US20160227785A1 - Bacteriostatic and fungistatic additive in masterbatch for application in plastics, and method for producing same - Google Patents
Bacteriostatic and fungistatic additive in masterbatch for application in plastics, and method for producing same Download PDFInfo
- Publication number
- US20160227785A1 US20160227785A1 US14/911,214 US201314911214A US2016227785A1 US 20160227785 A1 US20160227785 A1 US 20160227785A1 US 201314911214 A US201314911214 A US 201314911214A US 2016227785 A1 US2016227785 A1 US 2016227785A1
- Authority
- US
- United States
- Prior art keywords
- additive
- concentrate
- zinc oxide
- paste
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000654 additive Substances 0.000 title claims abstract description 105
- 230000000996 additive effect Effects 0.000 title claims abstract description 90
- 229920003023 plastic Polymers 0.000 title claims abstract description 35
- 239000004033 plastic Substances 0.000 title claims abstract description 35
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 230000003385 bacteriostatic effect Effects 0.000 title claims abstract description 16
- 230000001408 fungistatic effect Effects 0.000 title claims abstract description 16
- 239000004594 Masterbatch (MB) Substances 0.000 title claims description 13
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 127
- 239000011787 zinc oxide Substances 0.000 claims abstract description 63
- 229920000642 polymer Polymers 0.000 claims abstract description 45
- 239000012141 concentrate Substances 0.000 claims abstract description 42
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052709 silver Inorganic materials 0.000 claims abstract description 36
- 239000004332 silver Substances 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000008188 pellet Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 27
- 230000000813 microbial effect Effects 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 17
- 230000009467 reduction Effects 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 241000894006 Bacteria Species 0.000 claims description 11
- 241000233866 Fungi Species 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 7
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 6
- 229910001923 silver oxide Inorganic materials 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical compound [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 26
- 239000000047 product Substances 0.000 abstract description 10
- 239000004743 Polypropylene Substances 0.000 abstract description 9
- -1 polypropylene Polymers 0.000 abstract description 6
- 229920005669 high impact polystyrene Polymers 0.000 abstract description 5
- 239000004797 high-impact polystyrene Substances 0.000 abstract description 5
- 238000004806 packaging method and process Methods 0.000 abstract description 5
- 239000012467 final product Substances 0.000 abstract description 4
- 229920001155 polypropylene Polymers 0.000 abstract description 3
- 239000004814 polyurethane Substances 0.000 abstract description 3
- 229920002635 polyurethane Polymers 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004698 Polyethylene Substances 0.000 abstract description 2
- 239000004793 Polystyrene Substances 0.000 abstract description 2
- 229920000573 polyethylene Polymers 0.000 abstract description 2
- 239000002952 polymeric resin Substances 0.000 abstract description 2
- 229920002223 polystyrene Polymers 0.000 abstract description 2
- 229920003002 synthetic resin Polymers 0.000 abstract description 2
- 229920002959 polymer blend Polymers 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 230000000845 anti-microbial effect Effects 0.000 description 28
- 150000001875 compounds Chemical class 0.000 description 25
- 229920001684 low density polyethylene Polymers 0.000 description 18
- 239000004702 low-density polyethylene Substances 0.000 description 18
- 229940112824 paste Drugs 0.000 description 14
- 230000003115 biocidal effect Effects 0.000 description 12
- 239000004599 antimicrobial Substances 0.000 description 11
- 230000010354 integration Effects 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- XEFQLINVKFYRCS-UHFFFAOYSA-N Triclosan Chemical compound OC1=CC(Cl)=CC=C1OC1=CC=C(Cl)C=C1Cl XEFQLINVKFYRCS-UHFFFAOYSA-N 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 229960003500 triclosan Drugs 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 241000228245 Aspergillus niger Species 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 241000131448 Mycosphaerella Species 0.000 description 3
- 244000052616 bacterial pathogen Species 0.000 description 3
- 239000003139 biocide Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 241000222122 Candida albicans Species 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 241000223261 Trichoderma viride Species 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229940095731 candida albicans Drugs 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000002538 fungal effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 230000035755 proliferation Effects 0.000 description 2
- 229940100890 silver compound Drugs 0.000 description 2
- 150000003379 silver compounds Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 238000003856 thermoforming Methods 0.000 description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 2
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical class O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 1
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical class C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 description 1
- 241000228212 Aspergillus Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920003345 Elvax® Polymers 0.000 description 1
- 241000588722 Escherichia Species 0.000 description 1
- 239000005789 Folpet Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 241000087479 Pseudocercospora fijiensis Species 0.000 description 1
- 241000607142 Salmonella Species 0.000 description 1
- 241001138501 Salmonella enterica Species 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241000223259 Trichoderma Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- DMSMPAJRVJJAGA-UHFFFAOYSA-N benzo[d]isothiazol-3-one Chemical compound C1=CC=C2C(=O)NSC2=C1 DMSMPAJRVJJAGA-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- WIKQEUJFZPCFNJ-UHFFFAOYSA-N carbonic acid;silver Chemical compound [Ag].[Ag].OC(O)=O WIKQEUJFZPCFNJ-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000000254 damaging effect Effects 0.000 description 1
- NMCCNOZOBBWFMN-UHFFFAOYSA-N davicil Chemical compound CS(=O)(=O)C1=C(Cl)C(Cl)=NC(Cl)=C1Cl NMCCNOZOBBWFMN-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- HKIOYBQGHSTUDB-UHFFFAOYSA-N folpet Chemical compound C1=CC=C2C(=O)N(SC(Cl)(Cl)Cl)C(=O)C2=C1 HKIOYBQGHSTUDB-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 231100000957 no side effect Toxicity 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005596 polymer binder Polymers 0.000 description 1
- 239000002491 polymer binding agent Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- KQTXIZHBFFWWFW-UHFFFAOYSA-L silver(I) carbonate Inorganic materials [Ag]OC(=O)O[Ag] KQTXIZHBFFWWFW-UHFFFAOYSA-L 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 125000002348 vinylic group Chemical group 0.000 description 1
- 229940052228 zinc oxide paste Drugs 0.000 description 1
- 229940043810 zinc pyrithione Drugs 0.000 description 1
- 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 1
Images
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Definitions
- This invention refers to additives used in the plastics industry, particularly refers to an additive concentrate in the form of masterbatch with bacteriostatic and fungistatic activity manufactured by mixing a concentrate of nanoparticles of zinc oxide and a concentrate of metallic silver nanoparticles and a method for its manufactures.
- an antimicrobial composition comprising a silver compound selected from AgCl, AgBr, Ag2CO3 and Ag3PO4, deposited on a physiologically inert particle, selected from oxides of Ti, Mg , Al, Si, Ce, Hf, Nb and Ta, calcium hydroxyapatite and barium sulfate. It is disclosed that the compositions may be modified by the inclusion of other ingredients such as dispersion aids, and these compositions may be incorporated into polymeric materials in an amount of 5-60% by weight of compound.
