WO2000023528A1 - Materiau resistant aux salissures, procede et dispositif de production et composition de revetement - Google Patents
Materiau resistant aux salissures, procede et dispositif de production et composition de revetement Download PDFInfo
- Publication number
- WO2000023528A1 WO2000023528A1 PCT/JP1999/005766 JP9905766W WO0023528A1 WO 2000023528 A1 WO2000023528 A1 WO 2000023528A1 JP 9905766 W JP9905766 W JP 9905766W WO 0023528 A1 WO0023528 A1 WO 0023528A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- substrate
- coating
- antifouling
- coating composition
- heating
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 126
- 239000008199 coating composition Substances 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 144
- 239000000758 substrate Substances 0.000 claims abstract description 114
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 31
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 23
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 17
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims description 173
- 239000011248 coating agent Substances 0.000 claims description 161
- 238000010438 heat treatment Methods 0.000 claims description 159
- 230000003373 anti-fouling effect Effects 0.000 claims description 110
- 239000003921 oil Substances 0.000 claims description 65
- 239000002585 base Substances 0.000 claims description 44
- 239000010408 film Substances 0.000 claims description 42
- 239000011521 glass Substances 0.000 claims description 39
- 239000010410 layer Substances 0.000 claims description 28
- 229910052910 alkali metal silicate Inorganic materials 0.000 claims description 24
- 238000007654 immersion Methods 0.000 claims description 24
- 239000010409 thin film Substances 0.000 claims description 21
- 239000003513 alkali Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 230000001699 photocatalysis Effects 0.000 claims description 10
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 9
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 9
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000005642 Oleic acid Substances 0.000 claims description 9
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 9
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 9
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 9
- 238000011084 recovery Methods 0.000 claims description 9
- 230000000844 anti-bacterial effect Effects 0.000 claims description 8
- 239000005300 metallic glass Substances 0.000 claims description 8
- 239000000378 calcium silicate Substances 0.000 claims description 7
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 7
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 239000013618 particulate matter Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000002689 soil Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 238000010828 elution Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000002344 surface layer Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000003779 heat-resistant material Substances 0.000 claims description 3
- 239000012212 insulator Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- 239000004566 building material Substances 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000004568 cement Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 claims description 2
- 239000011147 inorganic material Substances 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims 2
- 239000011236 particulate material Substances 0.000 claims 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims 1
- 239000004567 concrete Substances 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 229910021332 silicide Inorganic materials 0.000 claims 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 15
- 235000019198 oils Nutrition 0.000 description 64
- 238000005299 abrasion Methods 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 22
- 238000004140 cleaning Methods 0.000 description 17
- 235000019353 potassium silicate Nutrition 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 240000008415 Lactuca sativa Species 0.000 description 15
- 239000004111 Potassium silicate Substances 0.000 description 15
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 description 15
- 229910052913 potassium silicate Inorganic materials 0.000 description 15
- 235000012045 salad Nutrition 0.000 description 15
- 239000007921 spray Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000010304 firing Methods 0.000 description 13
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 12
- 229910052912 lithium silicate Inorganic materials 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- 238000002411 thermogravimetry Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000005507 spraying Methods 0.000 description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- -1 alkali metal salt Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229910001413 alkali metal ion Inorganic materials 0.000 description 5
- 238000007664 blowing Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052845 zircon Inorganic materials 0.000 description 5
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 238000009736 wetting Methods 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000004453 electron probe microanalysis Methods 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910013504 M-O-M Inorganic materials 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000002781 deodorant agent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 239000008157 edible vegetable oil Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000001443 photoexcitation Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000238558 Eucarida Species 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 241001422033 Thestylus Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 125000005624 silicic acid group Chemical group 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
- C03C17/23—Oxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5041—Titanium oxide or titanates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/212—TiO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/229—Non-specific enumeration
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/71—Photocatalytic coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31678—Of metal
Definitions
- the present invention relates to an antifouling material having excellent antifouling properties on a surface, in particular, an antifouling property against dirt containing an oily component, a method for producing the same, and a coating composition and an apparatus therefor.
