JPH01306473A - Expandable thermoplastic resin composition - Google Patents
Expandable thermoplastic resin compositionInfo
- Publication number
- JPH01306473A JPH01306473A JP13817788A JP13817788A JPH01306473A JP H01306473 A JPH01306473 A JP H01306473A JP 13817788 A JP13817788 A JP 13817788A JP 13817788 A JP13817788 A JP 13817788A JP H01306473 A JPH01306473 A JP H01306473A
- Authority
- JP
- Japan
- Prior art keywords
- zeolite
- ions
- ion
- thermoplastic resin
- antibacterial
- 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.)
- Pending
Links
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 26
- 239000011342 resin composition Substances 0.000 title claims abstract description 20
- 239000010457 zeolite Substances 0.000 claims abstract description 55
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 52
- 150000002500 ions Chemical class 0.000 claims abstract description 27
- 230000000843 anti-fungal effect Effects 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 230000000844 anti-bacterial effect Effects 0.000 claims description 51
- -1 ammonium ions Chemical class 0.000 claims description 25
- 229910021645 metal ion Inorganic materials 0.000 claims description 17
- 238000005187 foaming Methods 0.000 claims description 6
- 239000004604 Blowing Agent Substances 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000000088 plastic resin Substances 0.000 claims 1
- 229940121375 antifungal agent Drugs 0.000 abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 4
- 239000004088 foaming agent Substances 0.000 abstract description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 abstract 2
- 150000001455 metallic ions Chemical class 0.000 abstract 2
- 239000004156 Azodicarbonamide Substances 0.000 abstract 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 abstract 1
- 235000019399 azodicarbonamide Nutrition 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 230000002085 persistent effect Effects 0.000 abstract 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 abstract 1
- 235000017557 sodium bicarbonate Nutrition 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- 238000005342 ion exchange Methods 0.000 description 8
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 7
- 229910001431 copper ion Inorganic materials 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 2
- 239000003429 antifungal agent Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 229910001603 clinoptilolite Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052675 erionite Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 1
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 description 1
- 241001103808 Albifimbria verrucaria Species 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- 241001465318 Aspergillus terreus Species 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 241000690372 Fusarium proliferatum Species 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 241000191940 Staphylococcus Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000004708 Very-low-density polyethylene Substances 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- WRYNUJYAXVDTCB-UHFFFAOYSA-M acetyloxymercury Chemical compound CC(=O)O[Hg] WRYNUJYAXVDTCB-UHFFFAOYSA-M 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- RAGLTCMTCZHYEJ-UHFFFAOYSA-K azanium;chromium(3+);disulfate Chemical compound [NH4+].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RAGLTCMTCZHYEJ-UHFFFAOYSA-K 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 229910001451 bismuth ion Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 1
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- PSIBWKDABMPMJN-UHFFFAOYSA-L cadmium(2+);diperchlorate Chemical compound [Cd+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O PSIBWKDABMPMJN-UHFFFAOYSA-L 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- ZKJMJQVGBCLHFL-UHFFFAOYSA-K chromium(3+);triperchlorate Chemical compound [Cr+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZKJMJQVGBCLHFL-UHFFFAOYSA-K 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910001987 mercury nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- DRXYRSRECMWYAV-UHFFFAOYSA-N nitrooxymercury Chemical compound [Hg+].[O-][N+]([O-])=O DRXYRSRECMWYAV-UHFFFAOYSA-N 0.000 description 1
- FYWSTUCDSVYLPV-UHFFFAOYSA-N nitrooxythallium Chemical compound [Tl+].[O-][N+]([O-])=O FYWSTUCDSVYLPV-UHFFFAOYSA-N 0.000 description 1
- 150000004045 organic chlorine compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- HSAJRDKFYZAGLU-UHFFFAOYSA-M perchloryloxymercury Chemical compound [Hg+].[O-]Cl(=O)(=O)=O HSAJRDKFYZAGLU-UHFFFAOYSA-M 0.000 description 1
- OWFNVXUZWJBPMP-UHFFFAOYSA-M perchloryloxythallium Chemical compound [Tl+].[O-]Cl(=O)(=O)=O OWFNVXUZWJBPMP-UHFFFAOYSA-M 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 239000002984 plastic foam Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- HAAYBYDROVFKPU-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.N.[Ag+].[O-][N+]([O-])=O HAAYBYDROVFKPU-UHFFFAOYSA-N 0.000 description 1
- 229910052665 sodalite Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- YTQVHRVITVLIRD-UHFFFAOYSA-L thallium sulfate Chemical compound [Tl+].[Tl+].[O-]S([O-])(=O)=O YTQVHRVITVLIRD-UHFFFAOYSA-L 0.000 description 1
- 229940119523 thallium sulfate Drugs 0.000 description 1
- HQOJMTATBXYHNR-UHFFFAOYSA-M thallium(I) acetate Chemical compound [Tl+].CC([O-])=O HQOJMTATBXYHNR-UHFFFAOYSA-M 0.000 description 1
- 229910000374 thallium(I) sulfate Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- KOECRLKKXSXCPB-UHFFFAOYSA-K triiodobismuthane Chemical compound I[Bi](I)I KOECRLKKXSXCPB-UHFFFAOYSA-K 0.000 description 1
- 229920001866 very low density polyethylene Polymers 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- RXBXBWBHKPGHIB-UHFFFAOYSA-L zinc;diperchlorate Chemical compound [Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O RXBXBWBHKPGHIB-UHFFFAOYSA-L 0.000 description 1
- MLVWCBYTEFCFSG-UHFFFAOYSA-L zinc;dithiocyanate Chemical compound [Zn+2].[S-]C#N.[S-]C#N MLVWCBYTEFCFSG-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は抗菌並びに防黴機能を有する発泡性熱可塑性樹
脂組成物に関する。さらに詳しくは、本発明は殺菌作用
を有する金属を保持したゼオライト即ち無機系の抗菌性
ゼオライトを含有してなることを特徴とする抗菌並びに
防黴機能を有する電線用発泡性熱可塑性樹脂組成物に関
する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a foamable thermoplastic resin composition having antibacterial and antifungal functions. More specifically, the present invention relates to a foamable thermoplastic resin composition for electric wires having antibacterial and antifungal functions, which is characterized by containing a zeolite holding a metal having a bactericidal effect, that is, an inorganic antibacterial zeolite. .