- the antimicrobial silver compound in contact with the polymeric article may interact with it producing undesirable effects, such as darkening due to reduction to metallic silver.
- Zeolites are aluminosilicates, of either natural or synthetic origin, which have sites at which cationic exchange may occur.
- an antimicrobial metal ion can be substituted in the zeolite structure.
- Polymeric articles having antimicrobial properties are made by incorporating the treated zeolites with the polymer or else, the zeolite can be mixed with the polymer and then treated with a solution of the desired antimicrobial metal ion.
- the use of zeolite particles in polymer articles is described in detail in U.S. Pat. No. 4,775,585 (Hagiwarn et al., 1988), and more specifically, U.S. Pat. No.
- 4,525,410 (Hagiwara et al., 1985) is directed to applications in fibers. Furthermore, it is recognized that zeolite powders tend to agglomerate and are inferior in dispersibility when mixed with resins.
- U.S. Pat. No. 4,741,779 discloses the addition of fine silica, dry or in sol form, to provide a zeolite powder having free flowability and low agglomerating properties. Such problems as aggregation and colour development in zeolite antimicrobial compositions also are addressed in other documents which relate to the use of additives such as fatty acid salts to aid in the dispersion of UV light absorbers to prevent color development.
- an antimicrobial coating which includes an inorganic antimicrobial additive, a colloidal polymer medium and water is described; the additive includes particles having a diameter of 2 to 3 microns which include one element of the group consisting of silver, platinum, gold, palladium, copper, zinc, boron and a compound of any of them.
- the colloidal polymer medium has a polymeric resins with a size similar to or smaller than the additive particles, preferably between 0.005 microns and less than 1 micron in diameter; the preferred polymer medium being a polyurethane, an acrylic or a polyester medium.
- U.S. Pat. 6,544,536 discloses processes for producing plastic bodies that can be processed further for medical uses, which exhibit an antimicrobial effective content of metal compounds of special type, from which an oligodynamic effect is known, such as silver, copper and gold, as well as heavy metals such as zinc and even lanthanides, which have, as intended in the invention, an effect on bacteria and fungi because they eliminate and prevent their multiplication and their adhesion or embedding in the plastic, or having at least a long lasting effect.
- metal compounds of special type from which an oligodynamic effect is known, such as silver, copper and gold, as well as heavy metals such as zinc and even lanthanides, which have, as intended in the invention, an effect on bacteria and fungi because they eliminate and prevent their multiplication and their adhesion or embedding in the plastic, or having at least a long lasting effect.
- One way to avoid high costs is not to subject all the plastic to antimicrobial treatment, but simply to coat the finished objects by any of the conventional methods such as physical vapour deposition, cathodic spraying (sputtering), plasma assisted vapour deposition, chemical methods such as currentless electroplating, reactive vapour deposition, reactive cathodic spraying, CVD, PACVD, which work only on the surfaces exposed to the source of the active substance to be applied, or as in the case of plasma assisted methods, at least one surface being open to the atmosphere being covered.
- the conventional methods such as physical vapour deposition, cathodic spraying (sputtering), plasma assisted vapour deposition, chemical methods such as currentless electroplating, reactive vapour deposition, reactive cathodic spraying, CVD, PACVD, which work only on the surfaces exposed to the source of the active substance to be applied, or as in the case of plasma assisted methods, at least one surface being open to the atmosphere being covered.
- the problem is solved in this patent using a method in which plastic bodies having a content of one or more oligodynamically active metals are produced, as a substance that is embedded in the plastic in the form of discrete particles, wherein the amount of active substance is not greater than 1.0% by weight, preferably not more than 0.5% by weight based on the total weight of the plastic body, and the maximum particle size of the active substance is less than 500 nm.
- Certain polymeric materials for example polyvinyl chloride, are susceptible to biological attack, especially from fungi.
- biocidal products have been developed for incorporation into plastics materials or paints to kill the responsible fungi or bacteria or to prevent their proliferation. It is also known to incorporate biocidal compounds into plastics to prevent the growth of bacteria or fungi to be found in food products.
- U.S. Pat. No. 5,433,424 and Japanese JP-A-06287403 and JP-A-07 071 869 among others examples are described of this latter type of product; and items such as surfaces for food preparation and household containers etc. are already widely available to consumers.
- WO 96/29361 patent application describes a biocidal polymeric matrix formed by a support matrix, an antimicrobial agent and a carrier agent, wherein the carrier agent and the antimicrobial agent are adapted to form at least one hydrogen bond or salt bridge between them.
- WO 96135205 patent application describes a white cover for piano keys formed by injection of a homogeneous dispersion of a methyl methacrylate resin and 0.5-2% of an antibacterial agent comprising a ceramic body prepared by sintering a mixture of phosphate calcium and metallic silver.
- WO 98/21253 patent application describes polymers which have antimicrobial properties and copolymers of vinyl monomers with non-functional vinyl comonomers of specified composition with ionic functionality.
- JP-A-08257493 patent application discloses the use of a steel plate having a layer of paint incorporating inorganic aggregates containing anti-bacterial compounds, as a lining for refrigerators, freezers or heating cabinets.
- JP-08145394 and JP-A08145392 patent applications describe the use of plastics incorporating anti-microbial compounds for use in ventilation apparatus.
- EP-A-606 762 patent application discloses a composition of a styrene polymer, an antibacterial agent and a compound having a specific functional group to produce an antibacterial resin composition.
- the invention disclosed by U.S. Pat. No. 6,632,855 patent application (Beverly et al, 2003) is directed towards improving the biocidal activity of acrylic materials containing known biocidal compounds.
- the selection of any particular biocide for articles of the invention is made according to the end use of the article and the properties of the product, for example its activity against certain types of microorganisms, toxicity, processability, etc.
- the biocide is preferably present in a concentration of at least 0.25% by weight, more preferably at least 1% by weight of the polymer, for example 0.5-3% by weight.
- the plastic material of the invention can have many applications. It is useful as a resin for moulding or extrusion applications, for example to make doors or panels for interior or exterior applications etc.
- plastic material of the invention may be especially useful as a coating on a substrate.
- One advantage of this form of the invention is that a relatively small amount of active biocide plastic can be used to confer a biocidal function to the surface of a non-biocidal substrate.
- biocidal compounds include triclosan, compounds based on heavy metals, especially silver, on inorganic carriers such as zeolites, hydroxyapatite, zinc oxide, titanium dioxide, zirconium phosphate, isothiazolones, derivates from benzisothiazolin-3-one, 10, 10 ‘oxibisphenoxiarsine, isothiazolines, zinc pyrithione, folpet (trichlormetil tio-phthalimide).
