 0.1~10 parts by weight.Biaxial tension polyethylene film of the invention has both excellent anti-microbial property, optical property and mechanical strength.
Description
Technical Field
The invention belongs to the field of biaxially oriented polyethylene films, and particularly relates to a biaxially oriented polyethylene antibacterial film and a preparation method thereof.
Background
The biaxially oriented polyethylene film (BOPE film) is processed and formed by adopting a flat-film biaxially oriented process, has large stretching magnification and high production efficiency, has excellent mechanical strength, optical property, heat sealability, water resistance and water-blocking and air-permeable performance, is an ideal packaging material, is widely used for packaging foods, vegetables, fruits, infant products and the like, and plays an important role in the market. In recent years, with the improvement of living standard and the enhancement of health consciousness, people pay more and more attention to the pursuit of healthy living environment, and therefore, the demand for the antibacterial BOPE film and the product thereof is increasing. At present, the method of adding an antibacterial agent into a biaxially oriented polyethylene film is generally adopted to endow the BOPE film with better antibacterial and mildew-proof properties.
The antibacterial agents used mainly include inorganic and organic antibacterial agents. Among them, the guanidine salt polymer is an antibacterial polymer having a guanidine group in its molecular structure, and its species mainly include polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine propionate, polyhexamethylene (bis) guanidine stearate, and other inorganic or organic salts of polyhexamethylene (bis) guanidine, polyoxyethylene guanidine, and the like. Because of its excellent solubility in water, guanidinium polymers are mostly used in the form of aqueous solutions, as in patents JP05209195, US4891423, CN101156586A, all as bactericides for water treatment. Compared with other organic antibacterial agents, the guanidine salt polymer has good thermal stability and high thermal decomposition temperature up to 280 ℃, so that the guanidine salt polymer can be used as an antibacterial additive to be applied to plastic, fiber and rubber products to obtain antibacterial products. However, most guanidinium polymers are very water soluble, making powder samples difficult, limiting their use in plastic, rubber, and fiber applications.
Patent document CN101037503A discloses a method for preparing a powdery guanidine salt polymer product, wherein a guanidine salt polymer is separated from an aqueous solution by an ion separation exchange membrane to prepare a powdery sample. Patent documents CN1350022A, CN1445270A, and US7282538B2 disclose a method for preparing polyamine and guanidinium polymer, wherein the guanidinium polymer contains double bonds, epoxy and other active groups in the molecular structure, and is used for performing melting, solution and solid phase grafting reaction with resin polymer to prepare antibacterial plastic products. Patent documents CN102453315A, CN102453316A, and CN102286176A disclose that a composite antibacterial agent is prepared by a method of coprecipitation of a guanidine salt polymer with pyridine sulfate, silicate, and the like, and the composite antibacterial agent is applied to film products and foam products such as polylactic acid and polypropylene.
It can be seen from the above patent documents that the conditions for preparing guanidine salt polymer powder in CN101037503A and CN1350022A are relatively harsh, and the process is relatively complicated; in CN1445270A and US7282538B2, guanidine salt polymer needs to be prepared into antibacterial master batches, so that the steps are complicated, and the cost is high; the CN102453315A and the CN102453316A need to use sodium pyrithione, so the cost is higher; CN102453273A needs to be operated at a certain temperature in the process of preparing the antibacterial agent, the energy consumption is large, and the control of the appearance and the particle size of the dried and crushed product is not good.
Therefore, the antibacterial BOPE film with good antibacterial effect and stable optical performance and mechanical performance cannot be prepared by adopting the existing antibacterial agent, and the application of the film in practice cannot be met.
Disclosure of Invention
The invention aims to overcome the problems that the existing polyethylene film has no antibacterial property or poor antibacterial property and the film strength is lower, and provides a biaxially oriented polyethylene antibacterial film and a preparation method thereof.
The invention provides a biaxially oriented polyethylene antibacterial film, which comprises a polyethylene core layer and an antibacterial surface layer attached to at least one side surface of the polyethylene core layer, wherein the antibacterial surface layer is a polyethylene layer dispersed with a guanidine salt composite antibacterial agent; wherein, the guanidine salt compound antibacterial agent contains a guanidine salt polymer, a zinc salt and/or a copper salt, an anti-migration agent, nano-powder rubber and a dispersing agent; in the guanidine salt composite antibacterial agent, based on 100 parts by weight of guanidine salt polymer, the content of zinc salt and/or copper salt is 0.01-40 parts by weight, the content of anti-migration agent is 0.1-10 parts by weight, the content of nano-powder rubber is 0.5-100 parts by weight, and the content of dispersing agent is 0.1-10 parts by weight; preferably, the content of the zinc salt and/or the copper salt is 5-25 parts by weight, the content of the anti-migration agent is 0.2-5 parts by weight, the content of the nano-scale powder rubber is 4.5-50 parts by weight, and the content of the dispersing agent is 0.5-5 parts by weight; more preferably, the anti-migration agent is contained in an amount of 0.3 to 2 parts by weight, and the nano-scale powder rubber is contained in an amount of 10 to 30 parts by weight.
The polyethylene is a thermoplastic resin produced by using ethylene as a raw material, has good low-temperature resistance (the lowest use temperature can reach-70 ℃ to-100 ℃), chemical stability and corrosion resistance, and is widely used for packaging materials. In the polyethylene film provided by the invention, the polyethylene raw material can be obtained by the polyethylene structure and the preparation method described in Chinese patents CN105623057A, CN105623056A, CN105623061A and CN 105623055A.
According to the target product of the invention, the melt index of the polyethylene in the polyethylene core layer and the antibacterial surface layer at 190 ℃ under the load of 2.16kg is 0.5g/10min-5g/10min, preferably 1g/10min-3.5g/10 min; further preferably, the polyethylene in the polyethylene core layer and the antibacterial surface layer has a melting temperature of 105-138 ℃.
According to the invention, the thickness of the polyethylene core layer and the thickness of the antibacterial surface layer can be properly selected according to the using conditions of the polyethylene film, and if the using conditions require that the polyethylene film has higher mechanical strength and higher antibacterial performance, the thickness of the polyethylene core layer and the thickness of the antibacterial surface layer can be thicker; if the conditions of use require that the polyethylene film has good light transmission performance, the thickness of the polyethylene core layer and the thickness of the antibacterial surface layer can be thinner. Typically, the polyethylene core layer may have a thickness of 5 to 100 micrometers, and the antimicrobial surface layer attached to at least one side surface of the polyethylene core layer may have a thickness of 0.1 to 10 micrometers, and accordingly, the antimicrobial agent has a particle diameter of 0.01 to 10 micrometers; in order to further improve the overall performance of the obtained polyethylene film, the thickness of the polyethylene core layer can be 10-60 microns, the thickness of the antibacterial surface layer on one side of the polyethylene core layer can be 1-5 microns, and correspondingly, the particle diameter of the antibacterial agent is 0.1-5 microns.