従来発泡樹脂であるプラスチックは、真菌（黴）や細菌
のような微生物に対して高い抵抗性を存するものである
と信じられてきたが、微生物による発泡電線の被害が報
告されている。又発泡電線には安定剤、充填剤、酸化防
止剤、紫外線吸収剤、滑剤、着色剤等が添加されている
が、これらも微性物に弱い０本発明者等は市販の熱可塑
性樹脂に発泡剤を入れて電線に成形し電線の黴抵抗試験
をＪ ｒ Ｓ Ｚ−２９１１の方法に準拠して実施した
所黴の発育がｉ認された。Conventionally, plastic foam resins have been believed to be highly resistant to microorganisms such as fungi (mold) and bacteria, but there have been reports of damage to foamed electric wires caused by microorganisms. In addition, stabilizers, fillers, antioxidants, ultraviolet absorbers, lubricants, colorants, etc. are added to foamed wires, but these are also sensitive to minute substances. When a foaming agent was added and molded into an electric wire, the electric wire was subjected to a mold resistance test according to the method of J.R.S. Z-2911, and mold growth was observed.
上記の欠点を克服するために、各種の抗菌、防黴剤を電
線用発泡樹脂の中に添加することが試みられた。すなわ
ち、有機塩素系、有機硫黄系化合物が用いられてきたが
、抗菌性、防黴性、低毒性は必ずしも満足されているも
のとはいえない。特に電線は１０年以上、あるものは半
永久的に使用されるものであるため抗菌性、防黴の効果
が長期間に持続される必要がある。In order to overcome the above-mentioned drawbacks, attempts have been made to add various antibacterial and antifungal agents to foamed resins for electric wires. That is, although organic chlorine and organic sulfur compounds have been used, their antibacterial properties, antifungal properties, and low toxicity are not necessarily satisfactory. In particular, since electric wires are used for more than 10 years, and some are used semi-permanently, their antibacterial and anti-mildew effects need to last for a long time.
この様な黴の発生を防止するために本発明者らは発泡を
線の抗菌、防黴剤について鋭意検討を行った結果、抗菌
性金属イオンを保持しているゼオライトを添加した発泡
性熱可塑性樹脂は、真菌（黴菌）のみならず一般の細菌
に対しても抗菌力が高く、かつ長期間にわたって抗菌力
が持続されること、なかでも抗菌性金属イオンを保持し
ているゼオライトとしてゼオライト中のイオン交換可能
なイオンの一部又は全部をアンモニウムイオン及び抗菌
性金属イオンで置換してなるものを用いると、発泡を線
成形後の経時的変色の少ない発砲性熱可塑性樹脂組成物
が得られ特に好ましいことを見い出し本発明を完成する
に至った。In order to prevent the generation of mold, the present inventors conducted extensive research on antibacterial and antifungal agents for foaming lines, and found that a foamable thermoplastic containing zeolite that retains antibacterial metal ions was developed. The resin has high antibacterial activity against not only fungi (molds) but also general bacteria, and its antibacterial activity is sustained over a long period of time. When a part or all of the ion-exchangeable ions are replaced with ammonium ions and antibacterial metal ions, a foamable thermoplastic resin composition that exhibits less discoloration over time after foaming and wire molding can be obtained. The present invention was completed based on these favorable findings.
すなわち、本発明は、抗菌性金属イオンを保持している
ゼオライト（以下、抗菌性ゼオライトと称す、）、好ま
しくはゼオライト中のイオン交換可能なイオンの一部又
は全部をアンモニウムイオン及び抗凹性金属イオンで置
換された抗菌性ゼオライトを含有して成る抗菌性並びに
防黴性に優れる発泡性熱可塑性樹脂組成物を提供するも
のである。That is, the present invention provides a zeolite that retains antibacterial metal ions (hereinafter referred to as antibacterial zeolite), preferably a part or all of the ion exchangeable ions in the zeolite are replaced with ammonium ions and anticoncave metals. The present invention provides a foamable thermoplastic resin composition containing antibacterial zeolite substituted with ions and having excellent antibacterial and antifungal properties.
本発明において「ゼオライト」としては、天然ゼオライ
ト及び合成ゼオライトのいずれも用いることができる。In the present invention, as the "zeolite", both natural zeolite and synthetic zeolite can be used.