- the antifouling technique of the conventional substrate surface physically by smoothing; and a method of forming a dirt flame surface adhesion frame of the superior oxidative decomposition ability of immobilized photocatalyst surface lend raw There are known methods for decomposing organic substances and washing off dirt adhered by superhydrophilization of photocatalysts. However, with these methods, sufficient antifouling properties may not be obtained in an environment where the load of oily dirt is large or in an environment where sufficient light for developing a photocatalytic function cannot be obtained.
- the following materials are known as materials having an inorganic coating formed on the surface, with or without relation to the antifouling property of the surface.
- Japanese Patent Application Laid-Open No. 53-983224 discloses that after coating a porous inorganic base material as a base coat, a porous silica base material is coated with an inorganic base paint as an overcoat.
- a technique of imparting heat resistance and the like by curing at room temperature or under heating is disclosed.
- Japanese Patent Application Laid-Open No. 5-123636 / 1991 discloses that a porous resin surface such as calcium silicate is coated with a synthetic resin coating as an undercoat and an inorganic coating as an intermediate coating.
- a technique for applying an inorganic coating mainly composed of silicate is disclosed.
- Japanese Patent Application Laid-Open No. Hei 9-2187843 discloses that the center line average roughness Ra 'value of the film surface is 0.
- a hydrophilic film mainly composed of irregularities having a thickness of 5 to 500 nm and a repetition length of irregularities on the surface in the plane direction of 0.5 or less.
- Japanese Patent Application Laid-Open No. Hei 9-212710 discloses a photocatalytic hydrophilic member in which a layer containing a photocatalytic titanium oxide and an amorphous oxide is formed.
- Japanese Unexamined Patent Publication No. 6-9995 discloses a method for removing dirt using a water-soluble alkali metal salt.
- a dirt remover containing the water-soluble alkali metal silicate By applying a dirt remover containing the water-soluble alkali metal silicate to dirt already adhered to the substrate surface, the dirt is included in the remover, and the dirt-removing remover is removed to remove the dirt. It is characterized by the ability to exhibit its characteristics. Since this remover is not adhered to the substrate, this stain removal method is only a temporary stain removal method similar to a detergent containing a surfactant.
- An object of the present invention is to provide a semi-permanently excellent antifouling property on the surface, especially antifouling property against dirt containing an oily component, irrespective of the use environment such as indoor and outdoor, and also provided with abrasion resistance.
- An object of the present invention is to provide an antifouling material, a method for producing the same, and a coating composition and an apparatus therefor.
- a first aspect of the present invention is a stain-proofing material having a substrate and an inorganic coating substantially consisting of an amorphous metal oxide.
- the present invention relates to a coating composition for forming an antifouling inorganic film on a substrate surface, which is used for producing the above antifouling material, comprising a solvent and a solute.
- the solute is an alkali silicate, an alkali aluminum
- a coating composition comprising, as a main component, at least one selected from the group consisting of alkali zirconate, alkali borate, alkali phosphate and alkali phosphonate.
- the present invention provides a method for applying the coating composition to a substrate surface, heating the substrate, and forming an application layer of the coating composition on the surface of the substrate.
- the present invention provides an application unit for applying the coating composition on a substrate surface, and rapidly heating the substrate to form an application layer of the coating composition on the substrate surface.
- An apparatus for producing an antifouling material comprising at least heating means for fixing the film as an antifouling inorganic film.
- FIG. 1 is a conceptual diagram of an inorganic coating according to an embodiment of the present invention.
- FIG. 2 is an explanatory diagram of a method for producing an antifouling material according to the present invention.
- (A) is the state before the heat treatment
- (b) is the state after the heat treatment.
- the coating composition layer 2a applied to the substrate 1 becomes a thin film 2b that imparts multiple functions to the substrate 1 by heat treatment.
- FIG. 3 is an explanatory diagram of a method for producing an antifouling material according to the present invention.
- (A) is the state before the heat treatment
- (b) is the state after the heat treatment.
- the layer 2a and the layer 4a of the coating composition applied to the substrate 1 become a thin film 2b that imparts multi-function to the substrate 1 by rapid heating, and the layer 4a has non-crosslinked oxygen.
- the layer 4b contributes to exhibiting hydrophilicity.
- FIG. 4 is an explanatory view of an apparatus for producing an antifouling material according to the present invention.
