JP6678032B2 - Membrane materials for tent structures - Google Patents
Membrane materials for tent structures Download PDFInfo
- Publication number
- JP6678032B2 JP6678032B2 JP2016000017A JP2016000017A JP6678032B2 JP 6678032 B2 JP6678032 B2 JP 6678032B2 JP 2016000017 A JP2016000017 A JP 2016000017A JP 2016000017 A JP2016000017 A JP 2016000017A JP 6678032 B2 JP6678032 B2 JP 6678032B2
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- Prior art keywords
- chelate complex
- mass
- film material
- compound
- zinc
- Prior art date
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- 239000000463 material Substances 0.000 title claims description 120
- 239000012528 membrane Substances 0.000 title claims description 27
- 150000004697 chelate complex Chemical class 0.000 claims description 130
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 102
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 66
- 229920005989 resin Polymers 0.000 claims description 62
- 239000011347 resin Substances 0.000 claims description 62
- 239000002245 particle Substances 0.000 claims description 57
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 55
- 229910052709 silver Inorganic materials 0.000 claims description 55
- 239000004332 silver Substances 0.000 claims description 55
- 150000002894 organic compounds Chemical class 0.000 claims description 47
- 230000000843 anti-fungal effect Effects 0.000 claims description 46
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 42
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 42
- -1 magnesium aluminate Chemical class 0.000 claims description 42
- 239000000377 silicon dioxide Substances 0.000 claims description 42
- 239000003446 ligand Substances 0.000 claims description 41
- 239000000126 substance Substances 0.000 claims description 41
- 239000011247 coating layer Substances 0.000 claims description 37
- 230000001699 photocatalysis Effects 0.000 claims description 37
- 229940121375 antifungal agent Drugs 0.000 claims description 35
- 230000003373 anti-fouling effect Effects 0.000 claims description 34
- 239000010410 layer Substances 0.000 claims description 34
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 27
- 229910021536 Zeolite Inorganic materials 0.000 claims description 26
- 239000010457 zeolite Substances 0.000 claims description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 19
- 239000004744 fabric Substances 0.000 claims description 18
- 239000005909 Kieselgur Substances 0.000 claims description 16
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 16
- 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 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 12
- 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 claims description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- 239000001506 calcium phosphate Substances 0.000 claims description 10
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 10
- 235000011010 calcium phosphates Nutrition 0.000 claims description 10
- IQBJFLXHQFMQRP-UHFFFAOYSA-K calcium;zinc;phosphate Chemical compound [Ca+2].[Zn+2].[O-]P([O-])([O-])=O IQBJFLXHQFMQRP-UHFFFAOYSA-K 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 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 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000000378 calcium silicate Substances 0.000 claims description 9
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 9
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 9
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 9
- 229960001545 hydrotalcite Drugs 0.000 claims description 9
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 150000001413 amino acids Chemical class 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 150000003983 crown ethers Chemical class 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 229960002026 pyrithione Drugs 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 239000004471 Glycine Substances 0.000 claims description 3
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- PGZIKUPSQINGKT-UHFFFAOYSA-N dialuminum;dioxido(oxo)silane Chemical compound [Al+3].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O PGZIKUPSQINGKT-UHFFFAOYSA-N 0.000 claims description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 3
- 229930182817 methionine Natural products 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- 150000004032 porphyrins Chemical class 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 239000004753 textile Substances 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims 1
- YBBJKCMMCRQZMA-UHFFFAOYSA-N pyrithione Chemical compound ON1C=CC=CC1=S YBBJKCMMCRQZMA-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 description 78
- 239000000835 fiber Substances 0.000 description 32
- 230000000855 fungicidal effect Effects 0.000 description 32
- 241000195493 Cryptophyta Species 0.000 description 29
- WJCNZQLZVWNLKY-UHFFFAOYSA-N thiabendazole Chemical compound S1C=NC(C=2NC3=CC=CC=C3N=2)=C1 WJCNZQLZVWNLKY-UHFFFAOYSA-N 0.000 description 28
- VCRZAKVGPJFABU-UHFFFAOYSA-N 10-phenoxarsinin-10-yloxyphenoxarsinine Chemical compound C12=CC=CC=C2OC2=CC=CC=C2[As]1O[As]1C2=CC=CC=C2OC2=CC=CC=C21 VCRZAKVGPJFABU-UHFFFAOYSA-N 0.000 description 27
- RMNCNUNUQBLASX-UHFFFAOYSA-N 2-aminoacetic acid;copper Chemical compound [Cu].NCC(O)=O RMNCNUNUQBLASX-UHFFFAOYSA-N 0.000 description 26
- 238000012360 testing method Methods 0.000 description 26
- 101100188540 Candida albicans (strain SC5314 / ATCC MYA-2876) OBPA gene Proteins 0.000 description 25
- 239000002759 woven fabric Substances 0.000 description 22
- 239000004014 plasticizer Substances 0.000 description 21
- 239000000843 powder Substances 0.000 description 20
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 239000011342 resin composition Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
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- 239000002904 solvent Substances 0.000 description 12
- 230000007774 longterm Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 239000000428 dust Substances 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 7
- 239000000417 fungicide Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 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 7
- BGYBONWLWSMGNV-UHFFFAOYSA-N 1,4,7,10,13,16,19,22-octaoxacyclotetracosane Chemical compound C1COCCOCCOCCOCCOCCOCCOCCO1 BGYBONWLWSMGNV-UHFFFAOYSA-N 0.000 description 6
- 239000013522 chelant Substances 0.000 description 6
- 230000012010 growth Effects 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
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- 229940043810 zinc pyrithione Drugs 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- VVYPIVJZLVJPGU-UHFFFAOYSA-L copper;2-aminoacetate Chemical compound [Cu+2].NCC([O-])=O.NCC([O-])=O VVYPIVJZLVJPGU-UHFFFAOYSA-L 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
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- 239000011241 protective layer Substances 0.000 description 5
- 238000013268 sustained release Methods 0.000 description 5
- 239000012730 sustained-release form Substances 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
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- 238000004140 cleaning Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
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- UNTITLLXXOKDTB-UHFFFAOYSA-N dibenzo-24-crown-8 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOCCOC2=CC=CC=C21 UNTITLLXXOKDTB-UHFFFAOYSA-N 0.000 description 4
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- 229910052919 magnesium silicate Inorganic materials 0.000 description 4
- 235000019792 magnesium silicate Nutrition 0.000 description 4
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- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 239000004114 Ammonium polyphosphate Substances 0.000 description 3
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- 235000019826 ammonium polyphosphate Nutrition 0.000 description 3
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- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 2
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- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- HDHLIWCXDDZUFH-UHFFFAOYSA-N irgarol 1051 Chemical compound CC(C)(C)NC1=NC(SC)=NC(NC2CC2)=N1 HDHLIWCXDDZUFH-UHFFFAOYSA-N 0.000 description 1
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- 238000004898 kneading Methods 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
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- 229930014626 natural product Natural products 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- XIKYYQJBTPYKSG-UHFFFAOYSA-N nickel Chemical compound [Ni].[Ni] XIKYYQJBTPYKSG-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000010627 oxidative phosphorylation Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000008029 phthalate plasticizer Substances 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000131 polyvinylidene Polymers 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 239000001965 potato dextrose agar Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- OGGMARVIJLWYIU-UHFFFAOYSA-N prop-2-enoyloxycarbonyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)OC(=O)C=C OGGMARVIJLWYIU-UHFFFAOYSA-N 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 229960001141 pyrithione zinc Drugs 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
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- 239000013049 sediment Substances 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940071575 silver citrate Drugs 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- TYTYIUANSACAEM-UHFFFAOYSA-M silver;2,4,6-trinitrophenolate Chemical compound [Ag+].[O-]C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O TYTYIUANSACAEM-UHFFFAOYSA-M 0.000 description 1
- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 description 1
- ODCWYMIRDDJXKW-UHFFFAOYSA-N simazine Chemical compound CCNC1=NC(Cl)=NC(NCC)=N1 ODCWYMIRDDJXKW-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- FNWBQFMGIFLWII-UHFFFAOYSA-N strontium aluminate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Sr+2].[Sr+2] FNWBQFMGIFLWII-UHFFFAOYSA-N 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- HYVWIQDYBVKITD-UHFFFAOYSA-N tolylfluanid Chemical compound CN(C)S(=O)(=O)N(SC(F)(Cl)Cl)C1=CC=C(C)C=C1 HYVWIQDYBVKITD-UHFFFAOYSA-N 0.000 description 1
- QUTYHQJYVDNJJA-UHFFFAOYSA-K trisilver;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ag+].[Ag+].[Ag+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QUTYHQJYVDNJJA-UHFFFAOYSA-K 0.000 description 1
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- MJIBOYFUEIDNPI-HBNMXAOGSA-L zinc 5-[2,3-dihydroxy-5-[(2R,3R,4S,5R,6S)-4,5,6-tris[[3,4-dihydroxy-5-(3,4,5-trihydroxybenzoyl)oxybenzoyl]oxy]-2-[[3,4-dihydroxy-5-(3,4,5-trihydroxybenzoyl)oxybenzoyl]oxymethyl]oxan-3-yl]oxycarbonylphenoxy]carbonyl-3-hydroxybenzene-1,2-diolate Chemical compound [Zn++].Oc1cc(cc(O)c1O)C(=O)Oc1cc(cc(O)c1O)C(=O)OC[C@H]1O[C@@H](OC(=O)c2cc(O)c(O)c(OC(=O)c3cc(O)c(O)c(O)c3)c2)[C@H](OC(=O)c2cc(O)c(O)c(OC(=O)c3cc(O)c(O)c(O)c3)c2)[C@@H](OC(=O)c2cc(O)c(O)c(OC(=O)c3cc(O)c(O)c(O)c3)c2)[C@@H]1OC(=O)c1cc(O)c(O)c(OC(=O)c2cc(O)c([O-])c([O-])c2)c1 MJIBOYFUEIDNPI-HBNMXAOGSA-L 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011746 zinc citrate Substances 0.000 description 1
- 235000006076 zinc citrate Nutrition 0.000 description 1
- 229940068475 zinc citrate Drugs 0.000 description 1
- 239000011670 zinc gluconate Substances 0.000 description 1
- 235000011478 zinc gluconate Nutrition 0.000 description 1
- 229960000306 zinc gluconate Drugs 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 239000011576 zinc lactate Substances 0.000 description 1
- 235000000193 zinc lactate Nutrition 0.000 description 1
- 229940050168 zinc lactate Drugs 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 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
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- 229940006174 zinc valerate Drugs 0.000 description 1
- VRGNUPCISFMPEM-ZVGUSBNCSA-L zinc;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Zn+2].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O VRGNUPCISFMPEM-ZVGUSBNCSA-L 0.000 description 1
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
- BUDAIZWUWHWZPQ-UHFFFAOYSA-L zinc;pentanoate Chemical compound [Zn+2].CCCCC([O-])=O.CCCCC([O-])=O BUDAIZWUWHWZPQ-UHFFFAOYSA-L 0.000 description 1
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 description 1
- GQLBMRKEAODAKR-UHFFFAOYSA-L zinc;selenate Chemical compound [Zn+2].[O-][Se]([O-])(=O)=O GQLBMRKEAODAKR-UHFFFAOYSA-L 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- BHTBHKFULNTCHQ-UHFFFAOYSA-H zinc;tin(4+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Sn+4] BHTBHKFULNTCHQ-UHFFFAOYSA-H 0.000 description 1
- OBOMINCSAYZPGH-UHFFFAOYSA-L zinc;undecanoate Chemical compound [Zn+2].CCCCCCCCCCC([O-])=O.CCCCCCCCCCC([O-])=O OBOMINCSAYZPGH-UHFFFAOYSA-L 0.000 description 1
- 229930007845 β-thujaplicin Natural products 0.000 description 1
Landscapes
- Tents Or Canopies (AREA)
- Laminated Bodies (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
本発明はテント構造物の美観維持技術に関するものであり、具体的に本発明は、中〜大型テント構造物(スタジアム屋根、ドーム球場、開閉式屋根ドーム、パビリオンなど)、日除けテント構造物(公共施設モニュメント、駅舎ホーム屋根、連絡通路屋根、アーケード屋根、店舗用、住居用など)、内照式テント構造物(電飾看板、映像投影ドーム、アート造型など)などのテント構造物(金属フレームに防水性の繊維複合シートを取り付けた構造)において、テント構造物への黴や藻の発生による外観汚染を長期に亘って防ぐことのできるテント構造物に適した防黴性と防藻性に優れた膜材に関するものである。 The present invention relates to a technique for maintaining the beauty of a tent structure. Specifically, the present invention relates to a medium to large tent structure (a stadium roof, a dome stadium, a retractable roof dome, a pavilion, etc.), a sunshade tent structure (public). Tent structures (metal frames, etc.) such as facility monuments, station building platform roofs, access passage roofs, arcade roofs, stores, residences, etc., and internally illuminated tent structures (electrical signs, video projection dome, art molding, etc.) (Waterproof fiber composite sheet attached structure) with excellent antifungal and antialgal properties suitable for tent structures that can prevent appearance contamination due to mold and algae generation on tent structures for a long time It relates to a film material.
テント構造物に使用される汎用シート状膜材は、繊維織物を基布として、その表面に軟質配合の塩化ビニル樹脂組成物を被覆加工して得られる複合シート素材であり、これらはテント構造物として10〜20年もの耐久性を有する。しかし、軟質配合の塩化ビニル樹脂は多量の可塑剤を配合に含むため、時間の経過と共にシート状膜材の表面に可塑剤がブリードし、ブリードした可塑剤に煤塵が蓄積することで、徐々にシート状膜材が汚れるという問題がある。このため、軟質配合の塩化ビニル樹脂製のシート状膜材の表面には、アクリル樹脂、ウレタン樹脂、フッ素系樹脂などの塗膜を設けることで可塑剤のブリードを制御し、防汚効果を確保する手段が一般的である。 The general-purpose sheet-like membrane material used for the tent structure is a composite sheet material obtained by coating the surface of a fiber woven fabric with a soft-blended vinyl chloride resin composition on a surface of the tent structure. Has a durability of 10 to 20 years. However, since the vinyl chloride resin of the soft blend contains a large amount of plasticizer in the blend, the plasticizer bleeds over the surface of the sheet-like film material over time, and dust gradually accumulates in the bleed plasticizer. There is a problem that the sheet-like film material becomes dirty. For this reason, the bleeding of the plasticizer is controlled by providing a coating film of acrylic resin, urethane resin, fluorine-based resin, etc. on the surface of the sheet-like film material made of soft blended vinyl chloride resin, and the antifouling effect is secured. The means to do it is common.
これらテント構造物は用途や規模によって様々なデザイン形態で設計されるため、シート状膜材による水平部、垂直部、アーチ部などを多様に含む立体構造物で、その耐用年数も様々である。これらテント構造物には、形状に応じてもシート状膜材表面に煤塵汚れが経年堆積するが、テント構造物が大型で複雑であるほど人が登ってのクリーニングを大掛かりなものとするため、クリーニングのタイミングは汚れが極度に目立ち始めてからというのが実情である。ところでテント構造物を構成するシート状膜材の温度が50℃以上となって軟質配合の塩化ビニル樹脂の軟化を最大とする夏を経過する度に、煤塵堆積がシート状膜材表面に固着して、降雨程度では容易に流れ落ちない堆積汚れとなる。そしてこの堆積汚れは黴や藻の胞子の菌床となり、テント構造物に黴や藻を発生させる要因となるが、黴や藻を放置することによって、シート状膜材表面を菌糸が侵食(分泌酵素による侵食)して、後でテント構造物をクリーニングしても劣化痕跡となって、テント構造物の外観を悪くする元凶となっていた。 Since these tent structures are designed in various design forms depending on the use and scale, they are three-dimensional structures including various portions such as a horizontal portion, a vertical portion, and an arch portion made of a sheet-like film material, and have various service lives. In these tent structures, dust and dirt accumulates on the surface of the sheet-like film material over time, depending on the shape, but the larger and more complex the tent structure, the more extensive cleaning by people climbs. The actual situation is that the cleaning is started after the dirt is extremely noticeable. By the way, each time the temperature of the sheet-like film material constituting the tent structure becomes 50 ° C. or more and the summer when the softening of the soft blended vinyl chloride resin is maximized, the dust accumulation adheres to the surface of the sheet-like film material. As a result, sediment that does not easily flow down when rainfall occurs is generated. The accumulated dirt becomes a bed of mold and algae spores, and causes mold and algae to be generated in the tent structure. When the mold and algae are left, the hyphae erode (secretion) the sheet-like membrane material surface. Even if the tent structure was cleaned later due to enzymatic erosion), the tent structure could become a sign of deterioration even if the tent structure was cleaned.