ゼオライトは、−Ｓに三次元骨格構造を有するアルミノ
シリケートであり、一般式％式％
れる。ここでＭはイオン交換可能なイオンを表わし通常
は１又は２価の金属のイオンである。ｎは（金属）イオ
ンの原子価である。ＸおよびＹはそれぞれの金属酸化物
、シリカ係数、Ｚは結晶水の数を表示している。ゼオラ
イトの具体例としては例えばＡ−型ゼオライド、Ｘ−型
ゼオライド、Ｙ−型ゼオライド、Ｔ−型ゼオライド、高
シリカゼオライト、ソーダライト、モルデナイト、アナ
ルサイム、クリノプチロライト、チャバサイト、エリオ
ナイト等を挙げることができる。ただしこれらに限定さ
れるものではない。これら例示ゼオライトのイオン交換
容量は、Ａ−型ゼオライド７ｍｅｑ／ｇ％Ｘ−型ゼオラ
イド６．４ｍｅｑ／ｇ、 Ｙ−型ゼオライド５ｍｅｑ／
ｇ−Ｔ−型ゼオライド３．４ｍｅｑ／ｇ、ソーダライト
１１．５＋ｅｑ／ｇ 、モルデナイト２．６ｍｅｑ／ｇ
、アナルサイム５＋ｅｑ／ｇ １クリノプチロライト２
．６ｍｅｑ／ｇ、チャバサイト５ｍｅｑ／ｇ、エリオナ
イト３．８ｍｅｑ／ｇであり、いずれも抗菌性金属イオ
ンでイオン交換するに充分の容量を有している。Zeolite is an aluminosilicate with a three-dimensional skeleton structure at -S, and has the general formula %. Here, M represents an ion exchangeable ion, and is usually a monovalent or divalent metal ion. n is the valence of the (metal) ion. X and Y represent the respective metal oxide and silica coefficients, and Z represents the number of water of crystallization. Specific examples of zeolites include A-type zeolide, can be mentioned. However, it is not limited to these. The ion exchange capacities of these exemplary zeolites are: A-type zeolide 7 meq/g, X-type zeolide 6.4 meq/g, Y-type zeolide 5 meq/g.
g-T-type zeolide 3.4 meq/g, sodalite 11.5+eq/g, mordenite 2.6 meq/g
, Analcyme 5 + eq/g 1 Clinoptilolite 2
．． 6 meq/g for chabasite, 5 meq/g for erionite, and 3.8 meq/g for erionite, all of which have sufficient capacity for ion exchange with antibacterial metal ions.
本発明で用いる抗菌性ゼオライトは、上記ゼオライト中
のイオン交換可能なイオン、例えばナトリウムイオン、
カルシウムイオン、カリウムイオン、マグネシウムイオ
ン、鉄イオン等のその一部又は全部を抗菌性金属イオン
、好ましくはアンモニウムイオン及び抗菌性金属イオン
で置換したものである。抗菌性金属イオンの例としては
、銀、銅、亜鉛、水銀、錫、鉛、ビスマス、カドミウム
、クロム又はタリウムのイオン、好ましくは銀、銅又は
亜鉛のイオンを挙げることができる。The antibacterial zeolite used in the present invention includes ion exchangeable ions in the zeolite, such as sodium ions,
Part or all of calcium ions, potassium ions, magnesium ions, iron ions, etc. are replaced with antibacterial metal ions, preferably ammonium ions and antibacterial metal ions. As examples of antimicrobial metal ions, mention may be made of ions of silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium or thallium, preferably ions of silver, copper or zinc.
抗菌性の点から、上記抗菌性金属イオンは、ゼオライト
中に０．１〜１５％含有されていることが適当である。From the viewpoint of antibacterial properties, it is appropriate that the antibacterial metal ions are contained in the zeolite in an amount of 0.1 to 15%.
銀イオン０．１〜１５％及び銅イオン又は亜鉛イオンを
０．１〜８％含有す含量菌性ゼオライトがより好ましい
。一方アンモニウムイオンは、ゼオライト中に２０％ま
で含有させることができるが、ゼオライト中のアンモニ
ウムイオンの含有量は０．５〜５％と、好ましくは０．
５〜２％とすることが、咳ゼオライトの変色を有効に防
止するという観点から適当である。向、木明ＩＩＢ書に
おいて、％とは１１０℃乾燥基準の重量％をいう。More preferred is a bacterial zeolite containing 0.1 to 15% silver ion and 0.1 to 8% copper ion or zinc ion. On the other hand, ammonium ions can be contained up to 20% in zeolite, but the content of ammonium ions in zeolite is 0.5 to 5%, preferably 0.5% to 5%.
A content of 5 to 2% is appropriate from the viewpoint of effectively preventing discoloration of cough zeolite. In Mukai and Kokumei IIB, % refers to % by weight on a dry basis at 110°C.