- the device shown in the figure is a device consisting of a molding device 5, a glaze device 6, and a baking device 7, which first produces so-called pottery as a base material, a coating composition coating device 8, a rapid heating device 9, and a cooling region 1.
- the apparatus according to the present invention comprising 0 is continuously provided, and further includes a transfer device 16 capable of continuously transferring the base material within each apparatus and between the apparatuses.
- FIG. 5 is a diagram schematically showing the structure of the rapid heating device 9 in FIG.
- the rapid heating device 9 holds the heating element 21, a heat-resistant material 22 that covers the heating element and forms a heating space, and a base material 23 to be heated in the heating space and in the direction of arrow A in the figure.
- Transport means 16 for transporting the substrate to the heating space; and a carry-in port 24 and a carry-out port 25 for carrying the substrate into and out of the heating space.
- FIG. 6 is a diagram showing an apparatus provided with a preheating device 11 for preheating the substrate and a drying device 12 for drying the substrate on which the coating composition has been applied, before applying the coating composition. is there.
- FIG. 7 is a schematic diagram of a method for measuring the contact angle of salad oil in water on an inorganic coating according to an embodiment of the present invention.
- FIG. 8 is a graph showing the results of Example C-11. The potassium ion elution test was performed on a tile applied with potassium silicate heat-treated at 150 ° C., 350 ° C., or 550 ° C. It is shown.
- FIG. 9 is a graph showing the results of Examples C-12 and C-13 and Comparative Example C-11. Measurement of the contact angle of salad oil in water on potassium silicate applied tiles heat treated at 150 ° C, 350 ° C, 450 ° C, 550 ° C, or 800 ° C It is a figure showing the result of thermogravimetry.
- the antifouling material of the present invention has a substrate and an outermost layer of an inorganic coating substantially consisting of an amorphous metal oxide.
- the functions of the antifouling material of the present invention include various functions, for example, hydrophilicity, antifouling properties, antifogging properties, antistatic functions, and the like. By exerting synergistic effects, better antifouling properties can be obtained.
- the substrate used in the present invention can be a metal, an inorganic material, an organic material, or a composite material thereof.
- an interior material, an exterior material, a tile, a sanitary ware, tableware, a calcium silicate sheet, and a cement extrusion can be used.
- Building materials such as molded plates or ceramic substrates, semiconductors, etc. New ceramics, insulators, glass, mirrors, wood, resin, etc.
- a base material having a surface glaze layer formed on a ceramic body it is preferable to use a base material having a surface glaze layer formed on a ceramic body.
- the preferred range of the composition of the surface glaze layer is as follows. That is,
- T I_ ⁇ tetravalent metal oxides such as 2: 25 to 90 wt%
- Divalent metal oxides such as Mg ⁇ , CaO, ZnO, and Ba ⁇ 0.1
- ⁇ ⁇ ⁇ Other components include fluoride, phosphorus-containing material, Mo compound, V compound, Sb compound, W compound, etc .: 0.1 to 70% by weight,
- the inorganic coating in the present invention is the outermost layer substantially composed of an amorphous metal oxide, and contains an alkali metal and a non-crosslinked oxygen in an amount effective to exhibit a desired antifouling property. It contains.
- the antifouling property of the material according to the present invention can be evaluated by an exhaust gas cleaning test using the diffuse reflectance of the surface as an index.
- the material according to the present invention has an antifouling property that satisfies the criterion of 75% or more, preferably 80% or more, more preferably 90% or more in terms of recovery of diffuse reflectance.
- the sample to be evaluated is subjected to a process of attaching dirt using exhaust gas and a cleaning process using running water, and the diffuse reflectance of the sample surface before and after these processes is measured.
- This is a test to evaluate the antifouling property of a sample by measuring the change in color difference and color difference. Specifically, the test is performed as follows.
- a sample whose surface diffuse reflectance has been measured in advance is placed in a vessel directly connected to the exhaust pipe of a diesel vehicle, and exhaust gas is introduced. Introduce the exhaust gas until the color difference on the sample surface reaches about 20 or the diffuse reflectance becomes 55% or less, and forcibly attach the exhaust gas to the sample surface.
- the tiles are washed with running water. Washing with running water is performed by sprinkling about 400 cc Zm 2 on the tile surface.