- biocidal compounds which are effective in the invention include those sold under the trademarks DENSILTM S (2356 tetrachloro-4 (methylsulphonyl) pyridine from Zeneca Ltd), SK-NOB-Z.TM. (Zirconium phosphate which contains silver, Sanai of Japan) and VANQUISHTM (n-butyl 1,2-benzisotiazoline, Zeneca Ltd).
- Still another object of the invention is to provide an additive that is effective when it is used in a proportion of between 0.01% and 0.5% on the total weight of the plastic formulation, depending on the type of polymer and its final application.
- masterbatch a concentrate containing ingredients that produce specific desired performance benefits either in the manufacture of the product or in the final product itself.
- Bacteriostatic means a substance that prevents cell reproduction of bacteria and therefore their proliferation.
- fungistatic is a substance that prevents or inhibits cellular reproduction of fungis.
- the present invention relates to an additive having fungistatic and bacteriostatic activities for the preparation of plastic items, especially for items that have direct contact with substances to be ingested or which come into direct contact with the skin, for instance drinking water reservoirs, cleaning accessories as well as tools and equipment for personal use.
- the additive is a concentrated masterbatch in pellet form, prepared starting from a mixture of concentrates of zinc oxide and silver oxide obtained from a paste of nanometric zinc oxide which is given a surface treatment to improve their properties for integration into the final compound and to prevent its degradation, as well as a paste of nanometric metallic silver.
- the additive may be incorporated directly and homogeneously to the plastic material to which it is added, ensuring the same activity across the exposed surface, and being integrated homogeneously in the polymer, the active agents (silver and zinc oxide) not being exhausted by migration to the surface, which extends the useful life of the item as to its bacteriostatic and fungistatic characteristics.
- the homogeneity in the integration of zinc oxide paste is ensured by a surface treatment of the nanoparticles with additives based on bifunctional a carbon hydrolyzable silane, for its affinity with a wide variety of inorganic substrates and its integration into a polymer carrier prior to mixing with a concentrate of nanometric metallic silver mixed with a thermoplastic polymer that acts as vehicle.
- FIG. 1 is a block diagram showing the process for producing the additive which is the object of the invention.
- FIG. 2 is a graph showing the comparative results of microbial reduction for 6 strains of organisms, for variable concentrations of ZnO/silver additive.
- FIG. 3 is a graph showing the effect of the concentration of the additive on the whiteness (L*) in containers with different contents of ZnO/Ag°.
- FIG. 4 shows the comparative results using the additive at concentrations of 0.0, 0.1 and 0.5%, in different polymer matrices on microbial activity for three strains of bacteria.
- FIG. 5 shows the comparative results using the additive at concentrations of 0.0, 0.1 and 0.5%, in different polymer matrices on microbial activity for two strains of fungi.
- FIG. 6 shows the effects of using the additive in polypropylene copolymer at concentrations of 0.15 and 0.3% before and after aging in an UV chamber.
- the present invention refers to an additive with bacteriostatic and fungistatic activity containing nanoparticles of ZnO/Ag°, in presentation of masterbatch in the form of pellets, used in the manufacture of plastic-based resins such as polypropylene, polyethylene, vinyl polychloride, polystyrene, high impact polystyrene, polyurethanes, etc. and the process for preparing the same.
- plastic-based resins such as polypropylene, polyethylene, vinyl polychloride, polystyrene, high impact polystyrene, polyurethanes, etc.
- the additive of the invention is directed to the manufacture of polymer products requiring to offer antimicrobial activity, for instance automobile parts, textiles, home appliances, toilet items, storage and transportation of water, packaging, etc.
- FIG. 1 the preferred production method for the fungistatic and bacteriostatic additive of the invention is shown, the method comprising the following process steps:
- a paste of nanometric zinc oxide ( 100 ) coming from a surface treatment based in silanes in a high intensity mixer ( 300 ) (for example, a mixer sold under the trademarks Draisswerke, Brabender, etc.) with the polymer or polymers which are compatible with the resin of the final application ( 200 ), until a 20% by weight concentrate of zinc oxide is obtained.
- a high intensity mixer for example, a mixer sold under the trademarks Draisswerke, Brabender, etc.
- step 2 with a resin compatible with the application to which the additive will be destined, permits said resin to act as a vehicle that can be easily integrated into the target resin and the percentage of concentrate added to the mixture should be such as to permit obtaining the desired ZnO:Ag° relation to incorporate into the final product.
- step 2 with a resin compatible with the application to which the additive will be destined, permits said resin to act as a vehicle that can be easily integrated into the target resin and the percentage of concentrate added to the mixture should be such as to permit obtaining the desired ZnO:Ag° relation to incorporate into the final product.
- step 5 To nix the zinc oxide concentrate from step I with the silver concentrate resulting from step II, in a twin screw extruder ( 700 ) (for example, the type marketed under the Brabender, Coperion, Werner & Pfleiderer etc. trademarks), for obtaining the additive concentrate of ZnO/Ag° in masterbatch in pellet form.
- a twin screw extruder 700
- the additive concentrate of ZnO/Ag° in masterbatch in pellet form for example, the type marketed under the Brabender, Coperion, Werner & Pfleiderer etc. trademarks
- Table 1 shows the preferred ranges for the specifications for the ZnO paste to be used in preparing the additive of the invention.
- Table 2 shows the preferred ranges for the specifications for the Ag° paste to be employed in preparing the additive of the invention, taking as an example the paste obtained from the method described in WO 2008/075933 patent application (Martinez et al, 2008).
- Table 3 are shown in summary, the comparative results obtained in the assessment of the effects on microbial activity (Drop Test) for strains of Staphylococcus aureus, Escherichia coli , and fungi Trichoderma viride, Aspergillus niger, Candida albicans and Mycosphaerella fijensis in low density polyethylene (LDPE) for use in packaging.
- Drop Test microbial activity
- FIG. 2 is a graph showing the comparative results of Table 3, for the percentage of microbial reduction in packaging of low density polyethylene (LDPE), on the vertical axis, where the first group of columns corresponds to LDPE without additive and the following six groups of columns refer to LDPE with 0.0 and 0.05% ZnO additive in relationships ZnO:Ag° from 10:90 to 90:10; the columns correspond, from left to right to Staphylococcus aureus, Escherichia coli, Trichoderma viride, Aspergillus niger, Candida albicans and Mycosphaerella fijensis .
- Table 3 showing the comparative results of Table 3, for the percentage of microbial reduction in packaging of low density polyethylene (LDPE), on the vertical axis, where the first group of columns corresponds to LDPE without additive and the following six groups of columns refer to LDPE with 0.0 and 0.05% ZnO additive in relationships ZnO:Ag° from 10:90 to 90:10; the columns correspond
- Table 4 is shown the effect of the content of the additive on the colour of the LDPE containers at different concentrations of ZnO/Ag°.