これらテント構造物における黴や藻の対策には、シート状膜材に有機系防黴剤を配合することが効果的で、有機系防黴剤が可塑剤と共にシート表面に逐次ブリードすることで、防黴や防藻の効果を効率的に発現するが、紫外線劣化したり、雨で溶出したり、長期間使用のうちにシート状膜材から有機系防黴剤が抜け出して防黴や防藻の効果が徐々に失われる問題を有している。一方で、ゼオライト、ハイドロキシアパタイトなどの多孔性セラミックス粒子の表面に銀などの金属元素を担持させた無機系防黴剤の練込配合系では、多孔性セラミックス粒子自体がブリードしない充填物となるため、シート表面への金属元素の逐次補填が非効率となって徐々に防黴性や防藻性が低下する傾向がある。そこで銀などの金属元素による抗菌効果が長期安定持続し、かつ変色防止の抗菌性組成物として、銀などの金属とフェノール性化合物との錯体を用いた抗菌性組成物(特許文献1)、銀などの金属とエチレンジアミン四酢酸による錯体とする無機酸化物コロイド溶液からなる抗菌剤(特許文献2)、水系溶媒に酸化銀およびフィチン酸を溶解させ、エチレンジアミン四酢酸などのキレート剤を含有させた有機錯体水溶液(特許文献3)などの錯体が提案され、その長期安定持続性を確かなものとしているが、液状錯体では可塑剤を含有する軟質配合の塩化ビニル樹脂との相性が悪く、混合不良を生じて実質的に使用困難である。従って、テント構造物用の膜材を製造するための軟質配合による塩化ビニル樹脂製の膜材として、特に防黴・防藻効果が長期安定持続可能な膜材が求められていた。 In order to prevent mold and algae in these tent structures, it is effective to add an organic fungicide to the sheet-like film material, and the organic fungicide bleeds sequentially with the plasticizer on the sheet surface. Effectively exerts the fungicidal and anti-algae effects, but deteriorates with ultraviolet rays, elutes with rain, and the organic anti-fungal agent comes out of the sheet-like membrane material during long-term use to prevent fungicide and alga. Has a problem that the effect of the above is gradually lost. On the other hand, in a kneading compound system of an inorganic fungicide in which a metal element such as silver is supported on the surface of porous ceramic particles such as zeolite and hydroxyapatite, the porous ceramic particles themselves become a non-bleeding filler. In addition, the sequential replenishment of the sheet surface with the metal element becomes inefficient, and the fungicidal and algal resistance tend to gradually decrease. Therefore, as an antibacterial composition in which the antibacterial effect of a metal element such as silver is stably maintained for a long period of time, and a discoloration prevention antibacterial composition using a complex of a metal such as silver and a phenolic compound (Patent Document 1), silver Antibacterial agent consisting of a colloidal solution of an inorganic oxide formed into a complex with a metal such as ethylenediaminetetraacetic acid (Patent Document 2), an organic solvent in which silver oxide and phytic acid are dissolved in an aqueous solvent and a chelating agent such as ethylenediaminetetraacetic acid is contained. Complexes such as aqueous complex solutions (Patent Document 3) have been proposed, and their long-term stability is ensured. However, liquid complexes have poor compatibility with a soft-blended vinyl chloride resin containing a plasticizer, and poor mixing may occur. It is practically difficult to use. Therefore, as a film material made of a soft-blended vinyl chloride resin for producing a film material for a tent structure, a film material having a long-term stable and stable mold- and alga-proof effect has been required.
本発明は、テント構造物が黴や藻の発生で外観汚染を生じることが無いようにするために、黴や藻の発生を最小限に抑止することができるテント構造物用の膜材を提供しようとするものである。 The present invention provides a membrane material for a tent structure capable of minimizing the generation of mold and algae so that the tent structure does not cause appearance contamination due to the generation of mold and algae. What you want to do.
本発明は、上記の現状に鑑みて研究、検討を重ねた結果、繊維織物を基材として、その少なくとも片面に軟質塩化ビニル樹脂被覆層を有する可撓性シートにおいて、軟質塩化ビニル樹脂被覆層が、銀配位子、銅配位子、亜鉛配位子、及びニッケル配位子から選ばれた1種以上のキレート錯体と、防黴性有機化合物とを含むことによって、上記従来技術で困難であったテント構造物用の膜材として、黴や藻を長期間最小限に抑止するという防黴効果の持続性向上の課題が解決できることを見い出して本発明を完成するに至った。 The present invention has been studied and studied in view of the above-mentioned situation, and as a result of repeating the studies, a flexible sheet having a soft vinyl chloride resin coating layer on at least one surface of a fiber woven fabric as a base material has a soft vinyl chloride resin coating layer. By containing at least one chelate complex selected from a silver ligand, a copper ligand, a zinc ligand, and a nickel ligand, and a fungicidal organic compound, As a film material for a tent structure, the present inventors have found that it is possible to solve the problem of improving the antifungal effect of suppressing mold and algae to a minimum for a long period of time, thereby completing the present invention.
すなわち本発明のテント構造物用膜材は、繊維織物を基材として、その少なくとも片面に軟質塩化ビニル樹脂被覆層を有する可撓性シートであって、前記軟質塩化ビニル樹脂被覆層が、銀配位子、銅配位子、亜鉛配位子、及びニッケル配位子から選ばれた1種以上のキレート錯体と、防黴性有機化合物とを含み、前記キレート錯体の配位子が少なくともクラウンエーテル及びアミノ酸であり、かつ前記キレート錯体がクラウンエーテル錯体及びアミノ酸錯体の併用であって、前記アミノ酸が、グリシン、ヒスチジン、メチオニンから選ばれた1種以上であることが好ましい。これによって銀、銅、亜鉛、及びニッケルなどの金属、金属イオンが安定化され、系外に排出され難くすることで、黴や藻の発生を長期間効果的に抑止可能なテント構造物用に適した膜材を得ることができる。
That is, the film material for a tent structure of the present invention is a flexible sheet having a fiber woven fabric as a base material and having a soft vinyl chloride resin coating layer on at least one surface thereof, wherein the soft vinyl chloride resin coating layer has a silver distribution. ligand, Dohaiiko, zinc ligands, and with one or more chelate complex selected from nickel ligands, see contains an antifungal organic compounds, ligands of the chelate complex is at least crown Preferably, the chelate complex is an ether and an amino acid, and the chelate complex is a combination of a crown ether complex and an amino acid complex, and the amino acid is at least one selected from glycine, histidine, and methionine . This stabilizes metals such as silver, copper, zinc, and nickel, and metal ions, and makes it difficult for them to be discharged out of the system. A suitable film material can be obtained.
本発明のテント構造物用膜材は、前記キレート錯体の配位子に、エチレンジアミン、トリエチレンテトラミン、ピピリジン、エチレンアミン酢酸、ピリチオン、フェナントロリン、ポルフィリン、及びクラウンエーテルから選ばれた1種以上をさらに含むことが好ましい。これによって銀、銅、亜鉛、及びニッケルなどの金属、金属イオンが安定化され、系外に排出され難くすることで、黴や藻の発生を長期間効果的に抑止可能なテント構造物用に適した膜材を得ることができる。 Tent structures for film material of the present invention, the ligand of the chelate complex, ethylenediamine, triethylenetetramine, Pipirijin, ethyleneamine acetate, pyrithione, further phenanthroline, porphyrin, and one or more species selected from crown ethers It is preferred to include . This stabilizes metals such as silver, copper, zinc, and nickel, and metal ions, and makes it difficult for them to be discharged out of the system. A suitable film material can be obtained.
本発明のテント構造物用膜材は、前記キレート錯体が、メソポーラスシリカ、(合成)ゼオライト、チタンゼオライト、リン酸ジルコニウム、リン酸カルシウム、リン酸亜鉛カルシウム、ハイドロタルサイト、ヒドロキシアパタイト、シリカアルミナ、ケイ酸カルシウム、ケイ酸アルミン酸マグネシウム、ケイソウ土、及びこれらのシランカップリング剤処理物、から選ばれた1種以上の無機多孔質粒子に担持されていることが好ましい。これによってキレート錯体が系外に排出され難くなり、かつ徐放性を発現することで、黴や藻の発生を長期間効果的に抑止可能なテント構造物用に適した膜材を得ることができる。 In the film material for a tent structure of the present invention, the chelate complex may be a mesoporous silica, a (synthetic) zeolite, a titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, and silicic acid. It is preferably supported on one or more inorganic porous particles selected from calcium, magnesium silicate aluminate, diatomaceous earth, and a treated product of these silane coupling agents. This makes it difficult for the chelate complex to be discharged out of the system, and by exhibiting a sustained release property, it is possible to obtain a membrane material suitable for a tent structure capable of effectively suppressing the generation of mold and algae for a long period of time. it can.
本発明のテント構造物用膜材は、前記防黴性有機化合物が、イミダゾール系化合物、チアゾール系化合物、イソチアゾリン系化合物、ピリジン系化合物、トリアジン系化合物、トリアゾール系化合物、N−ハロアルキルチオ系化合物、四級アンモニウム塩系化合物、及び有機金属系化合物から選ばれた1種以上であることが好ましい。これによって黴や藻の発生を長期間効果的に抑止可能なテント構造物用に適した膜材を得ることができる。 In the film material for a tent structure of the present invention, the antifungal compound is an imidazole compound, a thiazole compound, an isothiazoline compound, a pyridine compound, a triazine compound, a triazole compound, an N-haloalkylthio compound, It is preferably at least one selected from quaternary ammonium salt compounds and organometallic compounds. This makes it possible to obtain a film material suitable for a tent structure capable of effectively suppressing the generation of mold and algae for a long period of time.
本発明のテント構造物用膜材は、前記防黴性有機化合物が、メソポーラスシリカ、(合成)ゼオライト、チタンゼオライト、リン酸ジルコニウム、リン酸カルシウム、リン酸亜鉛カルシウム、ハイドロタルサイト、ヒドロキシアパタイト、シリカアルミナ、ケイ酸カルシウム、ケイ酸アルミン酸マグネシウム、ケイソウ土、及びこれらのシランカップリング剤処理物、から選ばれた1種以上の無機多孔質粒子に担持されていることが好ましい。これによって防黴性有機化合物が系外に排出され難くなり、かつ徐放性を発現することで、黴や藻の発生を長期間効果的に抑止可能なテント構造物用に適した膜材を得ることができる。 In the film material for a tent structure of the present invention, the antifungal organic compound is preferably mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina It is preferably carried on one or more inorganic porous particles selected from calcium silicate, magnesium silicate aluminate, diatomaceous earth, and a silane coupling agent-treated product thereof. This makes it difficult for the fungicidal organic compound to be discharged out of the system, and by exhibiting a sustained release property, a film material suitable for a tent structure capable of effectively suppressing the generation of mold and algae for a long period of time. Obtainable.
本発明のテント構造物用膜材は、前記軟質塩化ビニル樹脂被覆層の少なくとも1面上に、光触媒物質含有防汚層が形成され、光触媒物質含有防汚層に含む光触媒物質が、酸化チタン、過酸化チタン(ペルオキソチタン酸)、酸化亜鉛、酸化錫、チタン酸ストロンチウム、酸化タングステン、及び酸化ビスマスから選ばれた1種以上であることが好ましい。光触媒物質の酸化還元作用によって煤塵汚れを効果的にセルフクリーニング(光触媒による防汚層の親水性化による降雨による洗浄、及び光触媒による黴や藻などの分解作用による)し、黴や藻の発生を効果的、かつ長期間に亘り抑止可能なテント構造物用の膜材を得ることができる。 In the film material for a tent structure of the present invention, a photocatalytic substance-containing antifouling layer is formed on at least one surface of the soft vinyl chloride resin coating layer, and the photocatalytic substance contained in the photocatalytic substance-containing antifouling layer is titanium oxide; It is preferably at least one selected from titanium peroxide (peroxotitanic acid), zinc oxide, tin oxide, strontium titanate, tungsten oxide, and bismuth oxide. Effectively self-cleans dust and dirt by the redox effect of the photocatalytic substance (washing by rainfall by making the antifouling layer hydrophilic by the photocatalyst, and by decomposition of mold and algae by the photocatalyst), and reduces the generation of mold and algae A film material for a tent structure that is effective and can be suppressed for a long period of time can be obtained.
本発明のテント構造物用膜材は、前記光触媒物質含有防汚層が、銀配位子、銅配位子、亜鉛配位子、及びニッケル配位子から選ばれた1種以上のキレート錯体を含むことが好ましい。光触媒物質の酸化還元作用によって煤塵汚れを効果的にセルフクリーニング(光触媒による防汚層の親水性化による降雨による洗浄、及び光触媒による黴や藻などの分解作用による)し、黴や藻の発生を効果的、かつ更に長期間に亘り抑止可能なテント構造物用の膜材を得ることができる。 In the film material for a tent structure of the present invention, the photocatalytic substance-containing antifouling layer is preferably one or more chelate complexes selected from a silver ligand, a copper ligand, a zinc ligand, and a nickel ligand. It is preferable to include Effectively self-cleans dust and dirt by the redox effect of the photocatalytic substance (washing by rainfall by making the antifouling layer hydrophilic by the photocatalyst, and by decomposition of mold and algae by the photocatalyst), and reduces the generation of mold and algae It is possible to obtain a film material for a tent structure that is effective and can be suppressed for a long period of time.
本発明のテント構造物用膜材は、前記光触媒物質含有防汚層に含有する前記キレート錯体が、メソポーラスシリカ、(合成)ゼオライト、チタンゼオライト、リン酸ジルコニウム、リン酸カルシウム、リン酸亜鉛カルシウム、ハイドロタルサイト、ヒドロキシアパタイト、シリカアルミナ、ケイ酸カルシウム、ケイ酸アルミン酸マグネシウム、ケイソウ土、及びこれらのシランカップリング剤処理物、から選ばれた1種以上の無機多孔質粒子に担持されていることが好ましい。これによって煤塵汚れを効果的にセルフクリーニング(光触媒による防汚層の親水性化による降雨による洗浄、及び光触媒による黴や藻などの分解作用による)すると同時に、キレート錯体が系外に排出され難くなり、かつ徐放性を発現することで、黴や藻の発生を長期間効果的に抑止可能なテント構造物用に適した膜材を得ることができる。 In the membrane material for a tent structure of the present invention, the chelate complex contained in the photocatalytic substance-containing antifouling layer is a mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotal Site, hydroxyapatite, silica alumina, calcium silicate, magnesium silicate aluminate, diatomaceous earth, and a silane coupling agent-treated product thereof, and may be supported on one or more inorganic porous particles. preferable. As a result, dust and dirt are effectively self-cleaned (washing by rainfall due to hydrophilicity of the antifouling layer with the photocatalyst, and decomposition of mold and algae by the photocatalyst), and at the same time, the chelate complex is hardly discharged out of the system. By exhibiting a sustained release property, it is possible to obtain a film material suitable for a tent structure capable of effectively suppressing the generation of mold and algae for a long period of time.
本発明によれば、黴や藻の発生を長期間最小限に抑止するテント構造物用の膜材が得られるので、本発明の膜材は、中〜大型テント構造物(スタジアム屋根、ドーム球場、開閉式屋根ドーム、パビリオンなど)、日除けテント構造物(公共施設モニュメント、駅舎ホーム屋根、連絡通路屋根、アーケード屋根、店舗用、住居用など)、内照式テント構造物(電飾看板、映像投影ドーム、アート造型など)などのテント構造物(金属フレームに防水性の繊維複合シートを取り付けた構造)などに広く適して用いることができる。 According to the present invention, it is possible to obtain a membrane material for a tent structure that suppresses the generation of mold and algae to a minimum for a long period of time. Therefore, the membrane material of the present invention can be used for a medium to large tent structure (stadium roof, dome ballpark). , Openable dome, pavilion, etc.), awning tent structure (public facility monument, station building home roof, access passage roof, arcade roof, store, residence, etc.), internally illuminated tent structure (illuminated signboard, video It can be widely used for tent structures (structures in which a waterproof fiber composite sheet is attached to a metal frame) such as a projection dome and art molding.
本発明のテント構造物用膜材は、繊維織物を基材として、その少なくとも片面に軟質塩化ビニル樹脂被覆層を有する可撓性シートであって、軟質塩化ビニル樹脂被覆層が、銀配位子、銅配位子、亜鉛配位子、及びニッケル配位子から選ばれた1種以上のキレート錯体と、防黴性有機化合物とを含むもので、必要に応じてキレート錯体には、無機多孔質粒子にキレート錯体を担持させたものを使用し、必要に応じて防黴性有機化合物には、無機多孔質粒子に防黴性有機化合物を担持させたものを使用し、必要に応じて軟質塩化ビニル樹脂被覆層の上にキレート錯体を含有する光触媒物質含有防汚層を形成し、必要に応じてそのキレート錯体には、無機多孔質粒子にキレート錯体を担持させたものを使用することができる。 The membrane material for a tent structure of the present invention is a flexible sheet having a fiber woven fabric as a base material and having a soft vinyl chloride resin coating layer on at least one surface thereof, wherein the soft vinyl chloride resin coating layer has a silver ligand. And one or more chelate complexes selected from copper, zinc, and nickel ligands, and a fungicidal organic compound. If necessary, the chelate complex may contain an inorganic porous material. Use a material in which a chelate complex is supported on porous particles, and if necessary, use a material in which an inorganic porous particle supports a fungicide organic compound, and if necessary, use a soft A photocatalytic substance-containing antifouling layer containing a chelate complex is formed on the vinyl chloride resin coating layer, and if necessary, the chelate complex may be one in which inorganic porous particles carry the chelate complex. it can.