The biaxially oriented polyethylene antibacterial film of the present invention preferably has the following characteristics: the longitudinal tensile strength is more than or equal to 80MPa, the transverse tensile strength is more than or equal to 100MPa, and the antibacterial rate is more than or equal to 95%.
According to the present invention, the content of the complex antimicrobial agent in the polyethylene surface layer can vary within a wide range, and it should be understood by those skilled in the art that the larger the content of the guanidine salt complex antimicrobial agent, the better the antimicrobial property, but the optical and mechanical properties of the film will be reduced, so that from the comprehensive consideration of the properties of the present invention, it is found through experiments by the inventors that the guanidine salt complex antimicrobial agent is preferably 0.05 to 2.0 parts by weight based on 100 parts by weight of the polyethylene resin in the antimicrobial surface layer.
According to a preferred embodiment of the invention, the antimicrobial surface layer may also comprise other components, for example, the antimicrobial surface layer optionally comprises a mould inhibitor and/or other auxiliaries.
According to the present invention, the mildewcide may be selected from at least one of pyridylthione, isothiazolinone, 10 ' -oxodiphenol Oxazine (OBPA), 3-iodo-2-propynyl butylcarbamate (IPBC), 2,4,4 ' -trichloro-2 ' -hydroxydiphenyl ether (triclosan), and 2- (thiazol-4-yl) benzimidazole (thiabendazole); the pyrithione is preferably at least one of zinc pyrithione, copper pyrithione, and dipyrithione; the isothiazolinone is preferably at least one of 2-methyl-1-isothiazolin-3-one (MIT), 5-chloro-2-methyl-1-isothiazolin-3-one (CMIT), 2-n-octyl-4-isothiazolin-3-One (OIT), 4, 5-dichloro-2-n-octyl-3-isothiazolinone (DCOIT), 1, 2-benzisothiazolin-3-one (BIT), 4-methyl-1, 2-benzisothiazolin-3-one (MBIT) and 4-n-butyl-1, 2-benzisothiazolin-3-one (BBIT). The content of the mildewcide can be determined by referring to the conventional dosage in the prior art, for example, the content of the mildewcide can be 0 to 5.0 parts by weight, and preferably 0.05 to 0.5 part by weight.
In the present invention, the "other auxiliary agent" means other functional auxiliary agents than the auxiliary agents (e.g., antibacterial agents) specifically mentioned to be contained. For example, when the antibacterial surface layer does not contain a mildewcide, the other auxiliary agents may include a mildewcide, an antioxidant, a light stabilizer, a flame retardant, glass fiber, a toughening agent, a compatibilizer, a pigment, an inorganic filler. When the antibacterial surface layer contains the mildew inhibitor, the other auxiliary agents can comprise an antioxidant (such as a phenolic antioxidant, a phosphite antioxidant or a composite antioxidant consisting of the phenolic antioxidant and the phosphite antioxidant), a light stabilizer, a flame retardant, glass fibers, a toughening agent, a compatilizer, a pigment and an inorganic filler (such as nano calcium carbonate). The content of the other additives can also be determined by referring to the conventional amount in the prior art, for example, the content of the other additives can be 0 to 100 parts by weight, and preferably, the content of the other additives is 0.1 to 100 parts by weight.
According to the invention, the guanidine salt polymer can be various polyguanidine salts in the technical field of antibiosis, and preferably, the guanidine salt polymer is selected from at least one of inorganic acid salt and/or organic acid salt of polyhexamethylene (di) guanidine and polyoxyethylene guanidine; further preferably at least one selected from the group consisting of polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine phosphate, polyhexamethylene (bis) guanidine acetate, polyhexamethylene (bis) guanidine propionate, polyhexamethylene (bis) guanidine stearate, polyhexamethylene (bis) guanidine laurate, polyhexamethylene (bis) guanidine benzoate and polyhexamethylene (bis) guanidine sulfonate; still more preferably polyhexamethylene (bis) guanidine hydrochloride and/or polyhexamethylene (bis) guanidine propionate.
According to the present invention, the zinc salt and/or copper salt may be selected from various water-soluble zinc salts and/or copper salts, for example, at least one selected from zinc sulfate, zinc nitrate, zinc chloride, zinc acetate, copper sulfate, copper nitrate and copper chloride; preferably an inorganic zinc salt and/or an inorganic copper salt, for example at least one selected from zinc sulfate, zinc nitrate, zinc chloride, copper sulfate, copper nitrate and copper chloride; further preferably zinc sulfate and/or copper sulfate. The addition of the zinc salt and/or the copper salt obviously improves the antibacterial performance of the guanidine salt composite antibacterial agent.
The addition of the anti-migration agent can effectively improve the preparation of the guanidine salt polymerThe product has water resistance, and can achieve good antibacterial effect before and after water boiling even if the usage amount of the guanidine salt composite antibacterial agent is small. According to the present invention, preferably, the anti-migration agent is a blocked polyisocyanate, and further preferably at least one selected from the group consisting of a phenol-blocked polyisocyanate, a caprolactam-blocked polyisocyanate, and a butanone oxime-blocked polyisocyanate. In the present invention, the blocked polyisocyanate can be obtained commercially, for example, from Colesine2794 XP, bayer BL 5140.
The powder rubber in the guanidine salt composite antibacterial agent used by the invention is beneficial to reducing the water absorption of the guanidine salt composite antibacterial agent during storage, improving the moisture resistance of the guanidine salt composite antibacterial agent and improving the dispersibility of the antibacterial agent, thereby increasing the operability and the use timeliness of the antibacterial agent in practical application. In the invention, the nano-scale powder rubber can be various nano-sized powder rubber particles, and is preferably at least one of radiation-crosslinked fully-vulcanized styrene-butadiene rubber, fully-vulcanized carboxylated styrene-butadiene rubber, fully-vulcanized nitrile-butadiene rubber, fully-vulcanized carboxylated nitrile-butadiene rubber, fully-vulcanized acrylate rubber, fully-vulcanized ethylene vinyl acetate rubber, fully-vulcanized silicone rubber and fully-vulcanized vinylpyridine butadiene rubber; further preferred is fully vulcanized styrene-butadiene rubber and/or fully vulcanized silicone rubber.
According to the invention, the dispersant is used for improving the dispersibility of the antibacterial agent, and can be various dispersants which are conventional in the field, preferably nanoscale inorganic powder, and further preferably at least one selected from nanoscale calcium carbonate, silicon dioxide, montmorillonite, zinc oxide, talcum powder, titanium dioxide, carbon nano tubes, graphene, carbon fibers, boron nitride, zirconium dioxide, wollastonite and zeolite; more preferably nano-sized calcium carbonate and/or nano-sized fumed silica.