- the L* value refers to the colour settings for brightness ranging from zero (black colour) to 100 (white colour).
- FIG. 3 is a graph showing these results. It can be seen that the increase in additive content from 0%, for the columns on the left, 0.025% for the central columns up to 0.05%, for the columns to the right, does not significantly affect the value L*, shown on the vertical axis, associated with the whiteness of the compound. It is also important to note that the colour is not affected by the presence of silver because of the low doses used and also by the change in the ZnO/Ag° relationship.
- Tables 5 and 6 show comparative results on microbial activity, using two concentrations of the additive in various polymeric matrices, tested by the Test Drop method for three strains of bacteria (Table 5) and three strains of fungis (Table 6).
- the selected polymeric matrices for testing are as follows:
- Additive concentrations are such that an efficiency is achieved in the microbial reduction of more than 90%.
- FIGS. 4 and 5 are graphical representations of the results shown in Tables 5 and 6, respectively, the vertical axis showing the percentage of microbial reduction and the horizontal axis showing the percentages of additive employed for each polymer evaluated, showing FIG. 4 , groups of three columns for E. coli, S. choleraesuis and S. aureus, from left to right, and in FIG. 5 T., viride, A. niger and M. fijiensis , respectively, making it easier to appreciate the difference in microbial reduction.
- Table 7 shows the effects of using the additive at different concentrations (0.15 and 0.3%) of 340 RP polypropylene before and after aging in UV chamber, before aging for E. coli and after aging, for S. aureus .
- FIG. 6 graphically shows the difference in the count of bacterial colonies, vertical axis, before and after aging (left and right columns respectively in each pair of columns) as well as the effect of the additive and the variation in the concentration.
- the compound with triclosan considering the groups of sorted columns from left to right for the compound alone, the compound with triclosan, the compound with 0.15% of additive and the compound with 0.3% of additive, respectively, both the organic compound (triclosan) and the inorganic compound based on Zn/Ag° are highly efficient at inhibiting the growth of microorganisms with greater than 97% inhibition rates.
- the antimicrobial compound with the organic type additive starts decreasing its antimicrobial effectiveness as aging time reaches 120h, while the additive of inorganic nature Zn/Ag° remains active even after 120 h, this being due to the fact that the additive ZnO/Ag° is not consumed and does not migrate to the surface, but remains anchored to the polymer matrix and starts acting as the material wears out.
- the additive of the invention offers important advantages with respect to other additives conventionally employed in particular providing greater effectiveness in controlling fungi and bacteria, while maintaining without negative effects other properties of the target material; to one skilled in the art it will be apparent that the proportions of ZnO/Ag° in the final resin mixture shown in the examples are not limiting and are only intended to show a comparison of the effect of the presence of active elements as to its bacteriostatic and fungistatic activity and non damaging effects for other properties, so that such proportions can and should be adjusted to said target material, however, the method for preparing the additive is such that ensures dispersibility and permits better control of the amount of each of the active compounds in the final mix.
Abstract
Description
- This invention refers to additives used in the plastics industry, particularly refers to an additive concentrate in the form of masterbatch with bacteriostatic and fungistatic activity manufactured by mixing a concentrate of nanoparticles of zinc oxide and a concentrate of metallic silver nanoparticles and a method for its manufactures.
- People have been concerned for a long time to protect themselves from germs that can cause disease, infections and growth of bacteria and moulds. The manufacture of articles with antimicrobial additives helps to increase the protection against these microbes. Many products containing antimicrobial additives exist, including soaps, lotions and disinfectants and environment refreshing products. These products are used to clean surfaces that may have germs on them, which offers some protection benefits but do not prevent microbes to settle back. In the field of health care, medical devices and dental instruments as well as several surgical implants are manufactured with antimicrobial additives. These devices are in themselves impermeable to germs, but to thoroughly protect a surface, it should be possible to replace the entire surface with a new surface including antimicrobial additives.
- In the literature have been described polymeric articles with antimicrobial properties. Such articles are made in various shapes and dimensions, such as granules, films, fibers, containers, pipes, structural components, medical devices, etc. It is also known that certain metals such as silver, copper and zinc and its compounds are effective as antimicrobial agents. There have been many attempts to use this attribute in polymeric articles.
- For example, in U.S. Pat. No. 5,180,585 (Jacobson et al., 1993) an antibacterial composition and a method for its manufacture are described, comprising an inorganic particle with a first coating that provides antimicrobial properties and a second coating which provides a protective function, for incorporation into polymeric materials with antimicrobial properties. In the same patent some historical references on use patterns are presented; thus in U.S. Pat. No. 4,906,466 (Edwards et al, 1990) an antimicrobial composition is described comprising a silver compound selected from AgCl, AgBr, Ag2CO3 and Ag3PO4, deposited on a physiologically inert particle, selected from oxides of Ti, Mg , Al, Si, Ce, Hf, Nb and Ta, calcium hydroxyapatite and barium sulfate. It is disclosed that the compositions may be modified by the inclusion of other ingredients such as dispersion aids, and these compositions may be incorporated into polymeric materials in an amount of 5-60% by weight of compound. The antimicrobial silver compound in contact with the polymeric article may interact with it producing undesirable effects, such as darkening due to reduction to metallic silver.
- Several patents describe antimicrobial compositions in which zeolite particles as supports for antimicrobial metal ions are used. Zeolites are aluminosilicates, of either natural or synthetic origin, which have sites at which cationic exchange may occur.
- When treated with solutions of metal ions, an antimicrobial metal ion can be substituted in the zeolite structure. Polymeric articles having antimicrobial properties are made by incorporating the treated zeolites with the polymer or else, the zeolite can be mixed with the polymer and then treated with a solution of the desired antimicrobial metal ion. There are no barrier coatings on the particles to prevent interactions of the metal ions with the polymer to control the rate of release of the antimicrobial species or to facilitate dispersion of the particles into the polymer article. For example, the use of zeolite particles in polymer articles is described in detail in U.S. Pat. No. 4,775,585 (Hagiwarn et al., 1988), and more specifically, U.S. Pat. No. 4,525,410 (Hagiwara et al., 1985) is directed to applications in fibers. Furthermore, it is recognized that zeolite powders tend to agglomerate and are inferior in dispersibility when mixed with resins. U.S. Pat. No. 4,741,779 (Mita et al., 1988) discloses the addition of fine silica, dry or in sol form, to provide a zeolite powder having free flowability and low agglomerating properties. Such problems as aggregation and colour development in zeolite antimicrobial compositions also are addressed in other documents which relate to the use of additives such as fatty acid salts to aid in the dispersion of UV light absorbers to prevent color development. U.S. Pat. No. 8,105,688 (Liu, 2012) meanwhile, describes a combined solid phase inorganic powder, a masterbatch, a method for manufacturing the same, and a method for manufacturing a fiber that includes, in percentage: 10-20% of the masterbatch and 80-90% of a long chain polymer; the silver content in the fiber of the present invention reaching 3-10%, with a high kill rate, UV high blocking rate, is durable and safe efficiency and having no side or toxic effects.