本発明に使用する基材としての繊維織物は、織布、編布、不織布などの何れの形態でも使用でき、織布としては、平織物(経糸、緯糸とも最少2本ずつ用いた最小構成単位を有する)、バスケット織物(例えば2×2、3×3、4×4などの正則バスケット織、3×2、4×2、4×3、5×3、2×3、2×4、3×4、3×5などの不規則バスケット織)、綾織物(経糸、緯糸とも最少3本ずつ用いた最小構成単位を有する:3枚斜文、4枚斜文、5枚斜文、6枚斜文、8枚斜文など)、朱子織物(経糸、緯糸とも最少5本ずつ用いた最小構成単位を有する:2飛び、3飛び、4飛び、5飛びなどの正則朱子)、及び変化平織物、変化綾織物、変化朱子織物など、さらに蜂巣織物、梨子地織物、破れ斜文織物、昼夜朱子織物、もじり織物(紗織物、絽織物)、縫取織物、二重織物なども使用できるが、特に平織物、2×2バスケット織物が経緯物性バランスに優れ好ましい。上記の織物には精練、漂白、染色、柔軟化、撥水、防水、防炎、毛焼き、カレンダー、バインダー固着、接着剤塗布などの公知の繊維処理加工を単数、または複数を施したものを使用することもできる。 The fiber woven fabric as the base material used in the present invention can be used in any form such as a woven fabric, a knitted fabric, and a nonwoven fabric. As the woven fabric, a plain woven fabric (the minimum structural unit using a minimum of two warp yarns and two weft yarns) is used. ), Basket fabrics (eg, regular basket weaves such as 2 × 2, 3 × 3, 4 × 4, etc., 3 × 2, 4 × 2, 4 × 3, 5 × 3, 2 × 3, 2 × 4, 3) × 4, 3 × 5, etc., irregular basket weave), twill fabric (warp and weft have the minimum constitutional unit using at least 3 pieces: 3 pieces, 4 pieces, 5 pieces, 5 pieces, 6 pieces) Oblique, 8 oblique, etc.), satin fabric (having the minimum structural unit using a minimum of 5 each for both warp and weft: regular satin such as 2 jumps, 3 jumps, 4 jumps, 5 jumps), and changing plain fabrics , Change twill fabric, change satin fabric, etc., beehive fabric, rishiji fabric, torn oblique fabric, day and night satin fabric, woven fabric , Woven fabrics), sewing fabrics, double woven fabrics, etc., but plain woven fabrics and 2 × 2 basket woven fabrics are particularly preferred because of their excellent balance of properties. The above-mentioned woven fabric has been subjected to single or multiple known fiber treatment processes such as scouring, bleaching, dyeing, softening, water repellency, waterproofing, flameproofing, scalding, calendering, binder fixing, and adhesive application. Can also be used.
繊維織物を構成する糸条は、合成繊維、天然繊維、半合成繊維、無機繊維またはこれらの2種以上から成る混合繊維など、何れも使用できるが、ポリプロピレン繊維、ポリエチレン繊維、ポリビニルアルコール繊維、ポリエステル(PET、PBT、PNT)繊維、ナイロン繊維、全芳香族ポリアミド繊維、芳香族ヘテロ環ポリマー(PBI、PBO、PBT)繊維、アクリル繊維、ポリウレタン繊維、または、これらの混合繊維などの合成繊維が使用でき、特にポリエステル(PET:ポリエチレンテレフタレート)繊維が好ましい。これらの糸条の態様は、モノフィラメント、マルチフィラメント、短繊維紡績(スパン)、スプリット、テープなどであるが、膜材のフレキシブル性、及び引裂強度を確保するためにはマルチフィラメント、または短繊維紡績(スパン)が好ましい。また、ガラス繊維、シリカ繊維、アルミナ繊維、シリカアルミナ繊維、炭素繊維などのマルチフィラメント糸条も使用でき、これらの無機系繊維は特に国土交通大臣認定の不燃材料(テント構造物用不燃膜材)用に適し、特にガラス繊維マルチフィラメント糸条が好ましい。 As the yarn constituting the fiber woven fabric, any of synthetic fiber, natural fiber, semi-synthetic fiber, inorganic fiber or a mixed fiber of two or more of these can be used, but polypropylene fiber, polyethylene fiber, polyvinyl alcohol fiber, polyester Synthetic fibers such as (PET, PBT, PNT) fibers, nylon fibers, wholly aromatic polyamide fibers, aromatic heterocyclic polymer (PBI, PBO, PBT) fibers, acrylic fibers, polyurethane fibers, or mixed fibers thereof are used. In particular, polyester (PET: polyethylene terephthalate) fibers are preferable. The form of these yarns is monofilament, multifilament, short fiber spinning (spun), split, tape, etc. In order to secure the flexibility and tear strength of the membrane material, multifilament or short fiber spinning is used. (Span) is preferred. In addition, multifilament yarns such as glass fiber, silica fiber, alumina fiber, silica-alumina fiber, and carbon fiber can also be used. These inorganic fibers are particularly non-combustible materials approved by the Minister of Land, Infrastructure, Transport and Tourism (non-combustible film materials for tent structures). In particular, glass fiber multifilament yarn is preferable.
本発明に使用する繊維織物は、マルチフィラメント糸条からなる織物、または短繊維紡績布(スパン)であることが好ましく、マルチフィラメント糸条は、250〜3000デニール(277〜3333dtex)の範囲、特に500〜2000デニール(555〜2222dtex)が好ましく、必要に応じて無撚糸(断面が楕円または扁平)、または撚糸が使用できる。また短繊維紡績糸条は、10番手(591dtex)〜60番手(97dtex)の範囲、特に10番手(591dtex)、14番手(422dtex)、16番手(370dtex)、20番手(295dtex)、24番手(246dtex)、30番手(197dtex)など、これらの単糸、または双糸(片撚糸)、単糸2本以上による合撚糸(諸撚糸)などが好ましい。織物の経糸及び緯糸の打込み密度に制限は無く、用いる糸条の太さ(デニール、番手)に応じて任意の設計が可能であるが、織物の空隙率(目抜け)が、0〜30%の範囲となる打込み密度で、目付量100〜500g/m2の織物がテント構造物用膜材の基材に適している。空隙率は繊維織物の単位面積中に占める糸条の面積を百分率として求め、100から差し引いた値として求めることができる。マルチフィラメント糸条で製織された織物(空隙率7.5〜30%)の好ましくは両面に、軟質塩化ビニル樹脂フィルムを熱ラミネートして軟質塩化ビニル樹脂被覆層を形成する製造に適し、また短繊維紡績布(スパン)の場合、空隙率0〜5%の短繊維紡績布(スパン)の好ましくは両面に、軟質塩化ビニル樹脂ペーストゾルを用いてのコーティング〜ゲル化熱処理、またはデッピィング〜ゲル化熱処理による軟質塩化ビニル樹脂被覆層の形成に適している。 The fiber woven fabric used in the present invention is preferably a woven fabric composed of multifilament yarns or a staple fiber spun cloth (spun), and the multifilament yarn is in the range of 250 to 3000 denier (277 to 3333 dtex), particularly 500 to 2000 denier (555 to 2222 dtex) is preferable, and a non-twisted yarn (elliptical or flat in cross section) or a twisted yarn can be used as necessary. The short fiber spun yarn ranges from 10th (591 dtex) to 60th (97 dtex), particularly 10th (591 dtex), 14th (422 dtex), 16th (370 dtex), 20th (295 dtex), and 24th ( Preferred are such single yarns, such as 246 dtex and 30 count (197 dtex), or twin yarns (single twisted yarns), ply twisted yarns (twisted yarns) of two or more single yarns, and the like. There is no limitation on the driving density of the warp and the weft of the woven fabric, and any design is possible according to the thickness (denier, count) of the yarn to be used. However, the porosity (opening) of the woven fabric is 0 to 30%. A woven fabric having a basis weight of 100 to 500 g / m 2 at a driving density in the range of 1 to 2 is suitable as a base material of a membrane material for a tent structure. The porosity can be obtained as a value obtained by calculating the area of the yarn occupying in a unit area of the fiber woven fabric as a percentage and subtracting it from 100. Suitable for the production of a soft vinyl chloride resin coating layer by heat laminating a soft vinyl chloride resin film on both sides of a woven fabric (porosity 7.5 to 30%), preferably with a multifilament yarn. In the case of a fiber spun cloth (span), preferably, a short fiber spun cloth (span) having a porosity of 0 to 5% is coated on a both surfaces with a soft vinyl chloride resin paste sol to perform gelation heat treatment or depping to gelation. Suitable for forming a soft vinyl chloride resin coating layer by heat treatment.
軟質塩化ビニル樹脂被覆層は、少なくとも塩化ビニル樹脂と可塑剤からなる軟質塩化ビニル樹脂中に、必須成分としてキレート錯体と、防黴性有機化合物とを含む軟質塩化ビニル樹脂組成物から形成されるもので、ペースト塩化ビニル樹脂(乳化重合タイプ)を用いた塩化ビニル樹脂ペーストゾル〜ゲル化熱処理による形成、或いはストレート塩化ビニル樹脂(懸濁重合タイプ)を用いて、カレンダー圧延成型またはTダイス押出成型した塩化ビニル樹脂フィルム(シート)による形成が可能である。本発明において、軟質塩化ビニル樹脂被覆層には、塩化ビニル系共重合体樹脂を25質量%程度混用してもよく、さらにはウレタンエラストマー、アクリル系共重合体ゴム、塩素化ポリエチレン、クロロスルフォン化ポリエチレン、クロロプレン、EPDMなどのゴム成分を25質量%程度混用することもできる。また可塑剤は平均分子量380〜560のフタル酸エステル系可塑剤、イソフタル酸エステル系可塑剤、テレフタル酸エステル系可塑剤、シクロヘキサンジカルボン酸エステル系可塑剤、塩素化パラフィン系可塑剤、平均分子量1000〜3200のポリエステル系可塑剤、エチレン−酢酸ビニル−一酸化炭素3元共重合体樹脂、エチレン−(メタ)アクリル酸エステル−一酸化炭素3元共重合体樹脂などが使用でき、これらの可塑剤中に予めキレート錯体を混合したものを用いることがキレート錯体の分散性を観点において好ましい。軟質塩化ビニル樹脂被覆層は、本発明のテント構造物用膜材から繊維織物の質量を差し引いた値として、200〜2000g/m2、特に300〜1000g/m2が好ましい。 The soft vinyl chloride resin coating layer is formed of a soft vinyl chloride resin composition containing a chelate complex as an essential component and a fungicidal organic compound in a soft vinyl chloride resin comprising at least a vinyl chloride resin and a plasticizer. Then, a vinyl chloride resin paste sol using paste vinyl chloride resin (emulsion polymerization type) was formed by gelation heat treatment, or calender roll molding or T-die extrusion molding was performed using straight vinyl chloride resin (suspension polymerization type). It can be formed from a vinyl chloride resin film (sheet). In the present invention, about 25% by mass of a vinyl chloride copolymer resin may be mixed in the soft vinyl chloride resin coating layer, and further, urethane elastomer, acrylic copolymer rubber, chlorinated polyethylene, chlorosulfonated A rubber component such as polyethylene, chloroprene, and EPDM can be mixed at about 25% by mass. The plasticizer is a phthalate plasticizer having an average molecular weight of 380 to 560, an isophthalate ester plasticizer, a terephthalate ester plasticizer, a cyclohexanedicarboxylate ester plasticizer, a chlorinated paraffin plasticizer, and an average molecular weight of 1,000 to 5,000. 3200 polyester plasticizer, ethylene-vinyl acetate-carbon monoxide terpolymer resin, ethylene- (meth) acrylate-carbon monoxide terpolymer resin, etc. can be used. It is preferable from the viewpoint of the dispersibility of the chelate complex that a chelate complex is mixed in advance. Soft vinyl chloride resin coating layer, a value obtained by subtracting the weight of the textile fabric from tent structure membrane material of the present invention, 200 to 2000 g / m 2, in particular 300~1000g / m 2 is preferred.
軟質塩化ビニル樹脂被覆層に含むキレート錯体は、銀配位子、銅配位子、亜鉛配位子、及びニッケル配位子から選ばれた1種以上で、これらのキレート錯体(金属イオン)が黴菌表層の細胞透過性に関与するタンパク質のSH基と反応して生命活動に必要な酵素・タンパクを阻害する効果、或いは細胞内に侵入した金属イオンが黴菌の二本鎖DNAを架橋し、DNA複製を阻害することで黴や藻の繁殖を抑止する。銀イオンは臭化銀、塩化銀、クエン酸銀、沃化銀、乳酸銀、硝酸銀、酸化銀、ピクリン酸銀などの銀塩を供給源とし、銅はクエン酸二ナトリウム銅、トリエタノールアミン銅、炭酸銅、炭酸アンモニウム第一銅、水酸化第二銅、塩化銅、塩化第二銅、エチレンジアミン銅錯体、オキシ塩化銅、硫酸オキシ塩化銅、酸化第一銅、チオシアン酸銅などの銅塩を供給源とし、亜鉛は酢酸亜鉛、酸化亜鉛、炭酸亜鉛、塩化亜鉛、硫酸亜鉛、水酸化亜鉛、クエン酸亜鉛、フッ化亜鉛、沃化亜鉛、乳酸亜鉛、オレイン酸亜鉛、蓚酸亜鉛、燐酸亜鉛、プロピオン酸亜鉛、サリチル酸亜鉛、セレン酸亜鉛、珪酸亜鉛、ステアリン酸亜鉛、硫化亜鉛、タンニン酸亜鉛、酒石酸亜鉛、バレリアン酸亜鉛、グルコン酸亜鉛、ウンデシル酸亜鉛などの亜鉛塩を供給源とし、ニッケルは塩化ニッケル、水酸化ニッケル、硫酸ニッケル、酸化ニッケル、スルファミン酸ニッケルなどのニッケル塩を供給源とする。キレート錯体はこれらイオン供給源の金属塩と配位子とを適切な溶媒介してイオン結合させることで得られ、それを乾燥単離したものが本発明に用いられる。 The chelate complex contained in the soft vinyl chloride resin coating layer is at least one selected from a silver ligand, a copper ligand, a zinc ligand, and a nickel ligand, and these chelate complexes (metal ions) are used. The effect of inhibiting the enzymes and proteins necessary for life activity by reacting with the SH group of the protein involved in the cell permeability of the mold fungal surface, or the metal ions entering the cells crosslink the double-stranded DNA of the mold, Inhibiting replication prevents the growth of molds and algae. Silver ion is supplied from silver salts such as silver bromide, silver chloride, silver citrate, silver iodide, silver lactate, silver nitrate, silver oxide, silver picrate, and copper is disodium copper citrate, copper triethanolamine. Copper salts such as copper carbonate, cuprous ammonium carbonate, cupric hydroxide, copper chloride, cupric chloride, ethylenediamine copper complex, copper oxychloride, copper sulfate oxychloride, cuprous oxide, copper thiocyanate As a source, zinc is zinc acetate, zinc oxide, zinc carbonate, zinc chloride, zinc sulfate, zinc hydroxide, zinc citrate, zinc fluoride, zinc iodide, zinc lactate, zinc oleate, zinc oxalate, zinc phosphate, Sources zinc salts such as zinc propionate, zinc salicylate, zinc selenate, zinc silicate, zinc stearate, zinc sulfide, zinc tannate, zinc tartrate, zinc valerate, zinc gluconate, zinc undecylate, etc. , Nickel and sources of nickel chloride, nickel hydroxide, nickel sulfate, nickel oxide, nickel salts such as nickel sulfamate. The chelate complex is obtained by ion-bonding the metal salt of the ion source and the ligand via a suitable solvent, and the dried and isolated product is used in the present invention.