以下本発明で用いる抗菌性ゼオライトの製造方法につい
て説明する０例えば本発明で用いる抗菌性ゼオライトは
、予め調製した銀イオン、銅イオン、亜鉛イオン等の抗
菌性金属イオン、好ましくは更にアンモニウムイオンを
含有する混合水溶液にゼオライトを接触させて、ゼオラ
イト中のイオン交換可能なイオンと上記イオンとを置換
させる。The method for producing the antibacterial zeolite used in the present invention will be described below. For example, the antibacterial zeolite used in the present invention contains antibacterial metal ions such as silver ions, copper ions, and zinc ions prepared in advance, and preferably further contains ammonium ions. The zeolite is brought into contact with the mixed aqueous solution to replace the ion-exchangeable ions in the zeolite with the ions.
接触は、１０〜７０℃、好ましくは４０〜６０℃で３〜
２４時間、好ましくは１０〜２４時間バッチ式又は連続
式（例えばカラム法）によって行うことができる。Contacting is carried out at 10-70°C, preferably 40-60°C for 3-30°C.
It can be carried out for 24 hours, preferably for 10 to 24 hours, by a batch method or a continuous method (for example, a column method).
向上記混合水溶液のｐＨは３〜ＩＯ１好ましくは５〜７
に調整することが適当である。該調整により、恨の酸化
物等のゼオライト表面又は細孔内への析出を防止できる
ので好ましい。又、混合水溶液中の各イオンは、通常い
ずれも塩として供給される。The pH of the above mixed aqueous solution is 3 to IO1, preferably 5 to 7.
It is appropriate to adjust the This adjustment is preferable because it can prevent unwanted oxides from being deposited on the zeolite surface or in the pores. Further, each ion in the mixed aqueous solution is usually supplied as a salt.
例えばアンモニウムイオンは、硝酸アンモニウム、硫酸
アンモニウム、酢酸アンモニウム、過塩素酸アンモニウ
ム、チオ硫酸アンモニウム、リン酸アンモニウム等、恨
イオンは、硝酸銀、硫酸錫、過塩素酸銀、酢酸銀、ジア
ンミン銀硝酸塩、ジアンミン恨硫酸塩等、銅イオンは硝
酸１ｉｉ＜ＩＩ）、過塩素酸鋼、酢酸銅、テトラシアノ
＃ｊｊ４酸カリウム、硫酸銅等、亜鉛イオンは硝酸亜鉛
（■）、硫酸亜鉛、過塩素酸亜鉛、チオシアン酸亜鉛、
酢酸亜鉛等、水銀イオンは、過塩素酸水銀、硝酸水銀、
酢酸水銀等、錫イオンは、硫酸錫等、鉛イオンは、硫酸
鉛、硝酸鉛等、ビスマスイオンは、塩化ビスマス、ヨウ
化ビスマス等、カドミウムイオンは、過塩素酸カドミウ
ム、硫酸カドミウム、硝酸カドミウム、酢酸カドミウム
等、クロムイオンは、過塩素酸クロム、硫酸クロム、硫
酸アンモニウムクロム、硝酸クロム等、タリウムイオン
は、過塩素酸タリウム、硫酸タリウム、硝酸タリウム、
酢酸タリウム等を用いることができる。For example, ammonium ions include ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium perchlorate, ammonium thiosulfate, ammonium phosphate, etc., and anti-ion ions include silver nitrate, tin sulfate, silver perchlorate, silver acetate, diammine silver nitrate, diammine silver sulfate, etc. etc., copper ions include nitric acid 1ii<II), steel perchlorate, copper acetate, potassium tetracyano#jjtetraate, copper sulfate, etc., zinc ions include zinc nitrate (■), zinc sulfate, zinc perchlorate, zinc thiocyanate,
Mercury ions such as zinc acetate, mercury perchlorate, mercury nitrate,
Mercury acetate, etc., tin ions, tin sulfate, etc., lead ions, lead sulfate, lead nitrate, etc., bismuth ions, bismuth chloride, bismuth iodide, etc., cadmium ions, cadmium perchlorate, cadmium sulfate, cadmium nitrate, etc. Cadmium acetate, etc., chromium ions include chromium perchlorate, chromium sulfate, ammonium chromium sulfate, chromium nitrate, etc.; thallium ions include thallium perchlorate, thallium sulfate, thallium nitrate,
Thallium acetate or the like can be used.
ゼオライト中のアンモニウムイオン等の含有■は前記混
合水溶液中の各イオン（塩） ｔＭ度を調節することに
よって、適宜制御することができる。The content of ammonium ions, etc. in the zeolite can be appropriately controlled by adjusting the tM degree of each ion (salt) in the mixed aqueous solution.
例えば抗菌性ゼオライトがアンモニウムイオン及び恨イ
オンを含有する場合、前記混合水溶液中のアンモニウム
イオン１度を０．２Ｍ／ １〜２．５Ｍ／ ｌ、銀イオ
ン濃度を０．００２Ｍ／ １〜０．１５Ｍ／ ｉとする
ことによって、適宜、アンモニウムイオン含有量０．５
〜５％、銀イオン含有量０．１〜５％の抗菌性ゼオライ
トを得ることができる。又、抗菌性ゼオライトがさらに
銅イオン、亜鉛イオンを含有する場合、前記混合水溶液
中の銅イオン濃度は０．１Ｍ／ Ｉｌ〜０．８５Ｍ／
ｐ 、亜鉛イオン濃度は０．１５Ｍ／１〜１．２Ｍ／
１とすることによって、適宜銅イオン含を量０．１〜８
％、亜鉛イオン含有量０．１〜８％の抗菌性ゼオライト
を得ることができる。For example, when the antibacterial zeolite contains ammonium ions and antiseptic ions, the ammonium ion concentration in the mixed aqueous solution is 0.2M/1~2.5M/l, and the silver ion concentration is 0.002M/1~0.15M. /i, the ammonium ion content is 0.5 as appropriate.