- Another alternative for providing antimicrobial properties to the surfaces of various articles is disclosed in U.S. Pat. No. 8,282,951 (Redler, 2012), in which protective surface coatings and a method are described for applying such a coating, for example, to the external surfaces of a building. In one of the embodiments of the invention, an antimicrobial coating which includes an inorganic antimicrobial additive, a colloidal polymer medium and water is described; the additive includes particles having a diameter of 2 to 3 microns which include one element of the group consisting of silver, platinum, gold, palladium, copper, zinc, boron and a compound of any of them. The colloidal polymer medium has a polymeric resins with a size similar to or smaller than the additive particles, preferably between 0.005 microns and less than 1 micron in diameter; the preferred polymer medium being a polyurethane, an acrylic or a polyester medium.
- U.S. Pat. 6,544,536 (KraII et al., 2003) discloses processes for producing plastic bodies that can be processed further for medical uses, which exhibit an antimicrobial effective content of metal compounds of special type, from which an oligodynamic effect is known, such as silver, copper and gold, as well as heavy metals such as zinc and even lanthanides, which have, as intended in the invention, an effect on bacteria and fungi because they eliminate and prevent their multiplication and their adhesion or embedding in the plastic, or having at least a long lasting effect. The difficulty to find such materials commercially lies mainly in the high cost of the quantities of metal and/or metal compounds necessary to achieve the desired purpose, particularly in the case of silver, as these substances should be included in the plastic in powder form, in which case the lower limit of efficiency of metal/metal compound is often established set in the order of 1% by weight of the plastic, being used however higher amounts to make it more effective. Some examples of these applications are to be found in U.S. Pat. No. 4,054,139; WO-A-84/01721; EP-A-0190504 DE-A-: 37 25 728, EP-A-0251783 and DE-A-39 42 112. One way to avoid high costs is not to subject all the plastic to antimicrobial treatment, but simply to coat the finished objects by any of the conventional methods such as physical vapour deposition, cathodic spraying (sputtering), plasma assisted vapour deposition, chemical methods such as currentless electroplating, reactive vapour deposition, reactive cathodic spraying, CVD, PACVD, which work only on the surfaces exposed to the source of the active substance to be applied, or as in the case of plasma assisted methods, at least one surface being open to the atmosphere being covered. The problem is solved in this patent using a method in which plastic bodies having a content of one or more oligodynamically active metals are produced, as a substance that is embedded in the plastic in the form of discrete particles, wherein the amount of active substance is not greater than 1.0% by weight, preferably not more than 0.5% by weight based on the total weight of the plastic body, and the maximum particle size of the active substance is less than 500 nm.
- Certain polymeric materials, for example polyvinyl chloride, are susceptible to biological attack, especially from fungi. In order to reduce or to avoid the degradation of plastics resulting from such biological attack, biocidal products have been developed for incorporation into plastics materials or paints to kill the responsible fungi or bacteria or to prevent their proliferation. It is also known to incorporate biocidal compounds into plastics to prevent the growth of bacteria or fungi to be found in food products. In U.S. Pat. No. 5,433,424 and Japanese JP-A-06287403 and JP-A-07 071 869 among others, examples are described of this latter type of product; and items such as surfaces for food preparation and household containers etc. are already widely available to consumers.
- WO 96/29361 patent application describes a biocidal polymeric matrix formed by a support matrix, an antimicrobial agent and a carrier agent, wherein the carrier agent and the antimicrobial agent are adapted to form at least one hydrogen bond or salt bridge between them.
- WO 96135205 patent application describes a white cover for piano keys formed by injection of a homogeneous dispersion of a methyl methacrylate resin and 0.5-2% of an antibacterial agent comprising a ceramic body prepared by sintering a mixture of phosphate calcium and metallic silver.
- WO 98/21253 patent application describes polymers which have antimicrobial properties and copolymers of vinyl monomers with non-functional vinyl comonomers of specified composition with ionic functionality.
- WO 96/22023 patent application describes the use of derivatives of 2-alkyl or 2-aralkyl benzisothiazolin-3-one as fungicides for plastic materials.
- JP-A-08257493 patent application discloses the use of a steel plate having a layer of paint incorporating inorganic aggregates containing anti-bacterial compounds, as a lining for refrigerators, freezers or heating cabinets.
- The JP-08145394 and JP-A08145392 patent applications describe the use of plastics incorporating anti-microbial compounds for use in ventilation apparatus.
- EP-A-606 762 patent application discloses a composition of a styrene polymer, an antibacterial agent and a compound having a specific functional group to produce an antibacterial resin composition.
- U.S. Pat. No. 4,533,435 patent application describes an antimicrobial paper for packaging surgical supplies which incorporates antibacterial compounds in a vinylic polymer binder.
- The incorporation of antimicrobial agents is reviewed by D. Smock in Formulating and Compounding Plastics, March/April 1997 p. 16 and Plastics World March 1992 p. 58.
- The invention disclosed by U.S. Pat. No. 6,632,855 patent application (Beverly et al, 2003) is directed towards improving the biocidal activity of acrylic materials containing known biocidal compounds. The selection of any particular biocide for articles of the invention is made according to the end use of the article and the properties of the product, for example its activity against certain types of microorganisms, toxicity, processability, etc. The biocide is preferably present in a concentration of at least 0.25% by weight, more preferably at least 1% by weight of the polymer, for example 0.5-3% by weight. The plastic material of the invention can have many applications. It is useful as a resin for moulding or extrusion applications, for example to make doors or panels for interior or exterior applications etc. It can be supplied as a sheet material, for example, for providing walls, linings etc. or it may be suitable for forming into articles such as bathtubs for example by thermoforming. It may also be useful in the form of a primer, for example a polymethyl methacrylate resin dissolved in methyl methacrylate and optionally with a dispersion of fillers, colours and other functional particles for the manufacture of sinks, worktops, shower trays, etc. The plastic material of the invention may be especially useful as a coating on a substrate. One advantage of this form of the invention is that a relatively small amount of active biocide plastic can be used to confer a biocidal function to the surface of a non-biocidal substrate. Recommended biocidal compounds include triclosan, compounds based on heavy metals, especially silver, on inorganic carriers such as zeolites, hydroxyapatite, zinc oxide, titanium dioxide, zirconium phosphate, isothiazolones, derivates from benzisothiazolin-3-one, 10, 10 ‘oxibisphenoxiarsine, isothiazolines, zinc pyrithione, folpet (trichlormetil tio-phthalimide). Examples of biocidal compounds which are effective in the invention include those sold under the trademarks DENSIL™ S (2356 tetrachloro-4 (methylsulphonyl) pyridine from Zeneca Ltd), SK-NOB-Z.™. (Zirconium phosphate which contains silver, Sanai of Japan) and VANQUISH™ (n-butyl 1,2-benzisotiazoline, Zeneca Ltd).