- the diffuse reflectance and color difference of the obtained washed sample are measured.
- the diffuse reflectance refers to the ratio of the diffused light to the incident light on the sample surface, and is a value indicating the brightness of the surface color.
- the color difference is the amount of color change indicating the color of the sample surface using lightness and chromaticity.
- the diffuse reflectance recovery rate is a value obtained by calculating the change in the diffuse reflectance according to the following equation, and is an index of the cleaning recovery property of the sample.
- Recovery rate (%) diffuse reflectance after watering / initial diffuse reflectance X100
- the inorganic coating is fixed to the outermost layer of the antifouling material. As a result of being fixed, the inorganic coating has abrasion resistance.
- the degree of abrasion resistance in the present invention is not particularly limited as long as the surface is not deteriorated or damaged in a normal use state, and may be appropriately determined according to the use of the antifouling material.
- a predetermined pressure of an inorganic thin film surface of a sand eraser (e.g., l OOO gf Z cm 2 ( 9. 8 X 1 0 4 P a)) with good surface state after rubbing 1 0 0 times over If it is, it can be evaluated as good in abrasion resistance.
- a sand eraser e.g., l OOO gf Z cm 2 ( 9. 8 X 1 0 4 P a
- the durability and abrasion resistance of the coating surface may be further enhanced by combining Si 2 with AI 2 3 , Zr 0 2 , and B 2 0 3 while using Si 2 as a main component.
- the inorganic coating of the present invention has a sufficient film strength and, consequently, abrasion resistance because the three-dimensional network structure is appropriately developed.
- any of Li, Na, K, Rb, Cs, and Fr can be used, and one kind may be used alone, or two or more kinds thereof may be used in combination.
- K, Na or Li have stronger antifouling properties. It is considered that these alkali metals exhibit antifouling properties by a so-called builder effect.
- the alkali metal content in the inorganic coating is at least 10% by weight, based on the oxide, based on the composition of the coating surface.
- the oxide standard means that the content is calculated by converting the alkali metal ion in the inorganic coating into an alkali metal oxide.
- the amount of alkali metal can be calculated from the surface composition obtained by analyzing the surface layer of the inorganic coating by X-ray photoelectron spectroscopy (XPS).
- FIG. 1 shows a conceptual diagram of the inorganic coating of the present invention.
- the inorganic coating of the present invention has a two- or three-dimensional network structure of an oxide sufficient to exhibit abrasion resistance. Has metal and non-bridging oxygen.
- the non-crosslinked oxygen has the following meaning.
- Many of the coating compositions that are the raw materials of the inorganic coating are M— ⁇ H (where M represents a metal element, specifically, M is Si, Al, Zr, B, P, etc.) Is cross-linked by heating and polymerizes by forming M- ⁇ M bonds, and firmly adheres to the substrate surface to develop abrasion resistance. At this time, some M-OH remains in the hydroxyl group (M-MH) without forming an M-O-M bond, while being incorporated into the molecule of the formed polymer.
- M-OH is ionically bonded to a metal ion present in the coating composition and can be reversibly turned into M-OH M-0-X + (where X is an alkali metal ion). Represents metal).
- M—OH and M—0-X + Called non-crosslinked oxygen.
- This non-crosslinking oxygen is extremely compatible with water molecules, and even incorporates water molecules in the air onto the substrate surface. Furthermore, when water comes into contact with the substrate surface, the non-crosslinked oxygen is more likely to bind to water molecules than to the molecules that existed on the substrate surface earlier than water, so that the substrate surface becomes dirty first. The existing molecule and the water molecule are exchanged, whereby the molecular force previously existing on the substrate surface is dropped. Therefore, the presence of the non-crosslinkable oxygen on the surface of the substrate causes the surface of the substrate to exhibit extremely high hydrophilicity. As a result of this hydrophilicity, an advantage is obtained that, of course, lipophilic stains can be easily washed away with water, not to mention hydrophilic stains.
- the alkali metal on the surface of the inorganic film renders the oil-based stain water-soluble, and a part of the alkali metal is replaced by a replacement reaction with calcium ions and the like contained in water and the like, resulting in a builder effect. . It is thought that this makes it easier to remove dirt deposited on the surface of the inorganic coating.