According to the present invention, the guanidine salt complex antimicrobial agent is preferably prepared by a method comprising the steps of:
a. contacting an aqueous guanidinium polymer solution with an aqueous solution of a zinc salt and/or a copper salt to form a transparent liquid mixture;
b. mixing the liquid mixture obtained in the step a with a latex solution after radiation crosslinking, and then adding an anti-migration agent to obtain a mixture;
c. and c, carrying out spray drying on the mixture obtained in the step b to obtain solid powder, and then mixing the solid powder with a dispersing agent to obtain the guanidine salt composite antibacterial agent.
According to the invention, the mass concentration of the guanidine salt polymer aqueous solution is preferably 10-40%, preferably 15-25%; the mass concentration of the aqueous solution of the zinc salt and/or the copper salt is 15-30%, preferably 20-25%; the mass concentration of the latex solution is 30-40%, and the latex solution is directly used after radiation crosslinking.
A large number of experiments show that the concentrations of the guanidine salt polymer aqueous solution, the zinc salt and/or copper salt aqueous solution and the latex solution are within the range of the preparation method, so that the guanidine salt composite antibacterial agent can be better prepared. The concentrations of the aqueous solution of the guanidine salt polymer, the aqueous solution of the zinc salt and/or the copper salt and the latex emulsion used in the method are not too high, otherwise, the uniform stirring is not facilitated, the coagulation phenomenon can occur, and the subsequent spray drying operation cannot be carried out; the concentration should not be too low, otherwise, the production efficiency will be low, and water and energy resources will be wasted. The preparation and mixing of the solution are carried out at room temperature, and the spray drying operation can be carried out after mixing, so the preparation method of the guanidine salt composite antibacterial agent has low energy consumption, short time and high efficiency, and can be used for continuous production.
In the above method, the spray drying may be performed in a spray dryer. The mixing of the solid powder and the dispersing agent can be carried out in a high-speed stirrer, and the guanidine salt composite antibacterial agent of the invention is obtained after high-speed stirring and dispersing.
In the above method, the guanidine salt polymer aqueous solution can be obtained by dissolving a solid guanidine salt polymer in water, or can be directly obtained commercially.
In the above method, preferably, the weight ratio of the guanidine salt polymer in the aqueous solution of the guanidine salt polymer, the zinc salt and/or copper salt in the aqueous solution of the zinc salt and/or copper salt, the solid solution in the latex solution, the anti-migration agent and the dispersant is 100: 0.01-40: 0.5-100: 0.1-10: 0.1 to 10; preferably, the weight ratio of the guanidine salt polymer in the guanidine salt polymer aqueous solution, the zinc salt and/or copper salt in the zinc salt and/or copper salt aqueous solution, the solid solution in the latex solution, the anti-migration agent and the dispersant is 100: 5-25: 4.5-50: 0.5-5: 0.5 to 5.
In the above method, the latex may be determined according to the type of the finally required powdered rubber, and preferably, the latex is at least one of styrene-butadiene latex, carboxylic styrene-butadiene latex, nitrile-butadiene latex, carboxylic nitrile-butadiene latex, acrylate latex, ethylene vinyl acetate latex, silicone rubber latex and butadiene-styrene-pyridine latex; preferably styrene-butadiene latex and/or silicone rubber latex.
According to the invention, as the antibacterial components such as the guanidine salt polymer, the zinc salt and the like are uniformly dispersed in the latex and then are subjected to spray drying, the antibacterial components are more uniformly dispersed in the final product, and the method is also beneficial to better dispersing effect of the powdered rubber in the processing process and improving the antibacterial effect.
The second aspect of the present invention provides a method for preparing the biaxially oriented polyethylene antibacterial film, which comprises the following steps:
a. uniformly mixing polyethylene resin, a guanidine salt composite antibacterial agent and an optional mildew preventive and/or other auxiliary agents, melting, mixing and extruding the uniformly mixed materials for granulation to obtain an antibacterial surface layer raw material;
b. feeding the antibacterial surface layer raw material and the polyethylene raw material into an extrusion casting device with a multi-layer co-extrusion structure for extrusion casting to obtain a casting sheet comprising a polyethylene core layer and an antibacterial surface layer attached to at least one side surface of the polyethylene core layer;
c. and carrying out biaxial tension on the obtained casting sheet to obtain the biaxial tension polyethylene film. The biaxial stretching may be performed by a flat film method.
According to the present invention, in order to obtain a polyethylene film with more excellent performance, the method preferably further comprises drying the polyethylene and the composite antimicrobial agent before mixing the polyethylene and the composite antimicrobial agent and before feeding the antimicrobial surface layer raw material and the polyethylene resin to a casting machine. The drying method and conditions may be those well known to those skilled in the art, and for example, vacuum drying, forced air drying, etc. may be used, and the drying temperature may be 30 to 100 ℃. The drying apparatus is typically a drying apparatus including heating, a dry hot air purge, or a vacuum system, and may be, for example, a continuous dryer, a vacuum oven, a hot air oven, and the like.
Generally, the polyethylene resin and the composite antibacterial agent can be uniformly mixed by adding the polyethylene and the composite antibacterial agent into various existing mixing devices and stirring and blending the mixture uniformly. The mixing device may be, for example, a stirrer, a kneader, an open mill, an internal mixer, or the like. The temperature and time for stirring and blending are well known to those skilled in the art, for example, the temperature for stirring and blending can be 25-65 ℃, the time for stirring and blending can be 1-30 minutes, and the rotating speed for stirring and blending can be 50-300 r/min; preferably, the mixture is stirred for 1 to 15 minutes at a rotation speed of 50 to 100 rpm and then for 1 to 15 minutes at a rotation speed of 100 to 200 rpm.
According to the present invention, the method, conditions and extruder for obtaining the raw material of the antibacterial surface layer by melt-kneading and extrusion-granulating the mixture obtained by uniformly mixing the polyethylene and the composite antibacterial agent are well known to those skilled in the art. For example, a double screw extruder or a single screw extruder can be used, the screw rotation speed is 150-. The vacuum degree in the present invention means an absolute value of a difference between an absolute pressure and an atmospheric pressure.
It should be noted that the extrusion casting apparatus generally includes a plurality of extruders, different materials can be heated in the plurality of extruders, and the materials heated by the different extruders can be extrusion cast through the same multilayer composite die head including at least two layers, so as to obtain a casting sheet including multiple layers; wherein the material in each extruder is extruded from one of the layers of the multilayer composite die. Therefore, it should be easily understood by those skilled in the art that, when a polyethylene film with an antibacterial surface layer attached to one side surface of a polyethylene core layer is to be obtained, two different extruders may be used to melt the raw material of the antibacterial surface layer and polyethylene, and the molten product is extruded and cast through the same die head comprising two layers at the same time, and two layers obtained after extrusion are laminated together to obtain a cast sheet, and then biaxially stretched to obtain the polyethylene antibacterial film of the present invention; when a polyethylene film with the antibacterial surface layers attached to the two side surfaces of the polyethylene core layer is required to be obtained, three different extruders can be adopted to melt raw materials (wherein polyethylene is added into the main extruder, and antibacterial surface layer raw materials are added into the surface layer extruder), the molten product is extruded and cast through the same die head comprising three layers at the same time, the three layers of films obtained after extrusion are laminated to obtain a cast sheet, and the polyethylene antibacterial film can be obtained after biaxial stretching.