- From the above examples, it can be seen that no efficient and inexpensive method, is already available to enable the production of plastic articles with antimicrobial properties, especially fungistatic and bacteriostatic, producing no adverse side effects.
- In view of the limitations and disadvantages of the additives with biological action in articles made from plastic resins, it is an object of the present invention to provide an additive with fungistatic and bacteriostatic activity for use in the manufacture of plastic articles.
- It is another object of the present invention to exploit the biological, physical and chemical properties of metallic silver and zinc oxide in the preparation of an additive with bacteriostatic and fungistatic activity for use in the manufacture of plastic articles while not deteriorating the desired properties of the material.
- It is still an object of the present invention to provide an additive comprising metallic silver and zinc oxide nanoparticles.
- It is yet another object of the present invention to provide an additive with fungistatic and bacteriostatic activity in the form of pellets masterbatch, for easy handling and integration with the polymer to be used in the final application.
- Still another object of the invention is to provide an additive that is effective when it is used in a proportion of between 0.01% and 0.5% on the total weight of the plastic formulation, depending on the type of polymer and its final application.
- It is yet another object of the present invention to provides a fungistatic and bacteriostatic additive which does not migrate to the surface of finished plastic articles.
- It is yet another object of the present invention to provide an additive that is not degraded by ultraviolet rays.
- These and other objects of the invention will be apparent from the following description and accompanying figures.
- In the text that follows, some of the terms used have the meaning described below.
- “masterbatch”: a concentrate containing ingredients that produce specific desired performance benefits either in the manufacture of the product or in the final product itself.
- “bacteriostatic”: means a substance that prevents cell reproduction of bacteria and therefore their proliferation.
- “fungistatic” is a substance that prevents or inhibits cellular reproduction of fungis.
- The present invention relates to an additive having fungistatic and bacteriostatic activities for the preparation of plastic items, especially for items that have direct contact with substances to be ingested or which come into direct contact with the skin, for instance drinking water reservoirs, cleaning accessories as well as tools and equipment for personal use.
- The additive is a concentrated masterbatch in pellet form, prepared starting from a mixture of concentrates of zinc oxide and silver oxide obtained from a paste of nanometric zinc oxide which is given a surface treatment to improve their properties for integration into the final compound and to prevent its degradation, as well as a paste of nanometric metallic silver.
- Due to the characteristics acquired by the additive as a result of the manufacturing process, the additive may be incorporated directly and homogeneously to the plastic material to which it is added, ensuring the same activity across the exposed surface, and being integrated homogeneously in the polymer, the active agents (silver and zinc oxide) not being exhausted by migration to the surface, which extends the useful life of the item as to its bacteriostatic and fungistatic characteristics.
- Due to the non migration of the particles it is sufficient to provide an article with an active surface containing said active compounds, making it possible to use plastics processing techniques in which the treated polymer occupies the outer layer or external surface of the article, with thickness of between 40 and 50 microns, thus being preferred processes of coextrusion, coinjection and rotomoulding for the production of articles.
- The homogeneity in the integration of zinc oxide paste is ensured by a surface treatment of the nanoparticles with additives based on bifunctional a carbon hydrolyzable silane, for its affinity with a wide variety of inorganic substrates and its integration into a polymer carrier prior to mixing with a concentrate of nanometric metallic silver mixed with a thermoplastic polymer that acts as vehicle.
-
FIG. 1 is a block diagram showing the process for producing the additive which is the object of the invention. -
FIG. 2 is a graph showing the comparative results of microbial reduction for 6 strains of organisms, for variable concentrations of ZnO/silver additive. -
FIG. 3 is a graph showing the effect of the concentration of the additive on the whiteness (L*) in containers with different contents of ZnO/Ag°. -
FIG. 4 shows the comparative results using the additive at concentrations of 0.0, 0.1 and 0.5%, in different polymer matrices on microbial activity for three strains of bacteria. -
FIG. 5 shows the comparative results using the additive at concentrations of 0.0, 0.1 and 0.5%, in different polymer matrices on microbial activity for two strains of fungi. -
FIG. 6 shows the effects of using the additive in polypropylene copolymer at concentrations of 0.15 and 0.3% before and after aging in an UV chamber. - The present invention refers to an additive with bacteriostatic and fungistatic activity containing nanoparticles of ZnO/Ag°, in presentation of masterbatch in the form of pellets, used in the manufacture of plastic-based resins such as polypropylene, polyethylene, vinyl polychloride, polystyrene, high impact polystyrene, polyurethanes, etc. and the process for preparing the same.
- The additive of the invention is directed to the manufacture of polymer products requiring to offer antimicrobial activity, for instance automobile parts, textiles, home appliances, toilet items, storage and transportation of water, packaging, etc.
- In
FIG. 1 the preferred production method for the fungistatic and bacteriostatic additive of the invention is shown, the method comprising the following process steps: - I. Preparation of a Concentrate of Zinc Oxide.
- 1. To mix a paste of nanometric zinc oxide (100) coming from a surface treatment based in silanes, in a high intensity mixer (300) (for example, a mixer sold under the trademarks Draisswerke, Brabender, etc.) with the polymer or polymers which are compatible with the resin of the final application (200), until a 20% by weight concentrate of zinc oxide is obtained.
- 2. To mix the concentrate from the previous step to between 1 and 10% by weight, with a resin (500), of the same nature as that of the previous step in a twin screw extruder (400) (such as the type sold under the trademarks Brabender, Coperion, Werner & Pfleiderer, etc).
- The mixing of step 2 with a resin compatible with the application to which the additive will be destined, permits said resin to act as a vehicle that can be easily integrated into the target resin and the percentage of concentrate added to the mixture should be such as to permit obtaining the desired ZnO:Ag° relation to incorporate into the final product.
- II. Preparation of a Concentrate of Nanometric Metallic Silver.
- 3. To mix (350) a paste of nanometric metallic silver (150) with a thermoplastic polymer (250) that is compatible with the resin of the final application, to obtain a concentrate of 10% silver,
- 4. To mix (450) the resulting mixture in a twin screw extruder (for example, the type marketed under the Brabender, Coperion, Werner & Pfleiderer, etc. trademarks) with a resin (550) of the same nature as the resin of step above, until obtaining a paste with between 0.1 and 1% silver
- The mixing of step 2 with a resin compatible with the application to which the additive will be destined, permits said resin to act as a vehicle that can be easily integrated into the target resin and the percentage of concentrate added to the mixture should be such as to permit obtaining the desired ZnO:Ag° relation to incorporate into the final product.