配位子は、グリシン、ヒスチジン、メチオニンから選ばれた1種以上のアミノ酸、エチレンジアミン、トリエチレンテトラミン、ピピリジン、エチレンジアミン四酢酸、ヒドロキシエチルエチレンジアミン三酢酸、ジヒドロキシエチルエチレンジアミン二酢酸、1,3−プロパンジアミン四酢酸、ジエチルトリアミン五酢酸、トリエチレンテトラミン六酢酸から選ばれた1種以上のエチレンアミン酢酸、ピリチオン、フェナントロリン、ポルフィリン、及び9−クラウン−3、12−クラウン−4,15−クラウン−5,18−クラウン−6,21−クラウン−7、24−クラウン−8,27−クラウン−9,30−クラウン−10,33−クラウン−11、36−クラウン−12、ジベンゾ12−クラウン−4、ジベンゾ18−クラウン−6,トリベンゾ18−クラウン−6,ジベンゾ24−クラウン−8,トリベンゾ27−クラウン−9、ジベンゾ30−クラウン−10、ジベンゾ36−クラウン−12、トリベンゾ36−クラウン−12、テトラベンゾ36−クラウン−12(これらはクラウンエーテルのエーテル環を簡略表記したもので頭の数字は全原子数、末尾の数字は酸素原子数を表す)、複数のクラウンエーテルの立体構造体であるクリプタンド[2.2]、クリプタンド[2.2.2]、及びこれらのクラウンエーテルの酸素原子の一部または全部を窒素原子(NH)に置換したアザクラウンエーテル、及びこれらの誘導体から選ばれた1種以上のクラウンエーテル、から選ばれた1種以上が挙げられ、一個の金属原子に対して複数の配位子が配位したもの、一個の金属原子に対して複数のクラウンエーテルでサンドイッチしたものを包含する。具体的にはヒスチジン銀、グリシン銅、ピリチオン亜鉛、ピリチオン銅、トリエチレンテトラミン銅、ジベンゾ24−クラウン−8銅、ジベンゾ24−クラウン−8亜鉛、ジベンゾ24−クラウン−8ニッケルなどが例示できる。 The ligand is one or more amino acids selected from glycine, histidine, and methionine, ethylenediamine, triethylenetetramine, piperidine, ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, and 1,3-propanediamine. One or more ethyleneamine acetic acids selected from tetraacetic acid, diethyltriaminepentaacetic acid, and triethylenetetraminehexaacetic acid, pyrithione, phenanthroline, porphyrin, and 9-crown-3, 12-crown-4,15-crown-5. 18-crown-6,21-crown-7, 24-crown-8,27-crown-9,30-crown-10,33-crown-11, 36-crown-12, dibenzo12-crown-4, dibenzo 18-Crown- , Tribenzo18-crown-6, dibenzo24-crown-8, tribenzo27-crown-9, dibenzo30-crown-10, dibenzo36-crown-12, tribenzo36-crown-12, tetrabenzo36-crown-12 ( These are simplified representations of the ether rings of crown ethers. The numbers at the top indicate the total number of atoms, and the numbers at the end indicate the number of oxygen atoms.) Cryptands [2.2], which are three-dimensional structures of crown ethers, [2.2.2] and aza crown ethers obtained by substituting a part or all of the oxygen atoms of these crown ethers with nitrogen atoms (NH), and one or more crown ethers selected from derivatives thereof. One or more selected ones, one in which multiple ligands coordinate to one metal atom, one Including those sandwiched by a plurality of crown ether respect genus atoms. Specific examples include silver histidine, glycine copper, zinc pyrithione, copper pyrithione, copper triethylenetetramine, copper dibenzo24-crown-8, zinc zinc dibenzo24-crown-8, nickel nickel dibenzo24-crown-8, and the like.
また、銀配位子、銅配位子、亜鉛配位子、及びニッケル配位子などのキレート錯体は、軟質塩化ビニル樹脂被覆層に対して、0.05〜5質量%、特に0.1〜2質量%で存在することが好ましく、キレート錯体は予め可塑剤中に混合したものを用いて軟質塩化ビニル樹脂被覆層を形成することでキレート錯体の分散性を改善する。また一方、キレート錯体は無機多孔質粒子に担持された状態で存在することで、キレート錯体を安定な徐放性に改善し、それによって長期の防黴・防藻効果を安定持続させることができる。無機多孔質粒子は具体的に、メソポーラスシリカ、(合成)ゼオライト、チタンゼオライト、リン酸ジルコニウム、リン酸カルシウム、リン酸亜鉛カルシウム、ハイドロタルサイト、ヒドロキシアパタイト、シリカアルミナ、ケイ酸カルシウム、ケイ酸アルミン酸マグネシウム、ケイソウ土、及びこれらのシランカップリング剤処理物などが例示できる。無機多孔質粒子に担持させるに好ましい配位子は、アミノ酸、エチレンジアミン、トリエチレンテトラミン、ピピリジン、エチレンアミン酢酸、ピリチオンなどである。無機多孔質粒子にキレート錯体を担持させる方法は、キレート錯体の製造時の溶媒中に無機多孔質粒子を混合攪拌して無機多孔質粒子にキレート錯体を吸着担持させ、それを乾燥単離したものが本発明に用いられる。この方法によるキレート錯体の担持は、キレート錯体生成後に無機多孔質粒子に吸着担持させた2段階工程のもの、キレート錯体生成と吸着担持を無機多孔質粒子内で行う1段階工程、の何れであってもよい。無機多孔質粒子に対するキレート錯体の担持率は特に限定は無いが、0.1〜10質量%、特に1〜5質量%が好ましい。この際に無機多孔質粒子には防黴性有機化合物とキレート錯体を同時に吸着担持させることもでき、それによって無機多孔質粒子の配合量を集約することを可能とする。また無機多孔質粒子の粒子径は特に限定は無いが、0.1〜5μm、特に0.3〜2μmが好ましい。また軟質塩化ビニル樹脂被覆層に含むこれらの無機多孔質粒子の含有率は軟質塩化ビニル樹脂被覆層に対して、0.5〜50質量%、好ましくは1〜20質量%である。 The chelate complex such as a silver ligand, a copper ligand, a zinc ligand, and a nickel ligand is used in an amount of 0.05 to 5% by mass, especially 0.1% by mass, based on the soft vinyl chloride resin coating layer. Preferably, it is present in an amount of about 2% by mass, and the dispersibility of the chelate complex is improved by forming a soft vinyl chloride resin coating layer using a premixed chelate complex in a plasticizer. On the other hand, the chelate complex is present in a state of being supported on the inorganic porous particles, thereby improving the chelate complex to a stable sustained-release property, thereby stably maintaining a long-term antifungal / algae effect. . Specific examples of the inorganic porous particles include mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate, and magnesium aluminate silicate. , Diatomaceous earth, and a treated product of these silane coupling agents. Preferred ligands to be supported on the inorganic porous particles are amino acids, ethylenediamine, triethylenetetramine, pyridine, ethyleneamineacetic acid, and pyrithione. The method of supporting the chelate complex on the inorganic porous particles is a method in which the inorganic porous particles are mixed and stirred in a solvent during the production of the chelate complex, and the chelate complex is adsorbed and supported on the inorganic porous particles, and then dried and isolated. Is used in the present invention. The support of the chelate complex by this method is either a two-step process in which the chelate complex is adsorbed and supported on the inorganic porous particles, or a one-step process in which the chelate complex formation and the adsorption and support are performed in the inorganic porous particles. You may. The loading ratio of the chelate complex to the inorganic porous particles is not particularly limited, but is preferably 0.1 to 10% by mass, particularly preferably 1 to 5% by mass. At this time, the inorganic porous particles can simultaneously adsorb and support the fungicidal organic compound and the chelate complex, thereby making it possible to consolidate the compounding amount of the inorganic porous particles. The particle diameter of the inorganic porous particles is not particularly limited, but is preferably 0.1 to 5 μm, particularly preferably 0.3 to 2 μm. The content of the inorganic porous particles contained in the soft vinyl chloride resin coating layer is 0.5 to 50% by mass, and preferably 1 to 20% by mass, based on the soft vinyl chloride resin coating layer.
一方、軟質塩化ビニル樹脂被覆層に含む防黴性有機化合物として、黴、細菌(グラム陽性、グラム陰性)、真菌などの細胞壁、細胞膜、細胞質、及び細胞核などに対して、酸化的リン酸化阻害、電子伝達系阻害、−SH基阻害、DNA合成阻害、細胞表皮機能阻害、脂質代謝阻害、キレート形成などの作用を及ぼす有機化合物である。これらは具体的に、A).2−(4−チアゾリル)−ベンズイミダゾール(略称TBZ)、2−(カルボメトキシアミノ)ベンズイミダゾール(略称BCM)、1−(ブチルカルバモイル)−2−ベンズイミダゾールカルバミン酸メチルなどのイミダゾール系化合物、B).2−n−オクチル−4−イソチアゾリン−3−オン、2−メルカプトベンゾチアゾール、2−(4−チオシアノメチルチオ)ベンゾチアゾール、2−(チオシアノメチルスルホニル)ベンゾチアゾールなどのチアゾール系化合物、C).2−メチル−4−イソチアゾリン−3−オン、2−n−オクチル−4−イソチアゾリン−3−オン、5−クロロ−2−メチル−4−イソチアゾリン−3−オン、5−クロロ−2−n−オクチル−4−イソチアゾリン−3−オン、4−クロロ−2−n−オクチル−4−イソチアゾリン−3−オン、4,5−ジクロロ−2−n−オクチル−4−イソチアゾリン−3−オン、2−メチル−4,5−トリメチレン−4−イソチアゾリン−3−オン、1,2−ベンズイソチアゾリン−3−オン、N−n−ブチル−1,2−ベンズイソチアゾリン−3−オン、2−メチルチオ−4−t−ブチルアミノ−6−シクロプロピルアミノ−S−チアジンなどのイソチアゾリン系化合物、D).ビス(ピリジン−2−チオール−1−オキシド)亜鉛塩(略称ZPT)、(2−ピリジンチオール−1−オキサイド)ナトリウム塩、2,2′−ジチオ−ビスピリジン−1−オキサイド、2−ピリジルチオ−1−オキサイド銅塩、2,3,5,6−テトラクロロ−4−(メチルスルホニル)ピリジンなどのピリジン系化合物、E).ヘキサヒドロ−N,N′,N″−トリス(2−ヒドロキシエチル)−S−トリアジン、ヘキサヒドロ−N,N′,N″−トリエチル−S−トリアジン、2−メチルチオ−4−t−ブチルアミノ−6−シクロプロピルアミノ−S−トリアジン、2−クロロ−4,6−ジエチルアミノ−S−トリアジン、2−クロロ−4−エチルアミノ−6−イソプロピルアミノ−S−トリアジン、2−メチルチオ−4−エチルアミノ−6−(1,2−ジメチルプロピルアミノ)−S−トリアジンなどのトリアジン系化合物、F).α−[2−(4−クロロフェニル)エチル]−α−(1,1−ジメチルエチル)−1H−1,2,4−トリアゾール−1−エタノール、1−[[2−(2,4−ジクロロフェニル)−4−n−プロピル−1,3−ジオキソラン−2−イル]メチル]−1H−1,2,4−トリアゾール、1−[[2−(2,4−ジクロロフェニル)−1,3−ジオキソラン−2−イル]メチル]−1H−1,2,4−トリアゾール、α−(4−クロロフェニル)−α−(1−シクロプロピルエチル)−1H−1,2,4−トリアゾール−1−エタノールなどのトリアゾール系化合物、G).N−(フルオロジクロロメチルチオ)フタルイミド、N−トリクロロメチルチオテトラヒドロフタルイミド、N−(トリクロロメチルチオ)−4−シクロヘキサン1,2−ジカルボキシイミド、N,N−ジメチル−N′−(フルオロジメチルチオ)−N′−フェニルスルファミド、N−ジクロロフルオロメチルチオ−N’,N’−ジメチル−N−p−トリルスルファミドなどのN−ハロアルキルチオ系化合物、H).塩化ベンザコニウム、塩化ベンゼトニウム、N−デシル−N−イソノニル−N,N−ジメチルアンモニウムクロライドなどの四級アンモニウム塩系化合物、I).10,10′−オキシビスフェノキシアルシン(略称OBPA)、8−オキシキノリン銅、2−エチルヘキサン酸ニッケルなどが例示できるが、これらに限定されるものではなく、その他、アルデヒド系、フェノール系、ピグアナイド系、ニトリル系、有機ヨード系、アニリド系、ジスルフィド系、チオカルバメート系、ハロアリルスルホン系、有機スズ系、チアジアジン系、及び天然物抽出成分(ヒノキチオール、茶カテキン、キトサンなど)などと併用することもできる。軟質塩化ビニル樹脂被覆層に含むこれらの防黴性有機化合物の含有率は軟質塩化ビニル樹脂被覆層に対して、0.05〜5質量%、好ましくは0.1〜2質量%である。 On the other hand, as a fungicidal organic compound contained in the soft vinyl chloride resin coating layer, it inhibits oxidative phosphorylation of molds, bacteria (gram-positive, gram-negative), cell walls of fungi, etc. It is an organic compound that exerts effects such as electron transfer system inhibition, -SH group inhibition, DNA synthesis inhibition, cell epidermal function inhibition, lipid metabolism inhibition, and chelate formation. These are specifically described in A). Imidazole compounds such as 2- (4-thiazolyl) -benzimidazole (abbreviation: TBZ), 2- (carbomethoxyamino) benzimidazole (abbreviation: BCM), methyl 1- (butylcarbamoyl) -2-benzimidazolecarbamate, B ). Thiazole compounds such as 2-n-octyl-4-isothiazolin-3-one, 2-mercaptobenzothiazole, 2- (4-thiocyanomethylthio) benzothiazole and 2- (thiocyanomethylsulfonyl) benzothiazole, C) . 2-methyl-4-isothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2-n- Octyl-4-isothiazolin-3-one, 4-chloro-2-n-octyl-4-isothiazolin-3-one, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2- Methyl-4,5-trimethylene-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, Nn-butyl-1,2-benzisothiazolin-3-one, 2-methylthio-4- isothiazoline compounds such as t-butylamino-6-cyclopropylamino-S-thiazine; D). Bis (pyridin-2-thiol-1-oxide) zinc salt (abbreviation ZPT), (2-pyridine-1-oxide) sodium salt, 2,2 '- dithio - bispyridine-1-oxide, 2-pyridylthio -1 Pyridine compounds such as -oxide copper salts and 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine; E). Hexahydro-N, N ', N "-tris (2-hydroxyethyl) -S-triazine, hexahydro-N, N', N" -triethyl-S-triazine, 2-methylthio-4-t-butylamino-6 -Cyclopropylamino-S-triazine, 2-chloro-4,6-diethylamino-S-triazine, 2-chloro-4-ethylamino-6-isopropylamino-S-triazine, 2-methylthio-4-ethylamino- Triazine-based compounds such as 6- (1,2-dimethylpropylamino) -S-triazine; F). α- [2- (4-chlorophenyl) ethyl] -α- (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol, 1-[[2- (2,4-dichlorophenyl) ) -4-n-Propyl-1,3-dioxolan-2-yl] methyl] -1H-1,2,4-triazole, 1-[[2- (2,4-dichlorophenyl) -1,3-dioxolane) -2-yl] methyl] -1H-1,2,4-triazole, α- (4-chlorophenyl) -α- (1-cyclopropylethyl) -1H-1,2,4-triazole-1-ethanol and the like G). N- (fluorodichloromethylthio) phthalimide, N-trichloromethylthiotetrahydrophthalimide, N- (trichloromethylthio) -4-cyclohexane1,2-dicarboximide, N, N-dimethyl-N ' -(fluorodimethylthio) -N '- phenyl sulfamide, N- dichlorofluoromethylthio -N', N'-dimethyl -N-p-tolyl-sulfamide such as N- haloalkylthio compounds, H). Quaternary ammonium salt compounds such as benzalkonium chloride, benzethonium chloride, N-decyl-N-isononyl-N, N-dimethylammonium chloride; I). 10, 10 '- oxy bisphenoxy sialic Shin (abbreviation OBPA), 8- oxyquinoline copper, 2 although nickel ethylhexanoate, and others, is not limited to, other aldehydes, phenols, Piguanaido System, nitrile system, organic iodine system, anilide system, disulfide system, thiocarbamate system, haloallyl sulfone system, organic tin system, thiadiazine system, and natural product extraction components (hinokitiol, tea catechin, chitosan, etc.) Can also. The content of these fungicidal organic compounds contained in the soft vinyl chloride resin coating layer is 0.05 to 5% by mass, preferably 0.1 to 2% by mass, based on the soft vinyl chloride resin coating layer.