The conditions of the extrusion casting and the extruder used are well known to those skilled in the art according to the present invention. For example, a single screw extruder, a twin screw extruder, or the like can be used. The conditions for extrusion typically include extrusion temperatures including extruder temperature, screen change zone temperature and head temperature, and casting cooling temperatures, which may be 150-; the casting cooling temperature generally refers to the temperature of the casting roll and may be 10 to 95 ℃.
According to the invention, the biaxial stretching can be carried out in a biaxial stretching device, for example, a film biaxial stretching machine of Karo IV type available from Br ü ckner, Germany, the biaxial stretching can be carried out by simultaneous stretching, i.e., stretching in the longitudinal direction (MD) and the Transverse Direction (TD) of the film simultaneously, or by stepwise stretching, i.e., stretching in the longitudinal direction (MD) of the film first and then stretching in the Transverse Direction (TD) of the film second, or by simultaneous stretching in the Transverse Direction (TD) of the film first and then stretching in the longitudinal direction (MD) of the film second, wherein the simultaneous stretching in the MD and TD is carried out after the cast sheet obtained by extrusion casting is sufficiently preheated at 80-140 ℃, the stretching ratio in the MD can be 2-7 times, the stretching ratio in the TD can be 2-7 times, the stretching temperature can be 80-140 ℃, the stepwise stretching is carried out after the cast sheet is sufficiently preheated at 80-140 ℃, the stretching ratio in the TD can be 2-7 times, the stretching temperature can be 80-140 ℃, the stretching ratio after the cast sheet obtained by extrusion casting is sufficiently preheated at 80-140 ℃.
According to the invention, the obtained film can be annealed after the stretch forming, so that the obtained film is prevented from generating large shrinkage; or the stretched film is directly cut and rolled to obtain the polyethylene antibacterial film product.
The key point of the present invention is to provide the components of the biaxially oriented polyethylene antibacterial film, especially the antibacterial surface layer thereof, and those skilled in the art will understand that the preparation process of the biaxially oriented polyethylene antibacterial film can adopt various processes conventional in the art, as long as the polyethylene antibacterial film with the above structure and composition can be prepared.
On one hand, the added guanidine salt composite antibacterial agent is spherical, has regular appearance shape, smaller particle size and uniform particle size distribution. After the antibacterial agent and the polyethylene film prepared by the method are subjected to biaxial tension, the antibacterial agent is uniformly dispersed on the surface layer of the film, so that the obtained polyethylene film has better antibacterial effect and water resistance; furthermore, the polyethylene antibacterial film prepared by the method does not need to wait for the antibacterial agent to migrate to the surface layer of the film, and can improve the production and use efficiency of the film.
In addition, the guanidine salt composite antibacterial agent adopted by the invention has good fluidity and low moisture absorption, and in the preparation process of the polyethylene antibacterial film, the guanidine salt polymer is not adhered to the wall, the blanking is easy, the production operation is simple, and excessive production condition control is not needed. The prepared antibacterial film has good antibacterial effect and improved water resistance.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
Exemplary embodiments of the present invention will be described in more detail by referring to the accompanying drawings.
Fig. 1 shows an electron microscope image of a guanidine salt complex antimicrobial used in one embodiment of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below.
The hot air ovens used in the examples and comparative examples were obtained from Beijing Tokyo instruments and were designated DF205, the equipment used for extrusion granulation was a twin screw extruder and was designated ZSK25 from WP, Germany, the biaxial stretcher was designated Karo IV from Br ü ckner, Germany, the extrusion casting equipment was designated LCR400 from Labtech, Sweden, and the melt index of the polyethylene was determined by means of a melt index apparatus designated MP600 from TO, USA.
The raw materials and sources used in the examples and comparative examples are as follows:
polyhexamethylene guanidine hydrochloride: shanghai high polymer practice Co., Ltd
Polyhexamethylene guanidine propionate: shanghai high polymer practice Co., Ltd
Polyhexamethylene biguanide hydrochloride: utility Co Ltd of Shanghai mountain
Zinc sulfate: xilong chemical corporation
Zinc acetate: xilong chemical corporation
Zinc nitrate: xilong chemical corporation
Styrene-butadiene latex: china petrochemical Beijing chemical research institute
Nitrile latex: china petrochemical Beijing chemical research institute
Silicon rubber latex: china petrochemical Beijing chemical research institute
Anti-migration agent: scientific wound2794 XP
Nano-grade calcium carbonate: jiangxi Huaming nanometer calcium carbonate Co Ltd
Fumed silica: shanghai Kayin chemical Co Ltd
Zinc pyrithione: peak Fine chemical Co Ltd
MIT, DCOIT: dalianbaiao chemical Co Ltd
Compound antioxidant: antioxidant 1010 and antioxidant 168 (1: 1 by weight), BASF, Germany
Polyethylene: trade marks BOPE-1, BOPE-2, BOPE-3, the China petrochemical Beijing chemical research institute;
the antibacterial detection standard and the operation steps are as follows:
1. antibacterial test standard: QB/T2591-2003A test method and antibacterial effect of antibacterial plastic antibacterial performance, detection bacteria: escherichia coli (Escherichia coli) ATCC 25922, Staphylococcus aureus (Staphylococcus aureus) ATCC 6538.
2. An antibacterial testing step, which refers to an antibacterial plastic detection standard QB/T2591-: and (3) sterilizing a sample to be detected by using 75% ethanol, drying the sample, and diluting the strain into a bacterial suspension with a proper concentration by using sterile water for later use. 0.2mL of the bacterial suspension was dropped on the surface of the sample, and a polyethylene film (4.0 cm. times.4.0 cm) having a thickness of 0.1mm was coated thereon to form a uniform liquid film between the sample and the film. Culturing at 37 ℃ for 18-24 hours with the relative humidity of 90%. The bacterial liquid is washed by sterile water, diluted to a proper concentration gradient, and 0.1mL of the bacterial liquid is uniformly coated on the prepared sterile agar culture medium. The culture was carried out at 37 ℃ for 18 to 24 hours, and the results were observed. The negative control was replaced with a sterile plate and the other operations were identical.