- III. Preparation of the Additive.
- 5. To nix the zinc oxide concentrate from step I with the silver concentrate resulting from step II, in a twin screw extruder (700) (for example, the type marketed under the Brabender, Coperion, Werner & Pfleiderer etc. trademarks), for obtaining the additive concentrate of ZnO/Ag° in masterbatch in pellet form.
- Preferred Mode of the Invention
- To achieve the optimal effect of the additive of the invention, as to maximize the biological effect and to reduce the possible effects on the properties of the resins in the final article, it is important to control the raw material specifications and the conditions of the method. In the following the data reflecting the best performance of the additive are offered.
- Raw Material
- Table 1 shows the preferred ranges for the specifications for the ZnO paste to be used in preparing the additive of the invention.
-
TABLE 1 Specifications for ZnO paste Characteristic Specification Method Purity (%) 100 DRx Size of the particles D10 (micron) 0.04-0.09 Horiba D50 (micron) 0.050-0.087 Horiba D90 (micron) 0.1-0.13 Horiba Solid contents (weight %) 45-50 Gravimetric - Table 2 shows the preferred ranges for the specifications for the Ag° paste to be employed in preparing the additive of the invention, taking as an example the paste obtained from the method described in WO 2008/075933 patent application (Martinez et al, 2008).
-
TABLE 2 Specifications for Ag° paste Characteristic Specification Method Purity (%) 99-99.3 Gravimetric Size of the particles D10 nm 41.5 Coulter LS230 D50 nm 47.0 Coulter LS230 D90 nm 56.0 Coulter LS230 Solid contents (weight %) 80-85 Gravimetric - Examples are provided in the following for the preparation at laboratory scale of the additive of the invention.
- A. Preparation of the silver concentrate in low density polyethylene (LDPE).
- To prepare the silver concentrate an intensive mixing equipment for polymers is used.
-
- Step 1. Enter into the equipment 167 g of silver paste with 80% by weight of solids,
- Step 2. Add 1200 g of virgin LDPE resin to obtain a concentrate of about 10% by weight of silver,
- Step 3. Mix for 8 minutes ensuring the complete integration into the molten polymer,
- Step 4. Homogenize the material obtained by means of a twin screw extruder,
- Step 5. Check final concentration, which should be about 10% by weight.
- B. Preparation of the ZnO Concentrate in Low Density Polyethylene (LDPE)
- It is started from a paste of zinc oxide at 50% by weight solids with the above described specifications.
- Once the dough is obtained its integration into the polymer is carried out in an equipment for intensive mixing of polymers, performing the following steps:
-
- Step 1. Introduce 600 g of paste of zinc oxide surface treated with silane additives into the chamber of the equipment,
- Step 2. Introduce 1200 g of LDPE resin,
- Step 3. Mix for 15 min to ensure good integration of the paste of zinc oxide nanoparticles with the virgin resin obtaining a concentrate of 20% zinc,
- Step 4. Homogenize the material by means of a twin screw extruder.
-
-
- a. Mix 225 g of zinc oxide concentrate with 25 g of silver concentrate, prepared according to Example 1,
- b. For a final application of 1 kg of LDPE, 40 g of the mixture from the previous step will be added, diluting with 960 g of LDPE for final application in a twin screw extruder for the additive ZnO/Ag° to be 0.2% by weight of the final mixture.
-
-
- a. Mix 45 g of the zinc oxide concentrate with 5 g of silver concentrate, prepared according to Example 1,
- b. For a final application of 1 kg at 0.05%, 50 g of concentrate will be added, diluting 950 g of the final compound for a final application in a twin screw extruder for the additive ZnO/Ag° to be at 0.05%.
- It is to be noted that the above examples produce an additive in a ZnO/Ag° ratio of 90:10, which is the recommended ratio for best results in typical applications, however combinations up to 10:90 ZnO/Ag can be used passing through the intermediate ranges for different performances and applications.
- Results
- The additive obtained according to the described method was tested on several polymers, in accordance with Examples 2 and 3, which were exposed to three bacterial strains and four fungal strains with the results shown below.
- In Table 3 are shown in summary, the comparative results obtained in the assessment of the effects on microbial activity (Drop Test) for strains of Staphylococcus aureus, Escherichia coli, and fungi Trichoderma viride, Aspergillus niger, Candida albicans and Mycosphaerella fijensis in low density polyethylene (LDPE) for use in packaging.
-
FIG. 2 is a graph showing the comparative results of Table 3, for the percentage of microbial reduction in packaging of low density polyethylene (LDPE), on the vertical axis, where the first group of columns corresponds to LDPE without additive and the following six groups of columns refer to LDPE with 0.0 and 0.05% ZnO additive in relationships ZnO:Ag° from 10:90 to 90:10; the columns correspond, from left to right to Staphylococcus aureus, Escherichia coli, Trichoderma viride, Aspergillus niger, Candida albicans and Mycosphaerella fijensis. -
TABLE 3 Effects of the use of the additive on the microbial activity in LDPE (Drop Test) for two strains of bacteria and four fungal strains at a concentration of 0.05% of the additive with different relationships ZnO:Ag° Microbial Reduction (%) Relationship S. E. T. A. C. M. ZnO:Ag° aereus coli viride niger albicans fijensis 0 41.5 42.9 38.5 38.7 35.4 36.6 10:90 79.1 77.6 75.8 76.1 74.3 74.0 25:75 83.0 81.1 82.9 79.5 80.2 81.4 50:50 84.8 82.0 81.6 81.5 79.7 78.5 75:25 84.2 85.7 82.6 81.7 81.3 82.4 80:20 86.1 86.4 83.7 84.2 81.3 83.8 90:10 92.5 92.1 90.3 88.9 89.1 86.7 - It can be appreciated that the increased efficiency of the microbial reduction by the action of the additive is substantial for all strains. As to the increase in the ratio of ZnO in the relationship)(ZnO/Ag° a remarkable improvement in microbial reduction is observed, with the result that the 90/10 ratio ZnO/Ag° is where the highest microbial reduction is obtained, although the additive is effective even with the 10-90 ratio, compared to the reduction produced by the polymer alone.
- In Table 4 is shown the effect of the content of the additive on the colour of the LDPE containers at different concentrations of ZnO/Ag°. The L* value refers to the colour settings for brightness ranging from zero (black colour) to 100 (white colour).