また、上述の防黴性有機化合物は、軟質塩化ビニル樹脂被覆層に対して、0.05〜5質量%、特に0.1〜2質量%で存在することが好ましく、防黴性有機化合物は予め可塑剤中に混合したものを用いて軟質塩化ビニル樹脂被覆層を形成することで防黴性有機化合物の分散性を改善する。また一方、防黴性有機化合物を無機多孔質粒子に担持した状態とする使用系で防黴性有機化合物の徐放性を安定にコントロールし、それによって長期の防黴・防藻効果を安定持続させることを可能とする。無機多孔質粒子は具体的に、メソポーラスシリカ、(合成)ゼオライト、チタンゼオライト、リン酸ジルコニウム、リン酸カルシウム、リン酸亜鉛カルシウム、ハイドロタルサイト、ヒドロキシアパタイト、シリカアルミナ、ケイ酸カルシウム、ケイ酸アルミン酸マグネシウム、ケイソウ土、及びこれらのシランカップリング剤処理物などが例示できる。無機多孔質粒子に防黴性有機化合物を担持させる方法は、防黴性有機化合物を溶解して含む溶媒、または防黴性有機化合物を分散して含む溶媒中に無機多孔質粒子を混合攪拌して無機多孔質粒子に防黴性有機化合物を吸着担持させ、それを乾燥単離したもの、防黴性有機化合物を昇華、または熱融解させた状態での吸着担持などで得られたものが本発明に用いられる。この際に無機多孔質粒子には防黴性有機化合物とキレート錯体を同時に吸着担持させることもでき、それによって無機多孔質粒子の配合量を集約することを可能とする。無機多孔質粒子に対する防黴性有機化合物の担持率は特に限定は無いが、0.1〜10質量%、特に1〜5質量%が好ましい。また無機多孔質粒子の粒子径は特に限定は無いが、0.1〜5μm、特に0.3〜2μmが好ましい。また軟質塩化ビニル樹脂被覆層に含むこれらの無機多孔質粒子の含有率は軟質塩化ビニル樹脂被覆層に対して、0.5〜50質量%、好ましくは1〜20質量%である。 The above-mentioned fungicidal organic compound is preferably present at 0.05 to 5% by mass, particularly 0.1 to 2% by mass, based on the soft vinyl chloride resin coating layer. The dispersibility of the fungicidal organic compound is improved by forming a soft vinyl chloride resin coating layer using a material previously mixed in a plasticizer. On the other hand, in the use system in which the fungicidal organic compound is supported on the inorganic porous particles, the sustained release of the fungicidal organic compound is stably controlled, thereby stably maintaining the long-term fungicidal and anti-algal effects. It is possible to make. Specific examples of the inorganic porous particles include mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate, and magnesium aluminate silicate. , Diatomaceous earth, and a treated product of these silane coupling agents. The method of supporting the fungicidal organic compound on the inorganic porous particles is carried out by mixing and stirring the inorganic porous particles in a solvent containing the fungicidal organic compound dissolved therein or a solvent containing the fungicidal organic compound dispersed therein. The inorganic porous particles are made to adsorb and carry the antifungal organic compound on the inorganic porous particles, and are dried and isolated, and those obtained by adsorption and carrying of the antifungal organic compound by sublimation or heat melting are used in this study. Used in the invention. At this time, the inorganic porous particles can simultaneously adsorb and support the fungicidal organic compound and the chelate complex, thereby making it possible to consolidate the compounding amount of the inorganic porous particles. The loading ratio of the fungicidal organic compound to the inorganic porous particles is not particularly limited, but is preferably 0.1 to 10% by mass, and particularly preferably 1 to 5% by mass. The particle diameter of the inorganic porous particles is not particularly limited, but is preferably 0.1 to 5 μm, particularly preferably 0.3 to 2 μm. The content of the inorganic porous particles contained in the soft vinyl chloride resin coating layer is 0.5 to 50% by mass, and preferably 1 to 20% by mass, based on the soft vinyl chloride resin coating layer.
また、軟質塩化ビニル樹脂被覆層には難燃剤を配合することによって消防法に適合する防炎性を確保し、さらには国土交通大臣認定の不燃材料(テント構造物用不燃膜材)とすることが好ましい。塩化ビニル樹脂(可塑剤を含まない)100質量部に対し、リン含有化合物、窒素含有化合物、無機系化合物などの難燃剤を10〜100質量部配合すればよく、具体的にリン含有化合物としては、赤リン、(金属)リン酸塩、(金属)有機リン酸塩、ポリリン酸アンモニウムなどが挙げられ、また、窒素含有化合物としては、(イソ)シアヌレート系化合物、(イソ)シアヌル酸系化合物、グアニジン系化合物、尿素系化合物及びこれらの誘導体化合物であり、無機系化合物としては、金属酸化物(三酸化アンチモン、五酸化アンチモンなど)、金属水酸化物(水酸化アルミニウム、水酸化マグネシウムなど)、金属複合酸化物(ジルコニウム−アンチモン複合酸化物)、金属複合水酸化物(ヒドロキシスズ酸亜鉛、ハイドロタルサイトなど)などである。これらの難燃剤は2種以上を併用することで難燃性を向上させることができる。 In addition, the flame retardant that complies with the Fire Service Act shall be secured by blending a flame retardant into the soft vinyl chloride resin coating layer, and it shall be a nonflammable material (nonflammable film material for tent structures) certified by the Minister of Land, Infrastructure, Transport and Tourism. Is preferred. A flame retardant such as a phosphorus-containing compound, a nitrogen-containing compound, or an inorganic compound may be blended in an amount of 10 to 100 parts by mass with respect to 100 parts by mass of a vinyl chloride resin (not including a plasticizer). , Red phosphorus, (metal) phosphate, (metal) organic phosphate, ammonium polyphosphate, and the like. Examples of the nitrogen-containing compound include (iso) cyanurate compounds, (iso) cyanuric acid compounds, Guanidine-based compounds, urea-based compounds and derivatives thereof, and inorganic compounds include metal oxides (such as antimony trioxide and antimony pentoxide), metal hydroxides (such as aluminum hydroxide and magnesium hydroxide), Metal composite oxide (zirconium-antimony composite oxide), metal composite hydroxide (zinc hydroxystannate, hydrotalcite, etc.) ), And the like. The flame retardancy can be improved by using two or more of these flame retardants.
また、軟質塩化ビニル樹脂被覆層には軟質塩化ビニル樹脂用安定剤として、カルシウム亜鉛複合系、バリウム亜鉛複合系、有機錫ラウレート、有機錫メルカプタイト、エポキシ系などの安定剤を単独あるいは複数種併用して用いることが、本発明のテント構造物用膜材の製造時の熱劣化や変色を抑止し、さらに耐候性を向上させる。また本発明のテント構造物用膜材は顔料着色が自在で、特に白、パステル色などの着色はインクジェットプリントやマーキングフィルム文字入れのコントラストを鮮明とする。その他、軟質塩化ビニル樹脂被覆層には、塩化ビニル樹脂用の公知の添加剤を種々任意量配合することができ、必要に応じて、耐光安定剤(HALS)、紫外線吸収剤(ベンゾトリアゾール系、ベンゾフェノン系など)、酸化防止剤(フェノール系)、蛍光増白剤、帯電防止剤、硬化剤(イソシアネート系など)、防虫剤(ピレスロイド系など)、消臭剤(酸化珪素・金属酸化物複合系など)、遮熱フィラー(中空粒子、粗粒酸化チタンなど)、芳香剤、蓄光顔料(アルミン酸ストロンチウム系など)、アルミフレーク顔料、パール顔料、無機充填剤(炭酸カルシウム、硫酸バリウムなど)などを含むことができる。 In addition, the soft vinyl chloride resin coating layer may be used alone or in combination with a plurality of stabilizers such as a calcium zinc composite, a barium zinc composite, an organic tin laurate, an organic tin mercaptite, and an epoxy as a stabilizer for the soft vinyl chloride resin. When used, the thermal deterioration and discoloration during production of the film material for a tent structure of the present invention are suppressed, and the weather resistance is further improved. The film material for a tent structure of the present invention can be freely colored with a pigment. In particular, coloring such as white or pastel color makes the contrast of ink jet printing or marking film characters clear. In addition, in the soft vinyl chloride resin coating layer, various known additives for the vinyl chloride resin can be blended in various optional amounts. If necessary, a light stabilizer (HALS), an ultraviolet absorber (benzotriazole, Benzophenone type), antioxidant (phenol type), optical brightener, antistatic agent, curing agent (isocyanate type), insect repellent (pyrethroid type), deodorant (silicon oxide / metal oxide composite type) ), Thermal barrier fillers (hollow particles, coarse-grained titanium oxide, etc.), fragrances, luminous pigments (strontium aluminate, etc.), aluminum flake pigments, pearl pigments, inorganic fillers (calcium carbonate, barium sulfate, etc.) Can be included.
本発明のテント構造物用膜材の態様の1つとして、軟質塩化ビニル樹脂被覆層の少なくとも1面上に、光触媒物質含有防汚層が形成されていることが好ましく、光触媒物質の酸化還元作用によって煤塵汚れを効果的にセルフクリーニング(光触媒による防汚層の親水性化による降雨による洗浄、及び光触媒による黴や藻などの分解作用による)し、黴や藻の発生を効果的、かつ長期間に亘り抑止することでテント構造物の外観を安定維持することを可能とする。光触媒物質含有防汚層には、光触媒物質として、酸化チタン、過酸化チタン(ペルオキソチタン酸)、酸化亜鉛、酸化錫、チタン酸ストロンチウム、酸化タングステン、及び酸化ビスマスから選ばれた1種以上の粒子を含む以外、防黴、防藻に有効なキレート錯体として、銀配位子、銅配位子、亜鉛配位子、及びニッケル配位子から選ばれた1種以上のキレート錯体(段落〔0020〕、〔0021〕に記載のものと同一)を含むことが好ましい。光触媒物質含有防汚層は、光触媒物質10〜70質量%、金属酸化物ゲル及び/又は金属水酸化物ゲル(シリカゾル、アルミナゾル、ジルコニアゾル、酸化ニオブゾルなど)25〜90質量%、ケイ素化合物(ポリシロキサン、コロイダルシリカ、シリカなど)1〜20質量%、及びキレート錯体1〜10質量%の組成による、厚さ0.1〜15μmの無機物を主体とするキレート錯体含有ゾルゲル薄膜が好ましい。この場合、光触媒物質含有防汚層と軟質塩化ビニル樹脂被覆層との中間には、光触媒物質の酸化還元作用から軟質塩化ビニル樹脂被覆層を保護するための中間保護層が設けることが膜材の耐久性向上の観点において好ましく、中間保護層は光触媒物質含有防汚層の組成から光触媒物質を省いた組成物による厚さ0.1〜15μmの無機物を主体とするゾルゲル薄膜が好ましい。この他の光触媒物質含有防汚層は、フッ素含有共重合体樹脂(ポリフッ化ビニリデン、ポリフッ化ビニリデン−ヘキサフルオロプロピレン共重合体、ポリフッ化ビニリデン−ヘキサフルオロプロピレン−テトラフルオロエチレン共重合体など)に、光触媒物質粒子(好ましくは酸化チタン)の表面をシリカ、リン酸ジルコニウム、リン酸カルシウム、リン酸亜鉛カルシウム、ヒドロキシアパタイト、シリカアルミナ、ケイ酸カルシウム、ケイ酸アルミン酸マグネシウムなどの無機化合物で部分被覆してなる光触媒活性コントロールタイプの光触媒物質複合粒子を含有してなる厚さ5〜50μmの範囲のキレート錯体含有塗膜が使用できる。 As one aspect of the film material for a tent structure of the present invention, a photocatalytic substance-containing antifouling layer is preferably formed on at least one surface of the soft vinyl chloride resin coating layer, and the photocatalytic substance has a redox effect. Effective self-cleaning of dust and dirt (washing by rainfall by making the antifouling layer hydrophilic with a photocatalyst, and decomposition of molds and algae by the photocatalyst), and effective and long-term generation of molds and algae This makes it possible to stably maintain the appearance of the tent structure. The photocatalytic substance-containing antifouling layer includes, as the photocatalytic substance, at least one particle selected from titanium oxide, titanium peroxide (peroxotitanic acid), zinc oxide, tin oxide, strontium titanate, tungsten oxide, and bismuth oxide. And at least one chelate complex selected from a silver ligand, a copper ligand, a zinc ligand, and a nickel ligand (see paragraph [0020] ] And [0021]). The photocatalyst substance-containing antifouling layer comprises 10 to 70% by mass of a photocatalyst material, 25 to 90% by mass of a metal oxide gel and / or a metal hydroxide gel (silica sol, alumina sol, zirconia sol, niobium oxide sol, etc.), a silicon compound (poly) A sol-gel thin film containing an inorganic substance and having a thickness of 0.1 to 15 μm and having a composition of 1 to 20% by mass (siloxane, colloidal silica, silica, etc.) and 1 to 10% by mass of a chelate complex is preferable. In this case, an intermediate protective layer may be provided between the photocatalytic substance-containing antifouling layer and the soft vinyl chloride resin coating layer to protect the soft vinyl chloride resin coating layer from the redox action of the photocatalytic substance. It is preferable from the viewpoint of improving durability, and the intermediate protective layer is preferably a sol-gel thin film mainly composed of an inorganic substance having a thickness of 0.1 to 15 μm, which is a composition obtained by omitting the photocatalytic substance from the composition of the photocatalytic substance-containing antifouling layer. The other antifouling layer containing a photocatalytic substance is coated on a fluorine-containing copolymer resin (polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer, etc.). The surface of photocatalytic substance particles (preferably titanium oxide) is partially coated with an inorganic compound such as silica, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydroxyapatite, silica alumina, calcium silicate, magnesium silicate aluminate, etc. A chelate complex-containing coating film having a thickness of 5 to 50 μm containing the photocatalytic substance composite particles of the photocatalytic activity control type can be used.
光触媒物質含有防汚層に含有するキレート錯体は、メソポーラスシリカ、(合成)ゼオライト、チタンゼオライト、リン酸ジルコニウム、リン酸カルシウム、リン酸亜鉛カルシウム、ハイドロタルサイト、ヒドロキシアパタイト、シリカアルミナ、ケイ酸カルシウム、ケイ酸アルミン酸マグネシウム、ケイソウ土、及びこれらのシランカップリング剤処理物、から選ばれた1種以上の無機多孔質粒子に担持され、キレート錯体の徐放性がコントロールされた状態とすることで長期の防黴・防藻効果を安定持続させることが可能となる。無機多孔質粒子は段落〔0022〕に記載のものが同様の方法で使用できる。無機多孔質粒子に対するキレート錯体の担持率は特に限定は無いが、0.1〜10質量%、特に1〜5質量%が好ましい。無機多孔質粒子には防黴性有機化合物とキレート錯体を同時に吸着担持させることもできる。 The chelate complex contained in the photocatalytic substance-containing antifouling layer includes mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate, silica Magnesium aluminate, diatomaceous earth, and those treated with a silane coupling agent, are supported on one or more inorganic porous particles, and the controlled release of the chelate complex is controlled for a long time. Can stably maintain the fungicidal and anti-algae effects of. The inorganic porous particles described in paragraph [0022] can be used in the same manner. The loading ratio of the chelate complex to the inorganic porous particles is not particularly limited, but is preferably 0.1 to 10% by mass, particularly preferably 1 to 5% by mass. A fungicidal organic compound and a chelate complex can be simultaneously adsorbed and carried on the inorganic porous particles.
テント構造物を構築するために、本発明のテント構造物用膜材の接合(端部重ね合わせ接着)は、高周波ウエルダー機を用いて高周波振動によって接合を行うことができ、具体的に、2ヶ所の電極(一方の電極は、ウエルドバー)間に膜材を置き、ウエルドバーで加圧しながら高周波(1〜200MHz)で発振する電位差を印加することで膜材の樹脂層を分子摩擦熱で溶融軟化状態とすることで融合し、その状態で冷却固化して接合体を得る。また、超音波振動子から発生する超音波エネルギー(16〜30KHz)の振幅を増幅させ、膜材の境界面に発生する摩擦熱を利用して融合を行う超音波融着法、またはヒーターの電気制御によって、100〜700℃に無段階設定された熱風を、ノズルを通じて膜材間に吹き込み、膜材の表面を溶融軟化させ、ノズル通過直後膜材を圧着して融合を行う熱風融着法、軟質塩化ビニル樹脂被覆層の溶融温度以上にヒーター内蔵加熱した金型(こて)を用いて被着体を圧着し融合を行う熱板融着法などによって接合可能である。 In order to construct a tent structure, the bonding of the membrane material for a tent structure of the present invention (end overlapping bonding) can be performed by high-frequency vibration using a high-frequency welding machine. A resin material is placed between two electrodes (one electrode is a weld bar), and the resin layer of the film material is heated by molecular friction heat by applying a potential difference oscillating at a high frequency (1 to 200 MHz) while applying pressure with the weld bar. By being in a melt-softened state, they are fused and then cooled and solidified in that state to obtain a joined body. Also, an ultrasonic fusion method of amplifying the amplitude of ultrasonic energy (16 to 30 KHz) generated from the ultrasonic vibrator and performing fusion using frictional heat generated at a boundary surface of the film material, or an electric heater. A hot air fusion method in which hot air set in a stepless manner at 100 to 700 ° C. is blown between the film materials through a nozzle by control to melt and soften the surface of the film material, and to press and fuse the film material immediately after passing through the nozzle, It can be joined by a hot plate fusion method in which the adherend is pressed and fused using a mold (trowel) with a heater built in above the melting temperature of the soft vinyl chloride resin coating layer or higher.