- the non-crosslinked oxygen greatly contributes to the hydrophilicity
- the Alkyri metal makes the oily dirt water-soluble, and the builder effect prevents the re-adsorption of the dirt on the coating surface. It is thought that the anti-fouling property of the steel has been dramatically improved. Furthermore, the present inventors have found that when formed on the glaze layer, the antifouling properties are more significantly improved. These suggest that there is some synergistic effect between the inorganic coating and the underlying glaze layer.
- Non-crosslinked oxygen that is ionically bonded to an alkali metal ion can also be detected by photoelectron spectroscopy, but simply, when immersed in warm water at 50 ° C for 24 hours Approximate content can be measured by the amount of alkali metal eluted.
- the alkali metal elution rate from the inorganic coating when immersed in warm water at 50 ° C. for 24 hours is preferably 0.001 to 80%, more preferably 20 to 80%. is there. Within such a range, even when the amount of M-OH is small, a sufficient amount of M-0-X + is present, so that higher hydrophilicity and thus excellent antifouling property can be obtained.
- M- ⁇ H cross-links develop M-O-M bonds to ensure abrasion resistance, and a sufficient amount of non-cross-linked oxygen (M-0-X +) and suitable in the network structure Alkali metal ion X + presents excellent antifouling properties semipermanently. Can be maintained.
- the hydroxyl group (M- ⁇ H) can be determined by measuring the change in weight in the temperature range of weight loss due to dehydration between hydroxyl groups by thermogravimetric analysis (TG). it can. It can also be measured by differential thermal analysis (DTA). Hydroxyl groups may be detected by infrared spectroscopy or infrared absorption analysis. The amount of the hydroxyl group in the non-crosslinked oxygen is appropriately determined so that sufficient antifouling property and abrasion resistance can be obtained.
- TG thermogravimetric analysis
- DTA differential thermal analysis
- the contact angle of oil (for example, oleic acid) in water in the inorganic coating is preferably at least 100 °, more preferably at least 120 °.
- oil for example, oleic acid
- Such a state is realized by an excellent mouth-opening effect caused by the formation of a hydrophilic and oil-repellent microstructure by the supply of water in the inorganic coating.
- combustion products such as carbon black and diesel particulates and tire abrasion powder are basically hydrophobic, and therefore are less likely to adhere to the surface of the inorganic coating.
- the contact angle of oil (for example, oleic acid) in water is greater than 140 °
- the amount of oily dirt that has adhered is as small as water spray and the water level is small. This allows for quick cleaning. Accordingly, inorganic coatings having a contact angle of oil in water of more than 140 ° are more excellent in oily dirt cleaning properties.
- the contact angle of the oil (eg, oleic acid) in water is greater than 120 ° after immersion in warm water at 50 ° C for 6 hours.
- the center line average roughness (R a) of the surface of the inorganic coating is preferably set to R a ⁇ 500 nm, and more preferably, R a is 10 O nm.
- the average distance between particles (S m) is preferably 1 to S m and 500 nm.
- center line average roughness (Ra) means that a portion having a measurement length of 1 is extracted from a roughness curve in the direction of the center line, and the center line of the extracted portion is defined as the X axis and the vertical magnification.
- ⁇ ⁇ (X)
- the measurement of the center line average roughness Ra is performed according to the definition and display according to JIS-B0601 (1994), and the stylus type surface roughness conforming to JIS-B0651 (1996). is performed by the measuring device these JIS standards;. from the Japanese Industrial standards (Japan home Akasaka, Minato-ku, Tokyo 4 one 1 one 24), Ru readily available der with its English translation.
- the thickness of the surface layer is preferably 5 m or less, more preferably 0.01 to 5 m. With such a thickness, sufficient transparency can be ensured and the design can be improved, and at the same time, stains such as permeable dyes and black ink are hardly permeated, and the antifouling effect is improved.
- the charging half-life of the surface is preferably set to 10 seconds or less.
- the surface of the inorganic coating adsorbs moisture in the atmosphere and is less likely to be electrostatically charged, and thus has the advantage that it is difficult to electrostatically adsorb floating dust.
- the ⁇ potential when immersed in the water of ⁇ 7 is negative. This makes it difficult for bacteria and oily stains that are negatively charged in water to adhere. .