3. And (3) mildew resistance test: testing according to ASTM G21-96
The growth of the mold was observed for 28 days:
level 0: no growth, i.e. no growth observed under microscope (magnification 50);
level 1: trace growth, i.e., growth visible to the naked eye, but growth coverage area is less than 10%;
and 2, stage: the growth coverage area is not less than 10%.
Detection bacteria:
| serial number | Name (R) | Bacterial number |
| 1 | Aspergillus niger (Aspergillus niger) | AS 3.4463 |
| 2 | Aspergillus terreus (Aspergillus terreus) | AS 3.3935 |
| 3 | Aureobasidium Pullulans (Aureobasium Pullulans) | AS 3.3984 |
| 4 | Paecilomyces Varioti (Paecilomyces Varioti) | AS 3.4253 |
| 5 | Penicillium funiculosum (Penicillium funiculosum) | AS 3.3872 |
| 6 | Ball shell (Chaetomium globosum) | AS 3.4254 |
Example 1
This example illustrates the preparation of the polyethylene antimicrobial film provided by the present invention.
In this example, the polyethylene forming the polyethylene core layer and the antimicrobial surface layer was BOPE-1 from beijing chemical research institute of petrochemical origin, and had a melt index of 1g/10min and a melt temperature of 128 ℃ at 190 ℃ under a load of 2.16 kg.
(1) Preparing raw materials of the antibacterial surface layer:
the guanidine salt composite antibacterial agent is prepared as follows: a. dissolving 1000.0g of polyhexamethylene guanidine hydrochloride in water to prepare an aqueous solution with the mass concentration of 20%; 50.0g of zinc sulfate was prepared into an aqueous solution having a mass concentration of 25%. 125.0g of styrene-butadiene latex solution is directly used after radiation crosslinking, and the concentration is 40%. b. Adding the prepared guanidine salt polymer aqueous solution into a container containing zinc-containing and copper-containing aqueous solution, stirring while adding until uniformly mixing to form a transparent liquid mixture. c. And c, adding the liquid mixture obtained in the step b into the latex solution, and stirring while adding until the mixture is uniformly mixed. Then, 5.0g of an anti-migration agent was added to the mixture. d. C, drying the mixture obtained in the step c by using a spray dryer to obtain solid powder, wherein the particle diameter is 1-2 microns; transferring the obtained solid powder to a high-speed stirrer, adding 5.0g of fumed silica serving as a dispersing agent, and mixing and dispersing at a high speed to obtain the guanidine salt composite antibacterial agent 1# of the invention.
Drying polyethylene in a hot air oven, then adding 100 parts by weight of the dried polyethylene resin, 1.2 parts by weight of the guanidine salt compound antibacterial agent 1#, and 0.2 part by weight of the mildew preventive zinc pyrithione into a stirrer, and uniformly stirring at 25 ℃, wherein the stirrer firstly mixes for about 1 minute at a low speed of 100 revolutions per minute, and then mixes for 1 minute at a high speed of 200 revolutions per minute;
feeding the uniformly stirred mixture into a double-screw extruder. Adjusting the rotation speed of the screw to 350 r/min, and respectively controlling the temperature of each section to be as follows: 190 deg.C, 200 deg.C, 210 deg.C and 210 deg.C; the vacuum in each zone is maintained at 0.02 to 0.09 MPa; and melting, shearing, dispersing, compressing, exhausting, plasticizing and extruding the mixture in a screw and a barrel of the extruder, extruding the mixture through a die head at 210 ℃, and stretching, water-cooling and granulating to obtain the antibacterial surface layer raw material.
(2) Preparation of a cast sheet:
and (2) respectively drying the polyethylene and the antibacterial surface layer raw material obtained in the step (1) in a hot air oven, wherein the drying mode is that the polyethylene and the antibacterial surface layer raw material are continuously blown by dry hot air at the temperature of 80 ℃ for 8 hours. Adding the dried polyethylene into a main extruder of extrusion casting equipment, adding the antibacterial surface layer raw material obtained in the step (1) into a surface layer extruder of the extrusion casting equipment, carrying out melt extrusion, and carrying out casting molding by a casting roller to obtain a raw material sheet with the surface layer thickness of 35 micrometers and the core layer thickness of 350 micrometers. Wherein the temperature of the two extruders is set to be consistent, the temperature of each section of the extruder is 210 ℃, 220 ℃, 230 ℃ and 230 ℃, the temperature of the screen changing area is 240 ℃, the temperature of the machine head is 235 ℃, and the temperature of the casting roll is 25 ℃.
(3) And (3) bidirectional stretching and forming:
and (3) carrying out biaxial stretching on the raw material sheet obtained in the step (2) by using a biaxial stretcher. The stretching mode is that MD stretching is carried out first, and then TD stretching is carried out, wherein the preheating temperature of the MD stretching is 110 ℃, the stretching temperature is 100 ℃, and the stretching ratio is 5 times; the preheating temperature of TD stretching was 110 ℃, the stretching temperature was 100 ℃, and the stretching ratio was 7 times. Forming a polyethylene antibacterial film X1 comprising a polyethylene core layer and an antibacterial surface layer attached to one side surface of the polyethylene core layer, wherein the thickness of the polyethylene core layer is 10 microns, and the thickness of the antibacterial surface layer is 1 micron.
Cutting the prepared polyethylene antibacterial film X1 into standard sample strips, and then testing the tensile strength of the film to obtain: the film had a tensile strength of 85MPa in the machine direction and 103MPa in the transverse direction.
The prepared polyethylene antibacterial film X1 is cut into samples of 50mm multiplied by 50mm for antibacterial and mildewproof tests. Wherein part of samples are soaked in hot water at 50 ℃ for 16h before the antibacterial and mildewproof test.
And (3) antibacterial and mildewproof results:
before water boiling: the antibacterial rate of staphylococcus aureus is as follows: 99.9 percent; the antibacterial rate of escherichia coli is as follows: 99.9 percent; and (5) mildew prevention of 0 grade.
After water boiling: the antibacterial rate of staphylococcus aureus is as follows: 99.9 percent; the antibacterial rate of escherichia coli is as follows: 99.9 percent; and (5) mildew prevention of 0 grade.
Example 2
This example serves to illustrate the preparation of polyethylene films provided by the present invention.
In this example, the polyethylene forming the polyethylene core layer and the antimicrobial surface layer was BOPE-2 from beijing chemical research institute of the medium petrochemical industry, and had a melt index of 2 g/10min and a melt temperature of 123 ℃ at 190 ℃ under a load of 2.16 kg.