5% and an antibacterial zeolite with a silver ion content of 0.1-5%. Further, when the antibacterial zeolite further contains copper ions and zinc ions, the copper ion concentration in the mixed aqueous solution is 0.1M/Il to 0.85M/
p, zinc ion concentration is 0.15M/1-1.2M/
1, the copper ion content can be adjusted to 0.1 to 8 as appropriate.
%, an antibacterial zeolite with a zinc ion content of 0.1-8% can be obtained.
本発明においては、前記の如き混合水溶液以外に各イオ
ンを単独で含有する水溶液を用い、各水溶液とゼオライ
トとを逐次接触させることによって、イオン交換するこ
ともできる。各水溶液中の各イオンの濃度は、前記混合
水溶液中の各イオン濃度に準じて定めることができる。In the present invention, in addition to the mixed aqueous solution as described above, ion exchange can also be performed by using an aqueous solution containing each ion individually and bringing each aqueous solution into contact with the zeolite sequentially. The concentration of each ion in each aqueous solution can be determined according to the concentration of each ion in the mixed aqueous solution.
イオン交換が終了したゼオライトは、充分に水洗した後
、乾燥する。乾燥は、常圧で１０５℃〜１１５℃、又は
減圧（１〜３０ ｔｏｒｒ）下７０℃〜９０′ｃで行う
ことが好ましい。After ion exchange, the zeolite is thoroughly washed with water and then dried. Drying is preferably carried out at 105° C. to 115° C. under normal pressure or 70° C. to 90° C. under reduced pressure (1 to 30 torr).
尚、鉛、ビスマスなど適当な水溶性塩類のないイオンや
有機イオンのイオン交換は、アルコールやアセトンなど
の有機溶媒溶液を用いて難溶性の塩基性塩が析出しない
ように反応させることができる。Ion exchange of ions without suitable water-soluble salts such as lead and bismuth or organic ions can be carried out using an organic solvent solution such as alcohol or acetone so that hardly soluble basic salts are precipitated.
本発明の発泡性熱可塑性樹脂組成物中の熱可塑性樹脂と
しては特に限定なく熱可塑性樹脂なら何でもよく、好ま
しくは高密度ポリエチレン、中密度ポリエチレン、低密
度ポリエチレン、超低密度ポリエチレン、リニアポリエ
チレン等の全てのポリエチレン、エチレン酢酸ビニル共
重合体（ＥＵＡ）、エチレンエチルアセテ−１−（ＥＥ
Ａ） 、ポリプロピレン、ポリスチレン、エチレンプロ
ピレンブロック共重合体等があげられる。これらの発泡
性熱可塑性樹脂組成物中に紫外線吸収剤、酸化防止剤、
無機充填剤、着色剤、改質材、滑剤、分散剤等が添加さ
れていても勿論差し支えない。The thermoplastic resin in the foamable thermoplastic resin composition of the present invention is not particularly limited and may be any thermoplastic resin, preferably high density polyethylene, medium density polyethylene, low density polyethylene, very low density polyethylene, linear polyethylene, etc. All polyethylene, ethylene vinyl acetate copolymer (EUA), ethylene ethyl acetate-1-(EE
A), polypropylene, polystyrene, ethylene propylene block copolymer and the like. These foamable thermoplastic resin compositions contain ultraviolet absorbers, antioxidants,
Of course, inorganic fillers, colorants, modifiers, lubricants, dispersants, etc. may be added.
一方発泡性熱可塑性樹脂組成物中の発泡剤は、アブジカ
ルボンアミドＣＡＤＣＡ）、オキシビスベンゼンヒドラ
ジド（ＯＢＳ旧等のを機発泡剤や重炭酸ナトリウム等の
無機発泡剤が好ましく、添加量は０．０１〜２０重量％
、好ましくは０．１〜５重量％である。On the other hand, the blowing agent in the foamable thermoplastic resin composition is preferably a mechanical blowing agent such as abdicarbonamide CADCA), oxybisbenzene hydrazide (OBS), or an inorganic blowing agent such as sodium bicarbonate, and the amount added is 0. 01-20% by weight
, preferably 0.1 to 5% by weight.
発泡剤の添加量が０．０１重量％未満では発泡を機能と
した電線にならず、添加量が１５重世％を越えても発泡
効果はそれ以上向上しなかった。If the amount of the foaming agent added was less than 0.01% by weight, an electric wire with a foaming function could not be obtained, and even if the amount added exceeded 15% by weight, the foaming effect did not improve any further.
次に発泡性熱可塑性樹脂組成物中の抗菌性ゼオライトの
添加量は、発泡電線に使用した場合０．０３〜５０重量
％、好ましくは０１０５〜２０重量％である。Next, the amount of antibacterial zeolite added in the foamable thermoplastic resin composition is 0.03 to 50% by weight, preferably 0.105 to 20% by weight when used in a foamed electric wire.