- the surface ⁇ is preferably greater than 7.
- ⁇ is on the alkaline side, oily dirt is less likely to fit into the surface, weakens adhesion, and improves the ability to wash away due to rainfall.
- the heat of wetting of water on the surface of the inorganic coating is Preferably, the heat of wetting of the tile before formation is 1 erg Z cm 2 or more higher. This makes it easier for water to be attracted to the surface, improving hydrophilicity and improving oil repellency in the presence of water.
- the surface layer is preferably transparent. This maintains the design of the base.
- the inorganic coating may further contain a metal oxide having a photocatalytic function to further impart various properties (for example, hydrophilicity, bactericidal property, etc.) by photoexcitation.
- a metal oxide having a photocatalytic function to further impart various properties (for example, hydrophilicity, bactericidal property, etc.) by photoexcitation.
- photocatalytic metal oxide, T i 0 2 is appropriately illustrated.
- an antibacterial component may be added to the inorganic coating. This prevents contamination by fungi, molds and algae.
- silver, copper, zinc or the like can be suitably used as the antibacterial component.
- a base material on which a glaze layer containing a particulate matter and / or a transparent thin film layer is formed on a substrate may be used.
- a base material on which a glaze layer containing a particulate matter and / or a transparent thin film layer is formed on a substrate may be used.
- Examples of such a base include outdoor tiles and interior tiles.
- the particulate matter examples include Si, Al, Fe, Ti, Mg, Ca, Zr, Zn, Co, Mn, Cr, Cu, Ag, Pb, It is a substance containing an element such as Ni, and specific examples include pigment particles, emulsifier particles, and glaze raw material particles that remain without being dissolved in the glass component.
- Exterior tiles include exterior tiles, pavement tiles, and tunnel interior tiles.
- the inorganic coating of the present invention By forming the inorganic coating of the present invention on tiles containing unmelted particulate matter such as zircon and silica in the glaze present on the substrate, various types of exterior dirt can be removed by the hydrophilicity of the surface. it can.
- the inorganic coating exhibits oil repellency when coexisting with water, it is possible to suppress the adhesion of dirt such as urban exhaust gas and soot containing oil.
- the surface of the inorganic coating is made hydrophilic and oil-repellent in an environment where water or water vapor is present, it is possible to prevent floating dust from being electrostatically adsorbed.
- Another preferred substrate includes interior tile.
- the inorganic coating of the present invention By forming the inorganic coating of the present invention on tiles containing unmelted particulate matter such as zircon and silica in the glaze present on the substrate, it is possible to remove various stains on the interior due to the hydrophilicity of the surface. it can.
- this inorganic coating exhibits oil repellency when coexisting with water, it is possible to suppress the adhesion of dirt such as salad oil and the like, and bathroom dirt and the like.
- the surface of the inorganic coating is made hydrophilic and oil-repellent in an environment where water or water vapor exists, it is possible to prevent floating dust from being electrostatically adsorbed.
- the coating composition for forming the inorganic coating of the present invention comprises a solvent and a solute.
- the solute is selected from the group consisting of alkali silicate, alkali aluminate, alkali zirconate, alkali carboxylate, alkali phosphate and alkali phosphonate as metal salts capable of forming an amorphous metal oxide upon heating as described below. It contains at least one kind as a main component.
- the solute include alkali silicates represented by the general formula Me 2 ⁇ ⁇ n Si 2 (where Me represents an alkali metal) (for example, water glass, potassium silicate, Lithium silicate, sodium silicate, and silica).
- the coating composition comprises at least one metal selected from the group consisting of Fr, Cs, Rb, K, Na, and Li.
- Preferred examples of the alkali metal silicate include potassium silicate, sodium silicate and lithium silicate. When used alone, lithium silicate exhibits good oil-based soil cleaning properties, but when used in combination with various types of alkali metal silicates, improves the water resistance, alkali resistance, and acid resistance of the produced inorganic coating. Can be done.
- an alkali metal silicate which can be obtained industrially in the form of an aqueous solution can also be used.
- an inorganic coating film having high adhesion can be formed on the substrate surface even at a low temperature of about 150 ° C. Further, it is possible to form an inorganic coating having a high concentration of non-crosslinkable oxygen or metal. Such an inorganic coating shows excellent cleaning properties for oily stains.