(1) Preparing raw materials of the antibacterial surface layer:
the guanidine salt composite antibacterial agent is prepared as follows: a. dissolving 1000.0g of polyhexamethylene biguanide hydrochloride in water to prepare an aqueous solution with the mass concentration of 10%; 200.0g of zinc nitrate was prepared into an aqueous solution having a mass concentration of 30%. 125.0g of the silicone rubber latex solution was used directly after radiation crosslinking, the concentration being 40%. b. Adding the prepared guanidine salt polymer aqueous solution into a container containing a zinc-containing aqueous solution, stirring while adding until the guanidine salt polymer aqueous solution and the zinc-containing aqueous solution are uniformly mixed to form a transparent liquid mixture. c. And c, adding the liquid mixture obtained in the step b into the latex solution, and stirring while adding until the mixture is uniformly mixed. Then, 5.0g of an anti-migration agent was added to the mixture. d. C, drying the mixture obtained in the step c by using a spray dryer to obtain solid powder, wherein the particle diameter is 2-4 microns; and transferring the obtained solid powder into a high-speed stirrer, adding 30.0g of talcum powder serving as a dispersing agent, and mixing and dispersing at a high speed to obtain the guanidine salt composite antibacterial agent 2 #.
Drying polyethylene in a hot air oven, then adding 100 parts by weight of the dried polyethylene resin, 0.8 part by weight of the guanidine salt composite antibacterial agent 2#, and 0.5 part by weight of the mildew preventive 2-methyl-1-isothiazoline-3-ketone (MIT) into a stirrer, uniformly stirring at 25 ℃, mixing the mixture at a low speed of 80 revolutions per minute for about 2 minutes, and then mixing at a high speed of 150 revolutions per minute for 0.5 minute;
feeding the uniformly stirred mixture into a double-screw extruder. Adjusting the rotation speed of the screw to 350 r/min, and respectively controlling the temperature of each section to be as follows: 190 deg.C, 200 deg.C, 210 deg.C and 210 deg.C; the vacuum in each zone is maintained at 0.02 to 0.09 MPa; and melting, shearing, dispersing, compressing, exhausting, plasticizing and extruding the mixture in a screw and a barrel of the extruder, extruding the mixture through a die head at 210 ℃, and stretching, water-cooling and granulating to obtain the antibacterial surface layer raw material.
(2) Preparation of a cast sheet:
and (2) respectively drying the polyethylene and the antibacterial surface layer raw material obtained in the step (1) in a hot air oven, wherein the drying mode is that the polyethylene and the antibacterial surface layer raw material are continuously blown by dry hot air at the temperature of 80 ℃ for 8 hours. Adding the dried polyethylene into a main extruder of extrusion casting equipment, adding the antibacterial surface layer raw material obtained in the step (1) into a surface layer extruder of the extrusion casting equipment, carrying out melt extrusion, and carrying out casting molding by a casting roller to obtain a raw material sheet with the surface layer thickness of 70 micrometers and the core layer thickness of 875 micrometers. Wherein the temperature of the two extruders is set to be consistent, the temperature of each section of the extruder is 210 ℃, 220 ℃, 230 ℃ and 230 ℃, the temperature of the screen changing area is 240 ℃, the temperature of the machine head is 235 ℃, and the temperature of the casting roll is 35 ℃.
(3) And (3) bidirectional stretching and forming:
and (3) carrying out biaxial stretching on the raw material sheet obtained in the step (2) by using a biaxial stretcher. The stretching method is to simultaneously stretch the film in the Machine Direction (MD) and the Transverse Direction (TD), wherein the preheating temperature during stretching is 110 ℃, the stretching temperature is 100 ℃, the MD stretching ratio is 5 times, and the TD stretching ratio is 7 times. Forming a polyethylene film X2 comprising a polyethylene core layer and an antibacterial surface layer attached to one side surface of the polyethylene core layer, wherein the thickness of the polyethylene core layer is 25 microns, and the thickness of the antibacterial surface layer is 2 microns.
Cutting the prepared polyethylene antibacterial film X2 into standard sample strips, and then testing the tensile strength of the film to obtain: the film had a tensile strength of 90MPa in the machine direction and 110MPa in the transverse direction.
The prepared polyethylene antibacterial film X2 is cut into samples of 50mm multiplied by 50mm for antibacterial and mildewproof tests. Wherein part of samples are soaked in hot water at 50 ℃ for 16h before the antibacterial and mildewproof test.
And (3) antibacterial and mildewproof results:
before water boiling: the antibacterial rate of staphylococcus aureus is as follows: 99.9 percent; the antibacterial rate of escherichia coli is as follows: 99.9 percent; and (5) mildew prevention of 0 grade.
After water boiling: the antibacterial rate of staphylococcus aureus is as follows: 99.9 percent; the antibacterial rate of escherichia coli is as follows: 99.9 percent; and (5) mildew prevention of 0 grade.
Example 3
This example serves to illustrate the preparation of polyethylene films provided by the present invention.
In this example, the polyethylene forming the polyethylene core layer and the antimicrobial surface layer was BOPE-3 from beijing chemical research institute of petrochemical origin, and had a melt index of 3.5g/10min and a melt temperature of 118 ℃ at 190 ℃ under a load of 2.16 kg.
(1) Preparing raw materials of the antibacterial surface layer:
the guanidine salt composite antibacterial agent is prepared as follows:
a. dissolving 1000.0g of polyhexamethylene guanidine propionate in water to prepare an aqueous solution with the mass concentration of 40%; 100.0g of zinc acetate was prepared into an aqueous solution with a mass concentration of 15%. 150.0g of the nitrile latex solution was used directly after radiation crosslinking, the concentration being 30%. b. Adding the prepared guanidine salt polymer aqueous solution into a container containing a zinc-containing aqueous solution, stirring while adding until the guanidine salt polymer aqueous solution and the zinc-containing aqueous solution are uniformly mixed to form a transparent liquid mixture. c. And c, adding the liquid mixture obtained in the step b into the latex solution, and stirring while adding until the mixture is uniformly mixed. Then, 5.0g of an anti-migration agent was added to the mixture. d. C, drying the mixture obtained in the step c by using a spray dryer to obtain solid powder; and transferring the obtained solid powder into a high-speed stirrer, adding 15.0g of nano calcium carbonate serving as a dispersing agent, and mixing and dispersing at a high speed to obtain the guanidine salt composite antibacterial agent # 3.
Drying polyethylene in a hot air oven, then adding 100 parts by weight of the dried polyethylene resin, 0.1 part by weight of the guanidine salt composite antibacterial agent No. 3, 0.25 part by weight of the composite antioxidant and 1 part by weight of the mildew preventive DCOIT into a stirrer, and uniformly stirring at 25 ℃, wherein the stirrer is firstly mixed at a low speed of 80 revolutions per minute for about 2 minutes and then is mixed at a high speed of 150 revolutions per minute for 0.5 minute;
feeding the uniformly stirred mixture into a double-screw extruder. Adjusting the rotation speed of the screw to 350 r/min, and respectively controlling the temperature of each section to be as follows: 190 deg.C, 200 deg.C, 210 deg.C and 210 deg.C; the vacuum in each zone is maintained at 0.02 to 0.09 MPa; and melting, shearing, dispersing, compressing, exhausting, plasticizing and extruding the mixture in a screw and a barrel of the extruder, extruding the mixture through a die head at 210 ℃, and stretching, water-cooling and granulating to obtain the antibacterial surface layer raw material.