抗菌性ゼオライトの添加量が０．０３重量％未満では抗
菌及び防黴作用が低下する。一方添加量が３０重量％を
越えても抗菌及び防黴効果は変らなかった。If the amount of antibacterial zeolite added is less than 0.03% by weight, the antibacterial and antifungal effects will decrease. On the other hand, even when the amount added exceeded 30% by weight, the antibacterial and antifungal effects did not change.
発泡性熱可塑性樹脂組成物の製造方法は、特に限定され
ないが、たとえば熱可塑性樹脂と発泡剤と抗菌性ゼオラ
イトを予め混合機で混合しておき、押出機あるいはバン
バリーミキサ−等で混練し均一に分散させる方法等があ
る。The method for producing the foamable thermoplastic resin composition is not particularly limited, but for example, the thermoplastic resin, foaming agent, and antibacterial zeolite are mixed in advance in a mixer, and then kneaded in an extruder, Banbury mixer, etc., until the mixture is uniformly mixed. There are methods to disperse it.
本発明の発泡性熱可塑性樹脂組成物は発泡用途なら全て
に使用出来るが、とりわけ抗菌、防黴の効果が長期間に
わたって持続することを必要とする用途、たとえば電線
、食品物トレー、マツトレス、風呂用マ・ノド、断熱材
、手さげバッグ、フィルム、シート、パイプ等である。The foamable thermoplastic resin composition of the present invention can be used for all foaming applications, but especially for applications that require long-term antibacterial and antifungal effects, such as electric wires, food trays, pine tresses, and baths. These include handbags, insulation materials, handbags, films, sheets, pipes, etc.
本発明の発泡性熱可塑性樹脂組成物は、抗菌性ゼオライ
トを含有する故、すぐれた抗菌ならびに防黴性が長期に
わたって持続ししかも耐候性にすぐれるという利点があ
る。Since the foamable thermoplastic resin composition of the present invention contains antibacterial zeolite, it has the advantage of maintaining excellent antibacterial and antifungal properties over a long period of time, and has excellent weather resistance.
以下本発明を実施例によりさらに詳しく説明する。 The present invention will be explained in more detail below with reference to Examples.
参考例１ （抗菌性ゼオライトの調製法）ゼオライトは
、八−型ゼオライド（Ｎａ、０ ・Ａ１□０３・１．
９ｓｉ、ｏｔ ・ｘＨｚｏ：平均粒径１．５ 、ｃａ
ｍ）、Ｘ−型ゼオライド（ＮａｒＯ−ＡＩｚＯｔ −
２，３ＳｉＯｔ −ｘ ＨｔＯ：平均粒径２．５ μ
ＩＢ）、Ｙ−型ゼオライド（１，ＩＮａｚＯ・ＡＩｚＯ
ｚ・４ＳｉＯ＠ ・ｘ Ｈ，０：平均粒径０．７８層
）、天然クリノプチロライト（１５０〜２５０メツシユ
）の４種類を使用した。イオン交換の為の各イオンを提
供するための塩としてＮ Ｉｔ ＃ Ｎ Ｏ３、ＡｇＮ
Ｏｓ 、ＣｕＣＩＪＯｘ）ｘ及びＺｎ （Ｎｏ、）、の
４種類を使用した。Reference Example 1 (Preparation method of antibacterial zeolite) The zeolite was 8-type zeolide (Na, 0.A1□03.1.
9si,ot xHzo: Average particle size 1.5, ca
m), X-type zeolide (NarO-AIzOt −
2,3SiOt -x HtO: average particle size 2.5 μ
IB), Y-type zeolide (1, INazO・AIzO
Four types were used: z·4SiO@·x H,0: average particle size 0.78 layer) and natural clinoptilolite (150 to 250 mesh). N It # N O3, AgN as a salt to provide each ion for ion exchange
Four types were used: Os, CuCIJOx)x, and Zn(No,).
表１に各サンプル調製時に使用したゼオライトの種類と
混合水溶液に含まれる塩の種類及び濃度を示した。 Ｎ
ｏ、１”Ｎｏ、６の６種類の抗菌性ゼオライトのサンプ
ルを得た。Table 1 shows the type of zeolite used in preparing each sample and the type and concentration of salt contained in the mixed aqueous solution. N
Six types of antibacterial zeolite samples, No. 0, No. 1” and No. 6, were obtained.
各サンプルとも、１１０℃で加熱乾燥したゼオライト粉
末１ ｋｇに水を加えて、１．３ Ｉｌのスラリーとし
、その後攪拌して脱気し、さらに適量の０．５Ｎ硝酸溶
液と水とを加えてｐＨを５〜７に調整し、全容を１．８
１のスラリーとした。次にイオン交換の為、所定濃度の
所定の塩の混合水溶液３１を加えて全容を４．８ Ｉｌ
とし、このスラリー液を４０〜６０℃に保持し１０〜２
４時間攪拌しつつ平衡状態に到達させた状態に保持した
。イオン交換終了後ゼオライト粉を濾過し室温の水又は
温水でゼオライト相中の過剰の恨イオン又は銅イオン又
は亜鉛イオンがなくなる迄水洗した０次にサンプルを１
１０℃で加熱乾燥し、６種類のサンプルを得た。得られ
たＮｏ。For each sample, water was added to 1 kg of zeolite powder that had been heated and dried at 110°C to make a slurry of 1.3 Il, which was then stirred and degassed, and an appropriate amount of 0.5N nitric acid solution and water were added. Adjust pH to 5-7, total volume to 1.8
A slurry of No. 1 was prepared. Next, for ion exchange, a mixed aqueous solution 31 of a specified salt at a specified concentration was added to bring the total volume to 4.8 Il.