次ぎに実施例、比較例を挙げて本発明を具体的に説明するが、本発明はこれらの例の範囲に限定されるものではない。下記実施例及び比較例において、テント構造物用膜材の防黴性などの性能の評価に用いた基準は以下の試験方法による。
(I)屋外展張曝露による防黴・防藻性の評価
幅20cm×長さ2mのテント構造物用膜材を、北向きに設置した曝露台(土台は苔の生えたコンクリート製)の傾斜30°方向と垂直方向にそれぞれ1mずつ連続して展張し、屋外展張る曝露を18ヶ月間行った。展張12ヶ月後、24ヶ月後、36ヶ月後のテント構造物用膜材全体を観察し、黴と藻の発生の有無、及びその発育状態をランク分けすることで防黴性(または防藻性)の評価を行った。
※屋外展張は、埼玉県草加市内において4月より開始した。
1:黴(藻)の発生(痕跡)が認められない(初期の状態を維持)
2:僅かに黴(藻)の発生(痕跡)を認める
3:部分的(試験体の9%以内のエリア)に黴(藻)発生(痕跡)を認める
4:部分的(試験体の10%以上のエリア)に黴(藻)発生(痕跡)を認める
(II)防黴性の評価(JIS Z2911培養試験)
幅3cm×長さ3cmのテント構造物用膜材に、下記試験用黴の胞子を接種し、ポテト・デキストロース寒天培地上に置き、シャーレ中で28℃×7日間、及び14日間、黴の発生状況を観察し、以下の判定基準で評価した。
1:試験片の接種した部分に菌糸の発育が認められない
2:試験片の接種した部分に認められる菌糸の発育部分の面積が、
全面積の 1/3 を超えない
3:試験片の接種した部分に認められる菌糸の発育部分の面積が、
全面積の 1/3 を超える
〈試験用黴〉a+b+cの混合黴
a:Aspergillus niger NBRC 105649(黒黴)
b:Penicillium citrinum NBRC 6352(青黴)
c:Cladosporium cladosporioides NBRC 6348(クロカワ黴)
(III)防黴性の持続性評価(JIS Z2911準拠の培養試験)
幅3cm×長さ3cmのテント構造物用膜材を200ccの水(エタノール35%濃度)中に浸漬し、30℃で1週間静置する下処理を行ったものを試験片として、(II)の試験を実施した。
1:試験片の接種した部分に菌糸の発育が認められない
2:試験片の接種した部分に認められる菌糸の発育部分の面積が,
全面積の 1/3 を超えない
3:試験片の接種した部分に認められる菌糸の発育部分の面積が,
全面積の 1/3 を超える
Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the scope of these Examples. In the following Examples and Comparative Examples, the criteria used for evaluating the performance such as the antifungal property of the membrane material for tent structures are based on the following test methods.
(I) Evaluation of fungicidal and anti-algal properties by outdoor extension exposure The slope of an exposure table (base is made of moss-grown concrete) on a tent structure membrane with a width of 20 cm and a length of 2 m facing north. The film was continuously stretched 1 m each in the ° direction and the vertical direction, and exposed outdoors for 18 months. After 12 months, 24 months, and 36 months after the expansion, the entire membrane material for tent structures was observed, and the presence or absence of mold and algae, and the state of their growth were classified into ranks, whereby fungicidal (or algal) resistance was evaluated. ) Was evaluated.
* The outdoor exhibition started in April in Soka City, Saitama Prefecture.
1: No occurrence (trace) of mold (algae) is observed (maintain initial state)
2: Slight mold (algae) generation (trace) is observed. 3: Partial (area within 9% of test sample) mold (algae) generation (trace) is recognized. 4: Partial (10% of test sample). Mold (algae) generation (trace) in the above areas) (II) Evaluation of fungicide resistance (JIS Z2911 culture test)
The following test mold spores were inoculated into a membrane material for a tent structure having a width of 3 cm and a length of 3 cm, placed on a potato dextrose agar medium, and generated at 28 ° C. for 7 days and 14 days in a petri dish. The situation was observed and evaluated according to the following criteria.
1: No hyphal growth was observed in the inoculated portion of the test piece. 2: The area of the hyphal growth portion observed in the inoculated portion of the test piece was:
Not more than 1/3 of the total area 3: The area of the hyphal growth area observed in the inoculated part of the test piece is
<Test mold> More than 1/3 of the total area <Mold for test> a + b + c mixed mold a: Aspergillus niger NBRC 105649 (black mold)
b: Penicillium citrinum NBRC 6352 (blue mold)
c: Cladosporium cladosporioides NBRC 6348 (Kurokawa mold)
(III) Persistence evaluation of antifungal property (culture test according to JIS Z2911)
A test piece was prepared by immersing a membrane material for a tent structure having a width of 3 cm × a length of 3 cm in 200 cc of water (ethanol 35% concentration) and allowing it to stand at 30 ° C. for 1 week as a test piece (II). Was tested.
1: No hyphal growth was observed in the inoculated portion of the test piece. 2: The area of the hyphal growth in the inoculated portion of the test piece was:
Not more than 1/3 of the total area 3: The area of mycelial growth observed in the inoculated part of the test piece was
Over 1/3 of total area
[参考例1]
ポリエステル繊維平織基布(経糸1111dtexマルチフィラメント糸条:糸密度19本/2.54cm×緯糸1111dtexマルチフィラメント糸条:糸密度21本/2.54cm:空隙率12%:質量180g/m2)を基材として、その両面に下記軟質塩化ビニル樹脂組成物(1)を用いて180〜190℃の条件のカレンダー成型により得た厚さ0.2mmのフィルム(軟質塩化ビニル樹脂被覆層)を、180〜190℃の条件のラミネート機により熱プレスすることで、厚さ0.65mm、質量700g/m2の膜材を得た。
〈軟質塩化ビニル樹脂組成物(1)〉
塩化ビニル樹脂(重合度1050) 100質量部
1,2−シクロヘキサンジカルボン酸ジイソノニル(可塑剤) 50質量部
※商品名:ヘキサモールDINCH(BASF社製)
グリシン銅(キレート錯体) 0.5質量部
ヒスチジン銀(キレート錯体) 0.5質量部
※キレート錯体、またはその担持体は予め可塑剤中に混合したものを用いた
10,10′−オキシビスフェノキシアルシン(防黴性有機化合物)0.15質量部
2−(4−チアゾリル)−ベンズイミダゾール(防黴性有機化合物)0.15質量部
※防黴性有機化合物、またはその担持体は予め可塑剤中に混合したものを用いた
塩素化n−パラフィン(防炎可塑剤) 10質量部
エポキシ化大豆油(安定剤兼可塑剤) 5質量部
バリウム/亜鉛複合安定剤 2質量部
三酸化アンチモン(難燃剤) 10質量部
ルチル型酸化チタン(白顔料) 5質量部
ベンゾトリアゾール(紫外線吸収剤) 0.3質量部
[ Reference Example 1]
Polyester fiber plain woven base cloth (warp 1111 dtex multifilament yarn: yarn density 19 / 2.54 cm × weft 1111 dtex multifilament yarn: yarn density 21 / 2.54 cm: porosity 12%: mass 180 g / m 2 ) As a substrate, a film (soft vinyl chloride resin coating layer) having a thickness of 0.2 mm obtained by calender molding under the conditions of 180 to 190 ° C. using the following soft vinyl chloride resin composition (1) on both surfaces thereof was A film material having a thickness of 0.65 mm and a mass of 700 g / m 2 was obtained by hot pressing with a laminating machine at a temperature of 190 ° C.
<Soft vinyl chloride resin composition (1)>
Vinyl chloride resin (degree of polymerization 1050) 100 parts by mass Diisononyl 1,2-cyclohexanedicarboxylate (plasticizer) 50 parts by mass * Trade name: Hexamol DINCH (manufactured by BASF)
Glycine copper (chelate complex) 0.5 parts by mass Histidine silver (chelate complex) 0.5 parts by mass * A chelate complex or a carrier thereof was used by previously mixing in a plasticizer. 10,10'-oxybisphenoxy 0.15 parts by mass of arsine (antifungal organic compound) 0.15 parts by mass of 2- (4-thiazolyl) -benzimidazole (antifungal organic compound) * The antifungal organic compound or its carrier is a plasticizer in advance. Chlorinated n-paraffin (flameproof plasticizer) 10 parts by mass Epoxidized soybean oil (stabilizer and plasticizer) 5 parts by mass Barium / zinc composite stabilizer 2 parts by mass Antimony trioxide (difficult Combustion agent) 10 parts by mass Rutile type titanium oxide (white pigment) 5 parts by mass Benzotriazole (ultraviolet absorber) 0.3 parts by mass
[参考例2]
参考例1の軟質塩化ビニル樹脂組成物(1)において、グリシン銅(キレート錯体)0.5質量部をピリチオン亜鉛(キレート錯体)0.5質量部に置換えた以外は参考例1と同様にして厚さ0.65mm、質量700g/m2の膜材を得た。
[ Reference Example 2]
In the same manner as in Reference Example 1, except that 0.5 parts by mass of glycine copper (chelate complex) was replaced by 0.5 parts by mass of pyrithione zinc (chelate complex) in the soft vinyl chloride resin composition (1) of Reference Example 1. A film material having a thickness of 0.65 mm and a mass of 700 g / m 2 was obtained.
[実施例3]
参考例1の軟質塩化ビニル樹脂組成物(1)において、グリシン銅(キレート錯体)0.5質量部を24−クラウン−8銅(キレート錯体)0.5質量部に置換えた以外は参考例1と同様にして厚さ0.65mm、質量700g/m2の膜材を得た。
[Example 3]
In soft vinyl chloride resin composition of Reference Example 1 (1), except that replacing glycine copper (chelate complexes) 0.5 parts by mass of 24-crown -8 copper (chelate complexes) to 0.5 parts by weight Reference Example 1 In the same manner as in the above, a film material having a thickness of 0.65 mm and a mass of 700 g / m 2 was obtained.
[参考例4]
参考例1において、グリシン銅(キレート錯体)0.5質量部、及びヒスチジン銀(キレート錯体)0.5質量部を、予めメソポーラスシリカにグリシン銅(キレート錯体)0.5質量部及びヒスチジン銀(キレート錯体)0.5質量部を担持させた、グリシン銅(キレート錯体)・ヒスチジン銀(キレート錯体)担持メソポーラスシリカ31質量部に置換えた以外は参考例1と同様にして厚さ0.65mm、質量698g/m2の膜材を得た。
※グリシン銅(キレート錯体)・ヒスチジン銀(キレート錯体)担持メソポーラスシリカの調製
グリシン銅(キレート錯体)を0.5g、及びヒスチジン銀(キレート錯体)を0.5g含む水−エタノール溶液200mlに、メソポーラスシリカ(平均粒子径2.5μm)30gを加え、シランカップリング剤(γ−グリシドキシプロピルトリメトキシシラン)1gと共に、常温1時間撹拌し、水−エタノール溶媒を減圧除去後、100℃で乾燥し、粉末を約31g得た。この粉末31gが担持するグリシン銅(キレート錯体)の量、及びヒスチジン銀(キレート錯体)の量は各々0.5gである。
[ Reference Example 4]
In Reference Example 1, 0.5 parts by mass of glycine copper (chelate complex) and 0.5 parts by mass of histidine silver (chelate complex) were previously added to mesoporous silica by 0.5 parts by mass of glycine copper (chelate complex) and histidine silver ( (Chelate complex) A thickness of 0.65 mm was obtained in the same manner as in Reference Example 1 except that the glycine copper (chelate complex) / histidine silver (chelate complex) -supported mesoporous silica, which supported 0.5 part by mass, was replaced by 31 parts by mass. A film material having a mass of 698 g / m 2 was obtained.
* Preparation of mesoporous silica supporting glycine copper (chelate complex) / histidine silver (chelate complex) Mesoporous in 200 ml of a water-ethanol solution containing 0.5 g of glycine copper (chelate complex) and 0.5 g of histidine silver (chelate complex). 30 g of silica (average particle diameter 2.5 μm) was added, and the mixture was stirred at room temperature for 1 hour with 1 g of a silane coupling agent (γ-glycidoxypropyltrimethoxysilane). The water-ethanol solvent was removed under reduced pressure, and then dried at 100 ° C. As a result, about 31 g of a powder was obtained. The amount of copper glycine (chelate complex) and the amount of silver histidine (chelate complex) supported by 31 g of this powder are each 0.5 g.
[参考例5]
参考例4のグリシン銅(キレート錯体)・ヒスチジン銀(キレート錯体)担持メソポーラスシリカ11質量部を、グリシン銅(キレート錯体)・ヒスチジン銀(キレート錯体)担持リン酸ジルコニウム31質量部に置換えた以外は参考例4と同様にして厚さ0.65mm、質量698g/m2の膜材を得た。
※グリシン銅(キレート錯体)・ヒスチジン銀(キレート錯体)担持リン酸ジルコニウムの調製
グリシン銅(キレート錯体)を0.5g、及びヒスチジン銀(キレート錯体)を0.5g含む水−エタノール溶液200mlに、リン酸ジルコニウム(平均粒子径3μm)30gを加え、シランカップリング剤(γ−グリシドキシプロピルトリメトキシシラン)1gと共に、常温1時間撹拌し、水−エタノール溶媒を減圧除去後、100℃で乾燥し、粉末を約31g得た。この粉末31gが担持するグリシン銅(キレート錯体)の量、及びヒスチジン銀(キレート錯体)の量は各々0.5gである。
[ Reference Example 5]
Except that 11 parts by mass of mesoporous silica carrying glycine copper (chelate complex) / histidine silver (chelate complex) of Reference Example 4 was replaced by 31 parts by mass of zirconium phosphate carrying glycine copper (chelate complex) / histidine silver (chelate complex). In the same manner as in Reference Example 4, a film material having a thickness of 0.65 mm and a mass of 698 g / m 2 was obtained.
* Preparation of zirconium phosphate supporting glycine copper (chelate complex) and histidine silver (chelate complex) In a 200 ml water-ethanol solution containing 0.5 g of glycine copper (chelate complex) and 0.5 g of histidine silver (chelate complex), 30 g of zirconium phosphate (average particle size: 3 μm) was added, and the mixture was stirred at room temperature for 1 hour with 1 g of a silane coupling agent (γ-glycidoxypropyltrimethoxysilane). The water-ethanol solvent was removed under reduced pressure, followed by drying at 100 ° C. As a result, about 31 g of a powder was obtained. The amount of copper glycine (chelate complex) and the amount of silver histidine (chelate complex) supported by 31 g of this powder are each 0.5 g.
[参考例6]
参考例2のヒスチジン銀(キレート錯体)0.5質量部、及びピリチオン亜鉛(キレート錯体)0.5質量部を、ヒスチジン銀(キレート錯体)・ピリチオン亜鉛(キレート錯体)担持合成ゼオライト31質量部に置換えた以外は参考例2と同様にして厚さ0.65mm、質量698g/m2の膜材を得た。
※ヒスチジン銀(キレート錯体)・ピリチオン亜鉛(キレート錯体)担持合成ゼオライトの調製
ヒスチジン銀(キレート錯体)を0.5gと、ピリチオン亜鉛を0.5g含む水−エタノール溶液200mlに、合成ゼオライト(平均粒子径2μm)30gを加え、シランカップリング剤(γ−グリシドキシプロピルトリメトキシシラン)1gと共に、常温1時間撹拌し、水−エタノール溶媒を減圧除去後、100℃で乾燥し、粉末を約31g得た。この粉末31gが担持するヒスチジン銀(キレート錯体)の量、及びピリチオン亜鉛の量は各々0.5gである。
[ Reference Example 6]
0.5 parts by mass of silver histidine (chelate complex) and 0.5 parts by mass of zinc pyrithione (chelate complex) of Reference Example 2 were added to 31 parts by mass of synthetic zeolite supporting silver histidine (chelate complex) and zinc pyrithione (chelate complex). A film material having a thickness of 0.65 mm and a mass of 698 g / m 2 was obtained in the same manner as in Reference Example 2 except that the substitution was performed.
* Preparation of synthetic zeolites supporting silver histidine (chelate complex) and zinc pyrithione (chelate complex) In a 200 ml water-ethanol solution containing 0.5 g of histidine silver (chelate complex) and 0.5 g of zinc pyrithione, the synthetic zeolite (average particles 30 g was added thereto, and the mixture was stirred at room temperature for 1 hour with 1 g of a silane coupling agent (γ-glycidoxypropyltrimethoxysilane). The water-ethanol solvent was removed under reduced pressure, and the resultant was dried at 100 ° C. to obtain about 31 g of powder. Obtained. The amount of silver histidine (chelate complex) and the amount of zinc pyrithione carried by 31 g of this powder are each 0.5 g.