- the solvent may be one containing water as a main component, but is not particularly limited.
- the coating composition does not include a second component.
- the second component include Al, Ti, Si, Zr, Zn, Ce, Sn, Sb, Sr, Fe, Ci-, P, B, Co, Mn , Cu, Ag, Pt, Au, V, Ta, and Bi, and their metal compounds.
- Specific examples of these compounds include S I_ ⁇ 2, S I_ ⁇ 3, S i (OH), A 1 (OH) 3, T i C l 4, T i (OC 3 H 7) 4 , etc. .
- the addition of these second components can provide the desired function. For example, hydrophilicity, wet heat high A 1 2 ⁇ 3 for water, such as T I_ ⁇ 2 is preferred.
- Ce having ultraviolet light self-deactivation is preferable for ultraviolet absorption
- Cu and Ag oxides are preferable for antibacterial properties.
- Alkali metal oxides are highly effective in preventing stains such as oil stains and are preferred. Addition of P, B, etc. is preferable because the durability of the antifouling material can be improved.
- the concentration of the alkali metal silicate in the coating composition is preferably 0.001% by weight to 35% by weight, more preferably 0.1% by weight, in terms of solid content. It ranges from 001% to 20% by weight. By being in the above range, a surface having good performance and good strength can be obtained. In addition, an antifouling material having a uniform and smooth surface and good gloss can be obtained.
- the coating composition comprises
- the coating composition comprises a surfactant.
- the addition of the surfactant makes it possible to apply the coating composition uniformly.
- the average crystallite diameter of the second component is preferably 10 Onm or less.
- the upper limit is preferably about 2 Onm or less, more preferably about 1 Onm or less.
- the lower limit is preferably about 111 m or more, and more preferably about 3 nm or more.
- the above coating composition is applied to a substrate.
- a method for applying such a coating composition methods such as spray coating, dip coating, flow coating, spin coating, mouth coating, brush coating, and sponge coating are preferably used. Available.
- the coating composition is preferably applied by spraying.
- the substrate is preheated before applying the coating composition.
- the preheating is performed by heating the surface of the substrate to 20 ° C to 400 ° C.
- the coating composition applied to the heated substrate surface is advantageous because it spreads uniformly and a uniform coating film can be obtained.
- the substrate to which the coating composition has been applied may be dried before the heat treatment.
- a large amount of heat is applied to the substrate by the heat treatment described below. If excess water or solvent components are present on the substrate, the smoothness of the substrate surface may be lost due to rapid evaporation of water or solvent components due to rapid temperature changes. Therefore, it may be desirable to remove excess water or solvent components in advance by drying. Drying may be performed by blowing or heating.
- FIG. 2 (a) schematically shows a state in which a coating composition layer 2a is applied to a substrate 1.
- FIG. The layer 2 a of this coating composition becomes a thin film 2 b that imparts multiple functions to the substrate 1 by the heat treatment described later, and the antifouling material 3 is obtained.
- the coating composition on a substrate surface in a laminated or multilayered manner. Specifically, coating compositions having the same or different compositions are prepared, and they are sequentially applied to the surface of the base material. Coating in a laminated or multilayered form is a so-called multi-layer coating, which enables uniform and even coating. (b) Heat treatment
- the substrate on which the coating composition has been applied as described above is subjected to a heat treatment.
- the heat treatment is performed by crosslinking hydroxyl groups (1 ⁇ ⁇ [— ⁇ H (M is, for example, S i)) in the coating composition to appropriately develop a three-dimensional network structure of 1 M— ⁇ —M— This is a process performed to fix an inorganic thin film having excellent antifouling properties and abrasion resistance on a substrate.
- the temperature of the heat treatment is preferably 100 to 800 ° C., more preferably 150 to 600 ° C., and still more preferably 150 to 500 ° C. ° C, most preferably from 200 to 500 ° C, but is not limited thereto.
- the film strength of the inorganic thin film is improved and an excellent abrasion resistance can be obtained by moderate development of the three-dimensional network structure of 1 M—O—M—.