This slurry liquid was maintained at 40 to 60°C and heated to 10 to 2
The mixture was stirred for 4 hours and maintained at an equilibrium state. After ion exchange, the zeolite powder was filtered and washed with room temperature water or hot water until there were no excess ions, copper ions, or zinc ions in the zeolite phase.
Six types of samples were obtained by heating and drying at 10°C. Obtained no.
１〜Ｎ０１６の抗凹性ゼオライトサンプルに間するデー
タを表１に示す。The data for anti-concave zeolite samples No. 1 to No. 1 are shown in Table 1.
実施例１〜１１及び比較例１〜７
表１のサンプルＮｏ、１〜６の抗菌性ゼオライトをそれ
ぞれ１５０℃、ｌｍｎ１１ｇの減圧下で２時間乾燥した
０次に熱可塑性樹脂（リニアポリエチレン、高密度ポリ
エチレン、ポリスチレン等）と発泡剤（アゾジカルボン
アミド（ＡＤＣＡ）、オキシベンゼンスルホニルヒドラ
ジド（ＯＢＳＲ）等）と上記抗菌性ゼオライトを表２に
示す配合組成にて高速ミキサーで５分混合した後、１２
０〜１７０℃の温度で二軸押出機を用いて発泡性熱可塑
性樹脂組成物を得た。Examples 1 to 11 and Comparative Examples 1 to 7 Antibacterial zeolites of Samples No. and 1 to 6 in Table 1 were dried at 150° C. for 2 hours under reduced pressure of 11 g of lmn to form a zero-order thermoplastic resin (linear polyethylene, high density After mixing the above antibacterial zeolite with the composition shown in Table 2 for 5 minutes in a high-speed mixer,
A foamable thermoplastic resin composition was obtained using a twin screw extruder at a temperature of 0 to 170°C.
発泡性熱可塑性樹脂組成物を発泡電線成形機を用いて、
温度２００℃で、直径３■φ、発泡倍率１．３倍の電線
を作成した。Using a foam wire molding machine, the foamable thermoplastic resin composition is
At a temperature of 200° C., an electric wire with a diameter of 3 mm and an expansion ratio of 1.3 times was prepared.
ここに使用する熱可塑性樹脂、発泡剤の原料名及びメー
カー塩は次の通りである。The raw material names and manufacturer's salts of the thermoplastic resin and blowing agent used here are as follows.
本実施例の黴抵抗性試験評価は、日本工業規格ＪＴＳ
Ｚ ２９１１に準拠して行った。試験菌としては次の６
種類を使用した。The mold resistance test evaluation of this example is based on Japanese Industrial Standards JTS.
Z 2911. The following 6 test bacteria
type was used.
■アスペルギルス ニゲル
（Ａｓｐｅｒｇｉｌｌｕｓ ｎｉｇｅｒ）■アスペルギ
ルス テレウス
（Ａｓｐｅｒｇｉｌｌｕｓ ｔｅｒｒｅｕｓ）■ペニシ
リウム シトリナム
（Ｐｅｎｉｅｉｌｌｉｕｍ ｃｉｔｒｉｎｕｍ）■ケト
ミウム グロボスム
（Ｃｈａｅｊｏｍｉｕｍ ｇｌｏｂｏｓｕｍ）■フザリ
ウム プロリフエラーツム
（Ｆｕｓａｒｉｕｍ Ｐｒｏｌｉｆｅｒａｔｕｍ）■ミ
ロテシウム へルカリア
（Ｍｙｒｏｔｈｅｃｉｕｍ ｖｅｒｒｕｃａｒｉａ）試
験法は耐電圧試験を用いて評価した。■ Aspergillus niger ■ Aspergillus terreus ■ Penieillium citrinum ■ Chaejomium globosum ■ Fusarium Fusarium Proliferatum ■ Myrothecium verrucaria test method It was evaluated using a voltage test.
一般細菌に対する抗菌力試験は以下の方法によって行っ
た。Antibacterial activity tests against common bacteria were conducted using the following method.
細酊懸濁液（１０４個／ｍ ｌ ） Ｉｍ ｌを被験物
質懸濁液（ｉｏ’ｏｍｇ／ｍ １ ） ９ｍ ｌ中へ注
入混釈し３７℃２４時間作用させ、そのＱ、１ｍｆをＭ
ｕｅｌｌｅｒ−１（ｉｎｔｏｎ培地に分散させ、３７°
Ｃ２４時間後生存個体数を測定し死滅率を求めた。Inject and mix 1ml of Hosei suspension (104 pieces/ml) into 9ml of test substance suspension (io'omg/ml) and let it react for 24 hours at 37°C.
ueller-1 (dispersed in inton medium, 37°
C24 hours later, the number of surviving individuals was measured and the mortality rate was determined.
試験菌には以下の４種類の細菌を使用した。The following four types of bacteria were used as test bacteria.