[実施例7]
実施例3のヒスチジン銀(キレート錯体)0.5質量部、及び24−クラウン−8銅(キレート錯体)0.5質量部を、ヒスチジン銀(キレート錯体)・24−クラウン−8銅(キレート錯体)担持ケイソウ土31質量部に置換えた以外は実施例3と同様にして厚さ0.65mm、質量698g/m2の膜材を得た。
※ヒスチジン銀(キレート錯体)・24−クラウン−8銅(キレート錯体)担持ケイソウ土の調製
ヒスチジン銀(キレート錯体)を0.5gと、24−クラウン−8銅を0.5g含む水−エタノール溶液200mlに、ケイソウ土(平均粒子径2μm)30gを加え、シランカップリング剤(γ−グリシドキシプロピルトリメトキシシラン)1gと共に、常温1時間撹拌し、水−エタノール溶媒を減圧除去後、100℃で乾燥し、粉末を約31g得た。この粉末31gが担持するヒスチジン銀(キレート錯体)の量、及び24−クラウン−8銅の量は各々0.5gである。
[Example 7]
0.5 parts by mass of silver histidine (chelate complex) and 0.5 parts by mass of 24-crown-8 copper (chelate complex) of Example 3 were combined with silver histidine (chelate complex) / 24-crown-8 copper (chelate complex). ) A membrane material having a thickness of 0.65 mm and a mass of 698 g / m 2 was obtained in the same manner as in Example 3 except that the diatomaceous earth was replaced with 31 parts by mass of diatomaceous earth.
* Preparation of diatomaceous earth supporting histidine silver (chelate complex) / 24-crown-8 copper (chelate complex) Water-ethanol solution containing 0.5 g of histidine silver (chelate complex) and 0.5 g of 24-crown-8 copper To 200 ml, 30 g of diatomaceous earth (average particle size: 2 μm) was added, and the mixture was stirred with 1 g of a silane coupling agent (γ-glycidoxypropyltrimethoxysilane) at room temperature for 1 hour. , And about 31 g of a powder was obtained. The amount of silver histidine (chelate complex) supported by 31 g of this powder and the amount of 24-crown-8 copper are each 0.5 g.
[参考例8]
参考例4において、10,10′−オキシビスフェノキシアルシン(防黴性有機化合物:略称OBPA)0.15質量部、及び2−(4−チアゾリル)−ベンズイミダゾール(防黴性有機化合物:略称TBZ)0.15質量部を、予めメソポーラスシリカにOBPA0.15質量部、及びTBZ0.15質量部を担持させた、防黴性有機化合物担持メソポーラスシリカ10.5質量部に置換えた以外は参考例4と同様にして厚さ0.65mm、質量700g/m2の膜材を得た。
※OBPA・TBZ担持メソポーラスシリカの調製
OBPAを0.15g、及びTBZを0.15g含む水−エタノール溶液100mlに、メソポーラスシリカ(平均粒子径2.5μm)10gを加え、シランカップリング剤(γ−グリシドキシプロピルトリメトキシシラン)1gと共に、常温1時間撹拌し、水−エタノール溶媒を減圧除去後、100℃で乾燥し、粉末を約10.5g得た。この粉末10.5gが担持するOBPAの量、及びTBZの量は各々0.15gである。
[ Reference Example 8]
Reference Example 4, 10, 10 '- oxy bisphenoxy sialic Shin (antifungal organic compound: Abbreviation OBPA) 0.15 parts by weight, and 2- (4-thiazolyl) - benzimidazole (antifungal organic compound: Abbreviation TBZ Reference Example 4) except that 0.15 parts by mass was replaced with 10.5 parts by mass of a fungicidal organic compound-supported mesoporous silica in which 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ were previously supported on mesoporous silica. In the same manner as in the above, a film material having a thickness of 0.65 mm and a mass of 700 g / m 2 was obtained.
* Preparation of OBPA / TBZ-supported mesoporous silica To 100 ml of a water-ethanol solution containing 0.15 g of OBPA and 0.15 g of TBZ, 10 g of mesoporous silica (average particle diameter 2.5 μm) was added, and a silane coupling agent (γ- The mixture was stirred at room temperature for 1 hour together with 1 g of (glycidoxypropyltrimethoxysilane), the water-ethanol solvent was removed under reduced pressure, and dried at 100 ° C. to obtain about 10.5 g of powder. The amount of OBPA and the amount of TBZ carried by 10.5 g of this powder are each 0.15 g.
[参考例9]
参考例5において、OBPA0.15質量部、及びTBZ0.15質量部を、予めリン酸ジルコニウムにOBPA0.15質量部、及びTBZ0.15質量部を担持させた、防黴性有機化合物担持リン酸ジルコニウム10.5質量部に置換えた以外は参考例5と同様にして厚さ0.65mm、質量700g/m2の膜材を得た。
※OBPA・TBZ担持リン酸ジルコニウムの調製
OBPAを0.15g、及びTBZを0.15g含む水−エタノール溶液100mlに、リン酸ジルコニウム(平均粒子径3μm)10gを加え、シランカップリング剤(γ−グリシドキシプロピルトリメトキシシラン)1gと共に、常温1時間撹拌し、水−エタノール溶媒を減圧除去後、100℃で乾燥し、粉末を約10.5g得た。この粉末10.5gが担持するOBPAの量、及びTBZの量は各々0.15gである。
[ Reference Example 9]
In Reference Example 5, 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ were added to 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ in advance on zirconium phosphate. A film material having a thickness of 0.65 mm and a weight of 700 g / m 2 was obtained in the same manner as in Reference Example 5 except that the replacement was carried out with 10.5 parts by mass.
* Preparation of OBPA / TBZ-supported zirconium phosphate To 100 ml of a water-ethanol solution containing 0.15 g of OBPA and 0.15 g of TBZ, add 10 g of zirconium phosphate (average particle diameter: 3 μm), and add a silane coupling agent (γ- The mixture was stirred at room temperature for 1 hour together with 1 g of (glycidoxypropyltrimethoxysilane), the water-ethanol solvent was removed under reduced pressure, and dried at 100 ° C. to obtain about 10.5 g of powder. The amount of OBPA and the amount of TBZ carried by 10.5 g of this powder are each 0.15 g.
[参考例10]
参考例6において、OBPA0.15質量部、及びTBZ0.15質量部を、予め合成ゼオライトにOBPA0.15質量部、及びTBZ0.15質量部を担持させた、防黴性有機化合物担持合成ゼオライト10.5質量部に置換えた以外は参考例6と同様にして厚さ0.65mm、質量700g/m2の膜材を得た。
※OBPA・TBZ担持合成ゼオライトの調製
OBPAを0.15g、及びTBZを0.15g含む水−エタノール溶液100mlに、合成ゼオライト(平均粒子径2μm)10gを加え、シランカップリング剤(γ−グリシドキシプロピルトリメトキシシラン)1gと共に、常温1時間撹拌し、水−エタノール溶媒を減圧除去後、100℃で乾燥し、粉末を約10.5g得た。この粉末10.5gが担持するOBPAの量、及びTBZの量は各々0.15gである。
[ Reference Example 10]
9. In Reference Example 6, 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ were added to 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ in advance on a synthetic zeolite. A film material having a thickness of 0.65 mm and a mass of 700 g / m 2 was obtained in the same manner as in Reference Example 6, except that the amount was changed to 5 parts by mass.
* Preparation of OBPA / TBZ-supported synthetic zeolite To 100 ml of a water-ethanol solution containing 0.15 g of OBPA and 0.15 g of TBZ, 10 g of synthetic zeolite (average particle diameter 2 μm) was added, and a silane coupling agent (γ-glycidide) was added. The mixture was stirred at room temperature for 1 hour together with 1 g of (xypropyltrimethoxysilane), the water-ethanol solvent was removed under reduced pressure, and dried at 100 ° C. to obtain about 10.5 g of powder. The amount of OBPA and the amount of TBZ carried by 10.5 g of this powder are each 0.15 g.
[実施例11]
実施例7において、OBPA0.15質量部、及びTBZ0.15質量部を、予めケイソウ土にOBPA0.15質量部、及びTBZ0.15質量部を担持させた、防黴性有機化合物担持ケイソウ土10.5質量部に置換えた以外は実施例7と同様にして厚さ0.65mm、質量695g/m2の膜材を得た。
※OBPA・TBZ担持ケイソウ土の調製
OBPAを0.15g、及びTBZを0.15g含む水−エタノール溶液100mlに、ケイソウ土(平均粒子径2μm)10gを加え、シランカップリング剤(γ−グリシドキシプロピルトリメトキシシラン)1gと共に、常温1時間撹拌し、水−エタノール溶媒を減圧除去後、100℃で乾燥し、粉末を約10.5g得た。この粉末10.5gが担持するOBPAの量、及びTBZの量は各々0.15gである。
[Example 11]
9. In Example 7, 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ were added to diatomaceous earth in advance to carry 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ. A film material having a thickness of 0.65 mm and a weight of 695 g / m 2 was obtained in the same manner as in Example 7 except that the amount was changed to 5 parts by mass.
* Preparation of diatomaceous earth carrying OBPA / TBZ To 100 ml of a water-ethanol solution containing 0.15 g of OBPA and 0.15 g of TBZ, 10 g of diatomaceous earth (average particle diameter 2 μm) was added, and a silane coupling agent (γ-glycidide) was added. The mixture was stirred at room temperature for 1 hour together with 1 g of (xypropyltrimethoxysilane), the water-ethanol solvent was removed under reduced pressure, and dried at 100 ° C. to obtain about 10.5 g of powder. The amount of OBPA and the amount of TBZ carried by 10.5 g of this powder are each 0.15 g.
[参考例12]
参考例8において、グリシン銅(キレート錯体)・ヒスチジン銀(キレート錯体)担持メソポーラスシリカ10.5質量部、及びOBPA・TBZ担持メソポーラスシリカ10.5質量部を、予めメソポーラスシリカにグリシン銅(キレート錯体)0.5質量部とヒスチジン銀(キレート錯体)0.5質量部、及びOBPA0.15質量部とTBZ0.15質量部を担持させた、キレート錯体及び防黴性有機化合物担持メソポーラスシリカ41質量部に置換えた以外は参考例8と同様にして厚さ0.65mm、質量690g/m2の膜材を得た。
※キレート錯体及び防黴性有機化合物担持メソポーラスシリカの調製
グリシン銅(キレート錯体)0.5gとヒスチジン銀(キレート錯体)0.5g、及びOBPA0.15gとTBZ0.15gとを含む水−エタノール溶液100mlに、メソポーラスシリカ(平均粒子径2.5μm)40gを加え、シランカップリング剤(γ−グリシドキシプロピルトリメトキシシラン)1gと共に、常温1時間撹拌し、水−エタノール溶媒を減圧除去後、100℃で乾燥し、粉末を約41g得た。この粉末41gが担持するグリシン銅(キレート錯体)の量とヒスチジン銀(キレート錯体)の量は各々0.15gであり、OBPAの量、及びTBZの量は各々0.15gである。
[ Reference Example 12]
In Reference Example 8, 10.5 parts by mass of mesoporous silica supporting glycine copper (chelate complex) / histidine silver (chelate complex) and 10.5 parts by mass of mesoporous silica supporting OBPA / TBZ were previously added to mesoporous silica to form glycine copper (chelate complex). ) 41 parts by mass of mesoporous silica carrying a chelate complex and a fungicidal organic compound carrying 0.5 parts by mass and 0.5 parts by mass of histidine silver (chelate complex), and 0.15 parts by mass of OBPA and 0.15 parts by mass of TBZ A film material having a thickness of 0.65 mm and a mass of 690 g / m 2 was obtained in the same manner as in Reference Example 8 except that the film material was replaced.
* Preparation of mesoporous silica supporting chelate complex and antifungal organic compound 100 ml of a water-ethanol solution containing 0.5 g of glycine copper (chelate complex), 0.5 g of histidine silver (chelate complex), and 0.15 g of OBPA and 0.15 g of TBZ Was added with 40 g of mesoporous silica (average particle size 2.5 μm), and the mixture was stirred at room temperature for 1 hour with 1 g of a silane coupling agent (γ-glycidoxypropyltrimethoxysilane). It dried at ℃ and obtained about 41g of powder. The amount of glycine copper (chelate complex) and the amount of silver histidine (chelate complex) supported by 41 g of this powder are 0.15 g, and the amounts of OBPA and TBZ are each 0.15 g.
[参考例13,14、実施例15]
参考例1,2、及び実施例3の膜材に光触媒物質含有防汚層を形成したものを参考例13,14、及び実施例15とした。
※中間保護層の形成
下記ケイ素化合物含有樹脂の塗工液を80メッシユのグラビアロールを有するコーターで15g/m2塗布(wet)し、100℃の熱風炉中で1分間乾燥させ中間保護層を形成した。(固形分付着量3g/m2)
〈ケイ素化合物含有樹脂層塗工液〉
アクリル−シリコン共重合体樹脂溶液(固形分8質量%) 100質量部
メチルシリケート溶液(固形分20質量%) 8質量部
γ−グリシドキシプロピルトリメトキシシラン(シランカップリング剤) 1質量部
グリシン銅(キレート錯体) 0.5質量部
ヒスチジン銀(キレート錯体) 0.5質量部
※光触媒物質含有防汚層の形成
下記光触媒物質含有防汚層形成用の塗工液を80メッシユのグラビアロールを有するコーターで15g/m2塗布(wet)し、100℃の熱風炉中で1分間乾燥させ光触媒物質含有防汚層をゾルゲル形成(固形分付着量2g/m2)し、各々実施例13〜15の厚さ0.65mm、質量705g/m2の膜材を得た。
〈光触媒物質含有防汚層形成用の塗工液〉
硝酸酸性酸化チタンゾル(酸化チタン含有量10質量%相当) 100質量部
硝酸酸性シリカゾル(酸化ケイ素含有量10質量%相当) 100質量部
グリシン銅(キレート錯体) 0.5質量部
ヒスチジン銀(キレート錯体) 0.5質量部
[ Reference Examples 13 , 14 and Example 15]
The film materials of Reference Examples 1 and 2 and Example 3 with a photocatalytic substance-containing antifouling layer formed thereon were referred to as Reference Examples 13 and 14 and Example 15.
* Formation of intermediate protective layer A coating solution of the following silicon compound-containing resin is applied (wet) at 15 g / m 2 with a coater having a gravure roll of 80 mesh and dried in a hot air oven at 100 ° C. for 1 minute to form an intermediate protective layer. Formed. (Solid content 3g / m 2 )
<Silicon compound-containing resin layer coating liquid>
Acrylic-silicon copolymer resin solution (solid content 8% by mass) 100 parts by mass Methyl silicate solution (solid content 20% by mass) 8 parts by mass γ-glycidoxypropyltrimethoxysilane (silane coupling agent) 1 part by mass glycine Copper (chelate complex) 0.5 parts by mass Histidine silver (chelate complex) 0.5 parts by mass
* Formation of photocatalytic substance-containing antifouling layer 15 g / m 2 of a coating solution for forming a photocatalyst substance-containing antifouling layer is applied in a coater having a gravure roll of 80 meshes in a hot air oven at 100 ° C. After drying for 5 minutes, the photocatalytic substance-containing antifouling layer was formed into a sol-gel (solids adhesion amount: 2 g / m 2 ) to obtain a film material of Examples 13 to 15 having a thickness of 0.65 mm and a mass of 705 g / m 2 .
<Coating liquid for forming antifouling layer containing photocatalytic substance>
Nitric acid acidic titanium oxide sol (equivalent to 10% by mass of titanium oxide) 100 parts by mass Nitric acid acidic silica sol (equivalent to 10% by mass of silicon oxide) 100 parts by mass Glycine copper (chelate complex) 0.5 part by mass Histidine silver (chelate complex) 0.5 parts by mass
[参考例16〜18,20〜12,14、及び実施例15,19,23]
参考例4〜6,8〜10,12、及び実施例3,7,11の膜材に光触媒物質含有防汚層を形成したものを参考例16〜18,20〜12,14、及び実施例15,19,23とした。
※中間保護層の形成
参考例13,14、及び実施例15と同一の組成及び形成方法による。
※光触媒物質含有防汚層の形成
下記光触媒物質含有防汚層形成用の塗工液を80メッシユのグラビアロールを有するコーターで25g/m2塗布(wet)し、100℃の熱風炉中で1分間乾燥させ光触媒物質含有防汚層を形成(固形分付着量7g/m2)し、各々実施例16〜24の厚さ0.65mm、質量707g/m2の膜材を得た。
〈光触媒物質含有防汚層形成用の塗工液〉
フッ化ビニリデン樹脂溶液(固形分15質量%) 100質量部
光触媒性酸化チタン(平均粒子径1μm) 8質量部
※ヒドロキシアパタイトによる表面被覆率4〜10%の部分被覆)
グリシン銅(キレート錯体)・ヒスチジン銀(キレート錯体)担持メソポーラスシリカ
10質量部
※グリシン銅(キレート錯体)・ヒスチジン銀(キレート錯体)担持メソポーラスシリカの調製
グリシン銅(キレート錯体)を0.5g、及びヒスチジン銀(キレート錯体)を0.5g含む水−エタノール溶液200mlに、メソポーラスシリカ(平均粒子径2.5μm)30gを加え、シランカップリング剤(γ−グリシドキシプロピルトリメトキシシラン)1gと共に、常温1時間撹拌し、水−エタノール溶媒を減圧除去後、100℃で乾燥し、粉末を約31g得た。この粉末31gが担持するグリシン銅(キレート錯体)の量、及びヒスチジン銀(キレート錯体)の量は各々0.5gである。
[ Reference Examples 16 to 18, 20 to 12, 14, and Examples 15, 19, 23 ]
The photocatalytic substance-containing antifouling layer was formed on the film material of Reference Examples 4 to 6, 8 to 10, 12 and Examples 3 , 7, and 11 , and Reference Examples 16 to 18, 20 to 12, 14, and Examples 15 , 19, and 23 .