-
TABLE 4 Effect of additive concentration on the whiteness (L*) in containers with different contents ZnO/Ag° Whiteness(L*) Relationship Concentration of additive (%) (ZnO/Ag) 0 0.025 0.05 75:25 84 84 85 80:20 85 85 86 90:10 85 87 88 -
FIG. 3 is a graph showing these results. It can be seen that the increase in additive content from 0%, for the columns on the left, 0.025% for the central columns up to 0.05%, for the columns to the right, does not significantly affect the value L*, shown on the vertical axis, associated with the whiteness of the compound. It is also important to note that the colour is not affected by the presence of silver because of the low doses used and also by the change in the ZnO/Ag° relationship. - Tables 5 and 6 show comparative results on microbial activity, using two concentrations of the additive in various polymeric matrices, tested by the Test Drop method for three strains of bacteria (Table 5) and three strains of fungis (Table 6). The selected polymeric matrices for testing are as follows:
-
- an EVA polymer produced by Dupont under the
trade name Elvax 250®, - a PP polymer marketed under the brand Indelpro®,
- a HIPS polymer marketed under the brand Resirene®
- an EVA polymer produced by Dupont under the
- Additive concentrations are such that an efficiency is achieved in the microbial reduction of more than 90%.
-
TABLE 5 Effects of the use of the additive on microbial activity of three bacterial strains. Bacterial strains for the test % additive in % Microbial Reduction the final Escherichia Salmonella Staphylococcus Polymer application Coli Choleraesius Aureus EVA 0.0 11.9 11.5 10.6 0.1 91.2 90.7 92.8 PP 0.0 33.33 10 0 0.1 99.86 99.4 99.5 HIPS 0.0 81.8 79.6 78.8 0.5 99.4 98.6 96.5 - From the table is also evident that the effect of the additive is significant in low concentrations, although the effectiveness depends, as is well known, on the nature of the polymer in which it is applied.
-
TABLE 6 Effects of the use of the additive on microbial activity for three strains of fungi. Bacterial strains for the test % additive in % Microbial Reduction the final Trichoderma Aspergillus Mycosphaerella Polymer application Viride Niger Fijiensis EVA 0.0 11.2 10.4 10.7 0.1 92 90.3 90.1 PP 0.0 50 0 0 0.1 97.5 97 70 HIPS 0.0 79.1 78.6 79 0.5 95.3 93.2 93.7 -
FIGS. 4 and 5 are graphical representations of the results shown in Tables 5 and 6, respectively, the vertical axis showing the percentage of microbial reduction and the horizontal axis showing the percentages of additive employed for each polymer evaluated, showingFIG. 4 , groups of three columns for E. coli, S. choleraesuis and S. aureus, from left to right, and inFIG. 5 T., viride, A. niger and M. fijiensis, respectively, making it easier to appreciate the difference in microbial reduction. - Table 7 shows the effects of using the additive at different concentrations (0.15 and 0.3%) of 340 RP polypropylene before and after aging in UV chamber, before aging for E. coli and after aging, for S. aureus.
-
TABLE 7 Effects of the use of the additive in RP 340 polypropylene copolymer before and after aging Before aging After 120 h of aging Sample Inhibition %. Inhibition %. PP compound — — Compound with Triclosan 98.40% 88.06% PP compound with 0.15% 97.30% 93.28% additive PP compound with 0.3% 99.20% 95.52% additive -
FIG. 6 graphically shows the difference in the count of bacterial colonies, vertical axis, before and after aging (left and right columns respectively in each pair of columns) as well as the effect of the additive and the variation in the concentration. As can be seen in the table, considering the groups of sorted columns from left to right for the compound alone, the compound with triclosan, the compound with 0.15% of additive and the compound with 0.3% of additive, respectively, both the organic compound (triclosan) and the inorganic compound based on Zn/Ag° are highly efficient at inhibiting the growth of microorganisms with greater than 97% inhibition rates. However, the antimicrobial compound with the organic type additive (triclosan) starts decreasing its antimicrobial effectiveness as aging time reaches 120h, while the additive of inorganic nature Zn/Ag° remains active even after 120 h, this being due to the fact that the additive ZnO/Ag° is not consumed and does not migrate to the surface, but remains anchored to the polymer matrix and starts acting as the material wears out. After the discussions of these results it is to be concluded that some of the effects and/or advantages of using the additive of the invention are as follows: -
- it is a masterbatch additive in the form of pellets whose presentation makes it easily manageable during processing and application,
- it is compatible with a wide range of thermoplastic resins and “commodities” resins which are commonly used in the market for various applications,
- it can be used in various methods of plastics processing, either extrusion, injection, blow moulding, thermoforming, cast film, etc.
- it is highly efficient in controlling colonies of bacteria and fungi commonly found in nature,
- it is possible to achieve high rates of microbial inhibition at very low concentrations of additive in the final application starting from 0.05% and it is not required to exceed 0.5% by weight of the polymer-additive mixture,
- the effect of migration of the active compounds is removed, producing a lasting effect, beyond that expected for additives with similar action, for example, organic-based additives,
- photocatalytic reactions are prevented and therefore the premature degradation of the polymer due to its surface treatment in avoided, also facilitating its dispersibility and easy integration into the polymer into which it is to be applied,
- it does not have negative effects on the polymer properties, especially the colour of the polymer is not affected due to the presence of silver due to the low doses in which it is used,
- it is recyclable and its antimicrobial effect is not affected by reprocessing cycles and/or recycling.
- From the foregoing description and examples, it is evident that the additive of the invention offers important advantages with respect to other additives conventionally employed in particular providing greater effectiveness in controlling fungi and bacteria, while maintaining without negative effects other properties of the target material; to one skilled in the art it will be apparent that the proportions of ZnO/Ag° in the final resin mixture shown in the examples are not limiting and are only intended to show a comparison of the effect of the presence of active elements as to its bacteriostatic and fungistatic activity and non damaging effects for other properties, so that such proportions can and should be adjusted to said target material, however, the method for preparing the additive is such that ensures dispersibility and permits better control of the amount of each of the active compounds in the final mix.
Claims (6)
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US15/909,374 Active US11154063B2 (en) | 2013-06-25 | 2018-03-01 | Method for producing a bacteriostatic and fungistatic additive in masterbatch for application in plastics |
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WO2022172215A1 (en) * | 2021-02-12 | 2022-08-18 | Zinkh Nv | Dental apparatus with antimicrobial activity |
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Also Published As
Publication number | Publication date |
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CA2926945A1 (en) | 2014-12-31 |
EP3015422A1 (en) | 2016-05-04 |
WO2014209095A1 (en) | 2014-12-31 |
EP3015422A4 (en) | 2017-01-04 |
US11154063B2 (en) | 2021-10-26 |
US20180249715A1 (en) | 2018-09-06 |
WO2014209095A8 (en) | 2015-04-23 |
EP3575263A1 (en) | 2019-12-04 |
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