■大腸菌（Ｅｓｃｈｓｒｉｃｈｉａ ｃｏｌｉ）■緑膿
菌（Ｐｓｅｕｄｏｍｏｎａｓ ａｅｒｕｇｉｎｏｓａ
）■枯草菌（Ｂａｃｉｌｌｕｓ ５ｕｂＬｉｌｌｉｓ）
■黄色ブドウ球菌（Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ ａ
ｕｒｅｕｓ）〔変色試験〕
発泡電線中のゼオライトの色が加工前と比較して変色し
たかどうか、また作成後２ケ月の日光照射により変色し
たかどうかを確認した。■ Escherichia coli ■ Pseudomonas aeruginosa
) ■ Bacillus subtilis (Bacillus 5ubLillis)
■ Staphylococcus aureus (Staphylococcus a)
(ureus) [Discoloration test] It was confirmed whether the color of the zeolite in the foamed electric wire had changed compared to before processing, and whether the color had changed due to sunlight irradiation for 2 months after creation.
発泡を線を実用使用と同様の場所に屋外暴露した。１２
ケ月後において一切の黴類の発生は認められなかった。The foam wire was exposed outdoors in the same place as in practical use. 12
After several months, no mold was observed.
比較例として市販されているを機系の抗菌剤を使用した
ものについて試験を行った。As a comparative example, a test was conducted using a commercially available antibacterial agent.
以上の評価結果を表２にまとめた。The above evaluation results are summarized in Table 2.
Claims (1)
してなる抗菌並びに防黴性を備えた発泡性熱可塑性樹脂
組成物。 ２、抗菌性金属イオンを保持しているゼオライトがゼオ
ライト中のイオン交換可能なイオンの一部又は全部をア
ンモニウムイオン及び抗菌性金属イオンで置換して成る
ものである請求項１記載の発泡性熱可塑性樹脂組成物。 ３、抗菌性金属イオンを保持しているゼオライトがアン
モニウムイオンを０．５〜１５重量％含有するものであ
る請求項２記載の発泡性熱可塑性樹脂組成物。 ４、抗菌性金属イオンが銀、銅、亜鉛からなる群より選
ばれた一種または二種以上の金属イオンである請求項１
、２又は３記載の発泡性熱可塑性樹脂組成物。 ５、抗菌性金属イオンを保持しているゼオライトの含有
率が０．０３〜５０重量％である請求項１、２又は３記
載の発泡性熱可塑性樹脂組成物。 ６、熱可塑性樹脂中に発泡剤を０．０１〜２０重量％含
有する請求項１、２又は３記載の発泡性熱可塑性樹脂組
成物。[Scope of Claims] 1. A foamable thermoplastic resin composition having antibacterial and antifungal properties and containing zeolite retaining antibacterial metal ions. 2. The foaming heat according to claim 1, wherein the zeolite holding antibacterial metal ions is obtained by replacing some or all of the ion-exchangeable ions in the zeolite with ammonium ions and antibacterial metal ions. Plastic resin composition. 3. The foamable thermoplastic resin composition according to claim 2, wherein the zeolite holding antibacterial metal ions contains 0.5 to 15% by weight of ammonium ions. 4. Claim 1, wherein the antibacterial metal ion is one or more metal ions selected from the group consisting of silver, copper, and zinc.
, 2 or 3. The foamable thermoplastic resin composition according to . 5. The foamable thermoplastic resin composition according to claim 1, 2 or 3, wherein the content of zeolite holding antibacterial metal ions is 0.03 to 50% by weight. 6. The foamable thermoplastic resin composition according to claim 1, 2 or 3, wherein the thermoplastic resin contains 0.01 to 20% by weight of a blowing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13817788A JPH01306473A (en) | 1988-06-03 | 1988-06-03 | Expandable thermoplastic resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13817788A JPH01306473A (en) | 1988-06-03 | 1988-06-03 | Expandable thermoplastic resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01306473A true JPH01306473A (en) | 1989-12-11 |
Family
ID=15215848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13817788A Pending JPH01306473A (en) | 1988-06-03 | 1988-06-03 | Expandable thermoplastic resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01306473A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2460460A (en) * | 2008-05-30 | 2009-12-02 | Production Chemical Internat H | Use of azodicarbonamide for reducing sulphides in a fluid |
| JP2013523992A (en) * | 2010-04-14 | 2013-06-17 | エーブリー デニソン コーポレイション | Method for improving the effectiveness of antibacterial agents in polymer films |
| US10335308B2 (en) | 2011-12-22 | 2019-07-02 | Avery Dennison Corporation | Flexible barrier films containing cyclic olefins |
| US11220616B2 (en) | 2011-08-19 | 2022-01-11 | Avery Dennison Corporation | Barrier films |
-
1988
- 1988-06-03 JP JP13817788A patent/JPH01306473A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2460460A (en) * | 2008-05-30 | 2009-12-02 | Production Chemical Internat H | Use of azodicarbonamide for reducing sulphides in a fluid |
| JP2013523992A (en) * | 2010-04-14 | 2013-06-17 | エーブリー デニソン コーポレイション | Method for improving the effectiveness of antibacterial agents in polymer films |
| US11220616B2 (en) | 2011-08-19 | 2022-01-11 | Avery Dennison Corporation | Barrier films |
| US10335308B2 (en) | 2011-12-22 | 2019-07-02 | Avery Dennison Corporation | Flexible barrier films containing cyclic olefins |
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