(2) Preparation of a cast sheet:
and (2) respectively drying the polyethylene and the antibacterial surface layer raw material obtained in the step (1) in a hot air oven, wherein the drying mode is that the polyethylene and the antibacterial surface layer raw material are continuously blown by dry hot air at the temperature of 80 ℃ for 8 hours. Adding the dried polyethylene into a main extruder of extrusion casting equipment, adding the antibacterial surface layer raw material obtained in the step (1) into a surface layer extruder of the extrusion casting equipment, carrying out melt extrusion, and carrying out casting molding by a casting roller to obtain a raw material sheet with the surface layer thickness of 70 micrometers and the core layer thickness of 875 micrometers. Wherein the temperature of the two extruders is set to be consistent, the temperature of each section of the extruder is 210 ℃, 220 ℃, 230 ℃ and 230 ℃, the temperature of the screen changing area is 240 ℃, the temperature of the machine head is 235 ℃, and the temperature of the casting roll is 35 ℃.
(3) And (3) bidirectional stretching and forming:
and (3) carrying out biaxial stretching on the raw material sheet obtained in the step (2) by using a biaxial stretcher. The stretching method is to simultaneously stretch the film in the Machine Direction (MD) and the Transverse Direction (TD), wherein the preheating temperature during stretching is 110 ℃, the stretching temperature is 100 ℃, the MD stretching ratio is 5 times, and the TD stretching ratio is 7 times. Forming a polyethylene film X3 comprising a polyethylene core layer and an antibacterial surface layer attached to one side surface of the polyethylene core layer, wherein the thickness of the polyethylene core layer is 60 microns, and the thickness of the antibacterial surface layer is 5 microns.
Cutting the prepared polyethylene antibacterial film X3 into standard sample strips, and then testing the tensile strength of the film to obtain: the film had a tensile strength of 90MPa in the machine direction and 120MPa in the transverse direction.
The prepared polyethylene antibacterial film X3 is cut into samples of 50mm multiplied by 50mm for antibacterial and mildewproof tests. Wherein part of samples are soaked in hot water at 50 ℃ for 16h before the antibacterial and mildewproof test.
And (3) antibacterial and mildewproof results:
before water boiling: the antibacterial rate of staphylococcus aureus is as follows: 99.9 percent; the antibacterial rate of escherichia coli is as follows: 99.9 percent; and (5) mildew prevention of 0 grade.
After water boiling: the antibacterial rate of staphylococcus aureus is as follows: 99.9 percent; the antibacterial rate of escherichia coli is as follows: 99.9 percent; and (5) mildew prevention of 0 grade.
Comparative example 1
This comparative example serves to illustrate a reference preparation of a polyethylene film.
A polyethylene film was prepared in the same manner as in example 1, except that 1.2 parts by weight of the guanidine salt complex antimicrobial agent 1#1 of example 1 was replaced with 1.2 parts by weight of polyhexamethylene guanidine hydrochloride, and the film was cut into samples and subjected to the antimicrobial and antifungal test in the same manner as in example 1.
And (3) antibacterial results:
before water boiling: the antibacterial rate of staphylococcus aureus is as follows: 93.5 percent; the antibacterial rate of escherichia coli is as follows: 90.6 percent; and mildew resistance is 1 grade.
After water boiling: the antibacterial rate of staphylococcus aureus is as follows: 45.5 percent; the antibacterial rate of escherichia coli is as follows: 43.2 percent; and mildew resistance is grade 2.
The comparison result shows that the guanidine salt composite antibacterial agent not only improves the antibacterial and mildewproof effects of the film, but also has better water resistance, and the antibacterial and mildewproof effects of the antibacterial and mildewproof film before and after poaching are better than those of pure polyhexamethylene guanidine hydrochloride.
Comparative example 2
This comparative example serves to illustrate a reference preparation of a polyethylene film.
A polyethylene film was prepared according to the method of example 2, except that 0.8 parts by weight of guanidine salt complex antibacterial agent # 2 and 0.2 parts by weight of zinc pyrithione in example 2 were replaced with 1.0 part by weight of polyhexamethylene biguanide hydrochloride, and other steps were the same as in example 2, and the film was cut into samples and subjected to the antibacterial and antifungal test.
And (3) antibacterial and mildewproof results:
before water boiling: the antibacterial rate of staphylococcus aureus is as follows: 65.4 percent; the antibacterial rate of escherichia coli is as follows: 59.6 percent; and mildew resistance is 1 grade.
After water boiling: the antibacterial rate of staphylococcus aureus is as follows: 0; the antibacterial rate of escherichia coli is as follows: 0; and mildew resistance is grade 2.
The comparison result shows that after the dosage of the guanidine salt composite antibacterial agent is reduced and the mildew preventive zinc pyrithione is added, the film still has good antibacterial and mildew-proof effects, and the antibacterial and mildew-proof effects of the film before and after boiling are better than those of pure polyhexamethylene biguanide hydrochloride.
Comparative example 3
This comparative example serves to illustrate a reference preparation of a polyethylene film.
A polyethylene film was produced in the same manner as in example 3, except that 0.1 part by weight of the guanidine salt complex antibacterial agent # 3 and 1 part by weight of the fungicide DCOIT in example 3 were replaced with 1.1 part by weight of polyhexamethylene guanidine propionate, and the film was cut into specimens and subjected to an antibacterial and antifungal test in the same manner as in example 3.
And (3) antibacterial and mildewproof results:
before water boiling: the antibacterial rate of staphylococcus aureus is as follows: 70 percent; the antibacterial rate of escherichia coli is as follows: 55 percent; and mildew resistance is 1 grade.
After water boiling: the antibacterial rate of staphylococcus aureus is as follows: 0; the antibacterial rate of escherichia coli is as follows: 0; and mildew resistance is grade 2.
The comparison result shows that even if the dosage of the guanidine salt composite antibacterial agent is very low, the film still has good antibacterial and mildewproof effects, and the antibacterial and mildewproof effects of the film before and after poaching are better than those of pure polyhexamethylene guanidine propionate.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (12)
1. The biaxially oriented polyethylene antibacterial film is characterized by comprising a polyethylene core layer and an antibacterial surface layer attached to at least one side surface of the polyethylene core layer, wherein the antibacterial surface layer is a polyethylene layer dispersed with a guanidine salt composite antibacterial agent; wherein,
the guanidine salt composite antibacterial agent contains a guanidine salt polymer, zinc salt and/or copper salt, an anti-migration agent, nano-powder rubber and a dispersing agent; in the guanidine salt composite antibacterial agent, based on 100 parts by weight of guanidine salt polymer, the content of zinc salt and/or copper salt is 0.01-40 parts by weight, the content of anti-migration agent is 0.1-10 parts by weight, the content of nano-powder rubber is 0.5-100 parts by weight, and the content of dispersing agent is 0.1-10 parts by weight; preferably, the content of the zinc salt and/or the copper salt is 5-25 parts by weight, the content of the anti-migration agent is 0.2-5 parts by weight, the content of the nano-scale powder rubber is 4.5-50 parts by weight, and the content of the dispersing agent is 0.5-5 parts by weight.