* Formation of intermediate protective layer
The same composition and forming method as in Reference Examples 13 and 14 and Example 15 are used.
* Formation of photocatalytic substance-containing antifouling layer The following coating solution for forming a photocatalytic substance-containing antifouling layer is applied (wet) 25 g / m 2 with a coater having a gravure roll of 80 meshes, and is coated in a hot air oven at 100 ° C. minutes dried form a photocatalyst substance containing antifouling layer (solid content adhesion quantity 7 g / m 2), to give each thickness 0.65mm examples 16-24, the film material of mass 707 g / m 2.
<Coating liquid for forming antifouling layer containing photocatalytic substance>
100 parts by mass of vinylidene fluoride resin solution (solid content: 15% by mass) 8 parts by mass of photocatalytic titanium oxide (average particle size: 1 μm) * Partial coating of hydroxyapatite with a surface coverage of 4 to 10%)
Mesoporous silica supporting copper glycine (chelate complex) and silver histidine (chelate complex)
10 parts by mass
* Preparation of mesoporous silica supporting glycine copper (chelate complex) / histidine silver (chelate complex) Mesoporous in 200 ml of a water-ethanol solution containing 0.5 g of glycine copper (chelate complex) and 0.5 g of histidine silver (chelate complex). 30 g of silica (average particle diameter 2.5 μm) was added, and the mixture was stirred at room temperature for 1 hour with 1 g of a silane coupling agent (γ-glycidoxypropyltrimethoxysilane). The water-ethanol solvent was removed under reduced pressure, and then dried at 100 ° C. As a result, about 31 g of a powder was obtained. The amount of copper glycine (chelate complex) and the amount of silver histidine (chelate complex) supported by 31 g of this powder are each 0.5 g.
[実施例3,7,11の防黴効果]
軟質塩化ビニル樹脂被覆層にキレート錯体と、防黴性有機化合物とを含む実施例3,7,11のテント構造物用膜材はキレート錯体を用いることで全て、防黴試験(I):屋外展張曝露36ヶ月後にも黴や藻の発生(痕跡)が認められず、初期の状態を維持しており、また防黴試験(II):JIS Z2911培養試験においても菌糸の発育が認められないものであったことからテント構造物用膜材として十分な防黴効果が期待できることが明らかとなった。また長期使用を想定しての防黴試験(III):での優劣は、キレート錯体と防黴性有機化合物を無機多孔質粒子に担持させて用いた実施例11の膜材が最も防黴性の長期持続性を有し、次いでキレート錯体を無機多孔質粒子に担持させて用いた実施例7の膜材の防黴持続性が高く、実施例3の膜材は実施例中では幾分長期持続性に劣るものではあるが、従来の膜材よりも優れていることは明らかである。また、実施例3,7,11のテント構造物用膜材に光触媒物質含有防汚層を形成した実施例15,19,23のテント構造物用膜材は、煤塵汚れの蓄積や雨筋汚れなどの顕著な発生が長期間認められず、光触媒物質含有防汚層による降雨セルフクリ−ニングによる防汚効果、及び黴菌などの有機物分解効果によって、実施例3,7,11のテント構造物用膜材よりも更に初期外観を長期間安定持続可能とするものであり、特に実施例19,23のテント構造物用膜材では、実施例11,15のテント構造物用膜材よりも持続期間が優れていた。
[Antifungal effect of Examples 3 , 7 , 11 ]
The film materials for tent structures of Examples 3 , 7 , and 11 in which the soft vinyl chloride resin coating layer contains a chelate complex and a fungicide-resistant organic compound are all prepared by using a chelate complex. No molds or algae were found (traces) after 36 months of spreading exposure, and the initial state was maintained. No fungal growth was observed in the antifungal test (II): JIS Z2911 culture test. Thus, it was revealed that a sufficient antifungal effect can be expected as a film material for a tent structure. The superiority in the antifungal test (III) assuming long-term use is that the membrane material of Example 11 in which a chelate complex and an antifungal organic compound are supported on inorganic porous particles is the most antifungal. The film material of Example 7 using the chelate complex supported on inorganic porous particles has a high long-term durability, and the film material of Example 3 has a somewhat longer duration in Examples. Although poor in sustainability, it is clear that it is superior to the conventional film material. Further, the tent structure membrane materials of Examples 15 , 19 , and 23 in which the photocatalytic substance-containing antifouling layer was formed on the tent structure film materials of Examples 3 , 7 , and 11 showed accumulation of dust and rain streaks. No remarkable occurrence was observed for a long period of time, and the antifouling effect of rainfall self-cleaning by the photocatalytic substance-containing antifouling layer and the effect of decomposing organic substances such as fungi caused the membranes for tent structures of Examples 3 , 7 , and 11. The material for the tent structure of Examples 19 and 23 has a longer duration than the material of the tent structure of Examples 11 and 15 , particularly in the film material for tent structure of Examples 19 and 23. It was excellent.
[参考比較例1]
参考例1の軟質塩化ビニル樹脂組成物(1)から、グリシン銅(キレート錯体)0.5質量部、及びヒスチジン銀(キレート錯体)0.5質量部を省略した以外は参考例1と同様として、厚さ0.65mm、質量700g/m2の膜材を得た。参考比較例1の膜材はキレート錯体を省いたことで、防黴性有機化合物による防黴効果のみとなり、初期的な防黴効果は良好に発現するものの、防黴試験(I)36ヶ月後には防黴性有機化合物のブリード、降雨による洗い流れ、劣化などの要因で、部分的(試験体の6%程度のエリア)に黴の発生を認め、また防黴試験(III)では防黴性有機化合物の抽出により、試験片の接種した部分に認められる菌糸の発育部分の面積が全面積の1/3を超えるなど、実施例1の膜材に比較して防黴性の長期安定持続性を大きく損なうものであった。
[ Reference Comparative Example 1]
Same as Reference Example 1 except that 0.5 parts by mass of glycine copper (chelate complex) and 0.5 parts by mass of histidine silver (chelate complex) were omitted from the soft vinyl chloride resin composition (1) of Reference Example 1. A film material having a thickness of 0.65 mm and a mass of 700 g / m 2 was obtained. By omitting the chelate complex from the film material of Reference Comparative Example 1, only the antifungal effect of the antifungal organic compound was obtained, and the initial antifungal effect was well exhibited, but after 36 months of the antifungal test (I). Was found to be mildew due to factors such as bleeding of the antifungal organic compound, washing away due to rainfall, deterioration, etc., and the occurrence of fungi was partially observed (approximately 6% of the specimen). As a result of the extraction of the organic compound, the area of the growth portion of the hypha observed in the inoculated portion of the test piece exceeded one-third of the total area. Was greatly impaired.
[参考比較例2]
参考例1の軟質塩化ビニル樹脂組成物(1)から、グリシン銅(キレート錯体)0.5質量部、及びヒスチジン銀(キレート錯体)0.5質量部を省略し、替わりに銀イオン担持ゼオライト1質量部に変更した以外は参考例1と同様として、厚さ0.65mm、質量700g/m2の膜材を得た。参考比較例2の膜材は銀イオン担持ゼオライトと、防黴性有機化合物とを有することで比較的長期間の防黴性を発現可能であったが、防黴試験(I)36ヶ月後には防黴性有機化合物のブリード、降雨による洗い流れ、劣化などの要因で、黴の発生を認め、また防黴試験(III)では、防黴性有機化合物の抽出により、試験片の接種した部分に認められる菌糸の発育部分の面積が全面積の1/3を超えない程度で、比較例1よりは良好ではあるが、実施例1の膜材に比較すると防黴性の長期安定持続性は劣るものであった。
[ Reference Comparative Example 2]
From the soft vinyl chloride resin composition (1) of Reference Example 1, 0.5 parts by mass of copper glycine (chelate complex) and 0.5 parts by mass of silver histidine (chelate complex) were omitted, and instead, zeolite 1 carrying silver ion was used. A film material having a thickness of 0.65 mm and a mass of 700 g / m 2 was obtained in the same manner as in Reference Example 1 except that the amount was changed to parts by mass. The membrane material of Reference Comparative Example 2 was able to exhibit a relatively long-term antifungal property by having a silver ion-supporting zeolite and an antifungal organic compound, but after 36 months of the antifungal test (I), The occurrence of mold was recognized due to factors such as bleeding of the antifungal organic compound, washing away due to rainfall, deterioration, etc. In the antifungal test (III), extraction of the antifungal organic compound resulted in the inoculation of the test piece on the inoculated portion. Although the area of the growing portion of the hyphae does not exceed 1/3 of the total area, it is better than Comparative Example 1, but is inferior to the membrane material of Example 1 in terms of long-term stability of the antifungal property. Was something.
[参考比較例3]
参考例1の軟質塩化ビニル樹脂組成物(1)から、10,10′−オキシビスフェノキシアルシン(防黴性有機化合物)0.15質量部、及び2−(4−チアゾリル)−ベンズイミダゾール(防黴性有機化合物)0.15質量部を省略した以外は参考例1と同様として、厚さ0.65mm、質量700g/m2の膜材を得た。参考比較例3の膜材は、防黴性有機化合物を省いたことで、キレート錯体による防黴効果のみとなり、初期的な防黴効果が良好に発現するものの、防黴試験(I)36ヶ月後には部分的(試験体の6%程度のエリア)に黴の発生を認め、また防黴試験(III)では、試験片の接種した部分に認められる菌糸の発育部分の面積が全面積の1/3を超えるなど、実施例1の膜材に比較して防黴性の長期安定持続性を大きく損なうものであった。
[ Reference Comparative Example 3]
A soft vinyl chloride resin composition of Reference Example 1 (1), 10, 10 '- 0.15 part by weight oxy bisphenoxy sialic Shin (antifungal organic compound), and 2- (4-thiazolyl) - benzimidazole (proof (Moldy organic compound) A film material having a thickness of 0.65 mm and a mass of 700 g / m 2 was obtained in the same manner as in Reference Example 1 except that 0.15 parts by mass was omitted. The film material of Reference Comparative Example 3 had only the antifungal effect by the chelate complex by omitting the antifungal organic compound, and although the initial antifungal effect was well exhibited, the antifungal test (I) was 36 months. After that, the occurrence of mold was partially observed (about 6% of the specimen), and in the antifungal test (III), the area of the mycelial growth observed in the inoculated portion of the test piece was 1% of the total area. As a result, the long-term stability of the antifungal property was significantly impaired as compared with the film material of Example 1.
[参考比較例4]
参考例1の軟質塩化ビニル樹脂組成物(1)を、カレンダー成型タイプのポリウレタン樹脂組成物(1)に変更し、180℃のカレンダー成型に供したところ、グリシン銅(キレート錯体)とヒスチジン銀(キレート錯体)がカレンダー成型の熱ロールに焼き付き、フィルム加工が不能となって、膜材を得ることができないものであった。
〈ポリウレタン樹脂組成物(1)〉
ポリウレタン樹脂(エーテル型) 100質量部
グリシン銅(キレート錯体) 0.5質量部
ヒスチジン銀(キレート錯体) 0.5質量部
10,10′−オキシビスフェノキシアルシン(防黴性有機化合物)0.15質量部
2−(4−チアゾリル)−ベンズイミダゾール(防黴性有機化合物)0.15質量部
ポリリン酸アンモニウム(難燃剤) 10質量部
メラミンシアヌレート(難燃剤) 10質量部
ルチル型酸化チタン(白顔料) 5質量部
ベンゾトリアゾール(紫外線吸収剤) 0.3質量部
モンタン酸ワックス(滑剤) 0.5質量部
[ Reference Comparative Example 4]
When the soft vinyl chloride resin composition (1) of Reference Example 1 was changed to a calendar-molded type polyurethane resin composition (1) and subjected to calendar molding at 180 ° C., glycine copper (chelate complex) and histidine silver ( The chelate complex) was seized on a calender-molded heat roll, making it impossible to process the film and making it impossible to obtain a film material.
<Polyurethane resin composition (1)>
Polyurethane resin (ether type) 100 parts by mass Glycine copper (chelate complex) 0.5 parts by mass Histidine silver (chelate complex) 0.5 parts by mass 10,10'-oxybisphenoxyarsine (antifungal organic compound) 0.15 Parts by mass 2- (4-thiazolyl) -benzimidazole (mold-resistant organic compound) 0.15 parts by mass ammonium polyphosphate (flame retardant) 10 parts by mass melamine cyanurate (flame retardant) 10 parts by mass rutile-type titanium oxide (white) Pigment) 5 parts by mass Benzotriazole (UV absorber) 0.3 parts by mass Montanic acid wax (lubricant) 0.5 parts by mass
[参考比較例5]
参考例1の軟質塩化ビニル樹脂組成物(1)を、カレンダー成型タイプのポリエチレン樹脂組成物(1)に変更し、150℃のカレンダー成型に供したところ、グリシン銅(キレート錯体)とヒスチジン銀(キレート錯体)がカレンダー成型の熱ロールに焼き付き、フィルム加工が不能となって、膜材を得ることができないものであった。
〈ポリエチレン樹脂組成物(1)〉
ポリウレタン樹脂(エーテル型) 100質量部
グリシン銅(キレート錯体) 0.5質量部
ヒスチジン銀(キレート錯体) 0.5質量部
10,10′−オキシビスフェノキシアルシン(防黴性有機化合物)0.15質量部
2−(4−チアゾリル)−ベンズイミダゾール(防黴性有機化合物)0.15質量部
ポリリン酸アンモニウム(難燃剤) 10質量部
メラミンシアヌレート(難燃剤) 10質量部
ルチル型酸化チタン(白顔料) 5質量部
ベンゾトリアゾール(紫外線吸収剤) 0.3質量部
モンタン酸ワックス(滑剤) 0.5質量部
[ Reference Comparative Example 5]
When the soft vinyl chloride resin composition (1) of Reference Example 1 was changed to a calender-molded type polyethylene resin composition (1) and subjected to calender molding at 150 ° C., glycine copper (chelate complex) and histidine silver ( The chelate complex) was seized on a calender-molded heat roll, making it impossible to process the film and making it impossible to obtain a film material.
<Polyethylene resin composition (1)>
Polyurethane resin (ether type) 100 parts by mass Glycine copper (chelate complex) 0.5 parts by mass Histidine silver (chelate complex) 0.5 parts by mass 10,10'-oxybisphenoxyarsine (antifungal organic compound) 0.15 Parts by mass 2- (4-thiazolyl) -benzimidazole (mold-resistant organic compound) 0.15 parts by mass ammonium polyphosphate (flame retardant) 10 parts by mass melamine cyanurate (flame retardant) 10 parts by mass rutile-type titanium oxide (white) Pigment) 5 parts by mass Benzotriazole (UV absorber) 0.3 parts by mass Montanic acid wax (lubricant) 0.5 parts by mass
上記、実施例、及び比較例から明らかな様に、本発明によれば、黴や藻の発生を最小限に抑止することができる膜材が得られるので、本発明の膜材は、中〜大型テント構造物(スタジアム屋根、ドーム球場、開閉式屋根ドーム、パビリオンなど)、日除けテント構造物(公共施設モニュメント、駅舎ホーム屋根、連絡通路屋根、アーケード屋根、店舗用、住居用など)、内照式テント構造物(電飾看板、映像投影ドーム、アート造型など)などのテント構造物(金属フレームに防水性の繊維複合シートを取り付けた構造)などに広く適して用いることができる。 As is clear from the above examples and comparative examples, according to the present invention, a film material capable of minimizing the occurrence of mold and algae is obtained. Large tent structures (stadium roof, dome stadium, retractable roof dome, pavilions, etc.), awning tent structures (public facilities monuments, station building home roofs, access passage roofs, arcade roofs, stores, residences, etc.), interior lighting The present invention can be widely used for tent structures (structures in which a waterproof fiber composite sheet is attached to a metal frame) such as a tent structure (eg, an electric sign, an image projection dome, and art molding).
Claims (8)
The chelate complex contained in the photocatalytic substance-containing antifouling layer may be a mesoporous silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, zinc calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate 8. The film material for a tent structure according to claim 7, wherein the film material is supported on at least one kind of inorganic porous particles selected from the group consisting of silica, magnesium aluminate, diatomaceous earth, and a treated product of these silane coupling agents.
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