2. The biaxially oriented polyethylene antimicrobial film according to claim 1, wherein the polyethylene in the polyethylene core layer and the antimicrobial surface layer has a melt index of 0.5g/10min-5g/10min, preferably 1g/10min-3.5g/10min at 190 ℃ under a 2.16kg load; the polyethylene in the polyethylene core layer and the antibacterial surface layer has a melting temperature of 105-138 ℃.
3. The biaxially oriented polyethylene antimicrobial film according to claim 1, wherein the thickness of said polyethylene core layer is 5 to 100 microns, and the thickness of said antimicrobial surface layer attached to at least one side surface of said polyethylene core layer is 0.1 to 10 microns; the particle diameter of the guanidine salt composite antibacterial agent is 0.01-10 microns; preferably, the thickness of the polyethylene core layer is 10-60 microns, and the thickness of the antibacterial surface layer attached to at least one side surface of the polyethylene core layer is 1-5 microns; the particle diameter of the guanidine salt composite antibacterial agent is 0.1-5 microns.
4. The biaxially oriented polyethylene antimicrobial film according to claim 1, wherein the biaxially oriented polyethylene antimicrobial film has a longitudinal tensile strength of not less than 80MPa, a transverse tensile strength of not less than 100MPa, and an antimicrobial rate of not less than 95%.
5. The biaxially oriented polyethylene antimicrobial film of claim 1, wherein said antimicrobial surface layer comprises polyethylene, a guanidinium complex antimicrobial agent and optionally a mold inhibitor and/or other additives; preferably, the content of the guanidine salt composite antibacterial agent is 0.05-2.0 parts by weight, the content of the mildew preventive is 0-5.0 parts by weight, and the content of the other auxiliary agents is 0-100 parts by weight, based on 100 parts by weight of polyethylene.
6. The biaxially oriented polyethylene antimicrobial film according to any one of claims 1 to 5, wherein the guanidine salt polymer is at least one selected from the group consisting of inorganic acid salts and/or organic acid salts of polyhexamethylene (bis) guanidine, polyoxyethylene guanidine;
preferably at least one selected from the group consisting of polyhexamethylene (bis) guanidine hydrochloride, polyhexamethylene (bis) guanidine phosphate, polyhexamethylene (bis) guanidine acetate, polyhexamethylene (bis) guanidine propionate, polyhexamethylene (bis) guanidine stearate, polyhexamethylene (bis) guanidine laurate, polyhexamethylene (bis) guanidine benzoate and polyhexamethylene (bis) guanidine sulfonate;
further preferred is polyhexamethylene (bis) guanidine hydrochloride and/or polyhexamethylene (bis) guanidine propionate.
7. The biaxially oriented polyethylene antimicrobial film according to any one of claims 1 to 5, wherein the zinc salt and/or copper salt is an inorganic zinc salt and/or an inorganic copper salt; preferably at least one selected from the group consisting of zinc sulfate, zinc nitrate, zinc chloride, copper sulfate, copper nitrate and copper chloride; further preferably zinc sulfate and/or copper sulfate.
8. The biaxially oriented polyethylene antibacterial film according to any one of claims 1 to 5, wherein the migration resistant agent is a blocked polyisocyanate, preferably at least one selected from the group consisting of a phenol blocked polyisocyanate, a caprolactam blocked polyisocyanate and a butanone oxime blocked polyisocyanate.
9. The biaxially oriented polyethylene antimicrobial film according to any one of claims 1 to 5, wherein the nano-scale powder rubber is at least one of radiation-crosslinked fully-vulcanized styrene-butadiene rubber, fully-vulcanized carboxylated styrene-butadiene rubber, fully-vulcanized nitrile-butadiene rubber, fully-vulcanized carboxylated nitrile-butadiene rubber, fully-vulcanized acrylate rubber, fully-vulcanized ethylene vinyl acetate rubber, fully-vulcanized silicone rubber and fully-vulcanized vinylpyridine butadiene rubber; preferably fully vulcanized styrene-butadiene rubber and/or fully vulcanized silicone rubber.
10. The biaxially oriented polyethylene antibacterial film according to any one of claims 1 to 5, wherein the dispersing agent is a nanoscale inorganic powder, preferably at least one selected from nanoscale calcium carbonate, silica, montmorillonite, zinc oxide, talcum powder, titanium dioxide, carbon nanotube, graphene, carbon fiber, boron nitride, zirconium dioxide, wollastonite and zeolite; further preferred is nanoscale calcium carbonate and/or nanoscale fumed silica.
11. The biaxially oriented polyethylene antimicrobial film according to any one of claims 1 to 5, wherein the guanidine salt composite antimicrobial agent is prepared by a method comprising the steps of:
a. contacting an aqueous guanidinium polymer solution with an aqueous solution of a zinc salt and/or a copper salt to form a transparent liquid mixture;
b. mixing the liquid mixture obtained in the step a with a latex solution after radiation crosslinking, and then adding an anti-migration agent to obtain a mixture;
c. c, spray drying the mixture obtained in the step b to obtain solid powder, and then mixing the solid powder with a dispersing agent to obtain the guanidine salt composite antibacterial agent;
preferably, the mass concentration of the guanidine salt polymer aqueous solution is 10-40%, preferably 15-25%; the mass concentration of the aqueous solution of the zinc salt and/or the copper salt is 15-30%, preferably 20-25%; the mass concentration of the latex solution is 30-40%.
12. The method for preparing biaxially oriented polyethylene antimicrobial film according to any one of claims 1 to 11, wherein the method comprises the steps of:
a. uniformly mixing polyethylene resin, a guanidine salt composite antibacterial agent and an optional mildew preventive and/or other auxiliary agents, melting, mixing and extruding the uniformly mixed materials for granulation to obtain an antibacterial surface layer raw material;
b. feeding the antibacterial surface layer raw material and the polyethylene raw material into an extrusion casting device with a multi-layer co-extrusion structure for extrusion casting to obtain a casting sheet comprising a polyethylene core layer and an antibacterial surface layer attached to at least one side surface of the polyethylene core layer;
c. and carrying out biaxial tension on the obtained casting sheet to obtain the biaxial tension polyethylene film.
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| CN109705424B (en) | 2021-11-19 |
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