- the presence of a sufficient amount of non-crosslinked oxygen M- ⁇ -X + and a sufficient amount of alkali metal ions X in the network structure enhances hydrophilicity and detergency. Improved antifouling properties are obtained. That is, it is considered that abrasion resistance and antifouling property can be realized in a well-balanced manner.
- the heat treatment time may be appropriately determined according to the heat treatment temperature, and is not particularly limited.
- the heat treatment is preferably performed by “rapid heating”.
- rapid heating refers to heating the coating composition on the substrate in such a manner that the amount of heat is distributed evenly, but the entire substrate is not heated to the same temperature as the surface. means. Therefore, it is preferable that the rapid heating is performed by applying heat in a concentrated manner only to the surface of the substrate.
- the time of the rapid heating is preferably about 2 to 60 seconds, more preferably 5 to 60 seconds.
- the heating temperature is kept substantially constant during the rapid heating.
- the atmosphere temperature at which the substrate is placed during rapid heating is preferably 100 ° C. to 100 ° C., more preferably 200 ° C. ° C to 100 ° C.
- the rapid heating has a heating value per unit area.
- the rapidly heated substrate is then cooled to the final antifouling material. According to a preferred embodiment of the present invention, this cooling may be performed rapidly.
- the heating time may be 1 to 60 minutes instead of the rapid heating.
- an inorganic coating excellent in antifouling property and abrasion resistance can be obtained at a lower temperature than the rapid heating.
- the ambient temperature is preferably set to 150 to 700 ° C.
- the heat of immersion of the inorganic coating in water after the heat treatment is preferably larger than that before the heat treatment.
- the heat of immersion in water includes the heat of hydration of ionic non-crosslinking oxygen (M-0-X +), the heat of adsorption caused by hydrogen bonding between hydroxyl non-crosslinking oxygen (M-OH) and water molecules, and the like. It is.
- M-0-X + ionic non-crosslinking oxygen
- M-OH hydroxyl non-crosslinking oxygen
- the heat of immersion of the inorganic coating in water is greater than the heat of immersion in oil.
- the hydrophilicity of water to the inorganic coating is greater than the adhesion of the oily component to the inorganic coating. Oily stains can be easily removed.
- Equipment for manufacturing antifouling materials According to the present invention, there is provided a preferred apparatus for carrying out the above-described method for producing an antifouling material.
- FIG. 4 is an explanatory view of an apparatus for producing an antifouling material according to the present invention.
- the apparatus shown in the figure is an apparatus in which an apparatus according to the present invention and an apparatus for manufacturing a base material are continuously arranged.
- the apparatus shown in the figure is composed of a molding device 5, a glaze device 6, and a baking device 7 that first produce so-called pottery as a base material, a coating composition coating device 8, a rapid heating device 9, and a cooling device.
- the apparatus according to the present invention comprising the region 10 is disposed continuously, and further includes a transfer device 16 capable of continuously transferring the base material within each device and between the devices.
- an apparatus for producing a substrate comprising the substrate forming apparatus 5, the glaze apparatus 6, and the firing apparatus 7 may be appropriately selected according to the substrate to which the method according to the present invention is applied, and may have another configuration.
- the apparatus according to the present invention includes not only an apparatus including a coating composition coating apparatus 8, a rapid heating apparatus 9, and a cooling area 10, but also a base material as shown in FIG. This is used to include equipment that can consistently produce antifouling materials. That is, a configuration in which a device including the coating composition coating device 8, the rapid heating device 9, and the cooling region 10 is disposed immediately downstream of the substrate manufacturing device is also included in the scope of the present invention. It is.
- the base material is formed by the forming device 5 in the figure and the glaze is applied by the glaze device 6, the base material is fired by the firing device 7.
- the substrate fired by the firing device 7 still has a high temperature. According to a preferred embodiment of the present invention, it is preferable that the coating composition is applied in a state in which the substrate is at a certain high temperature.
- the coating device 8 in the figure may be configured according to the method selected as the coating method.
- the apparatus when spray coating is selected, the apparatus includes a device for spraying the coating composition.
- FIG. 5 schematically shows the structure of the rapid heating device 9 in FIG.
- This rapid heating device 9 holds a heating element 21, a heat-resistant material 22 that covers the heating element and forms a heating space, and a base material 23 to be heated in the heating space and an arrow in FIG. It is basically composed of a transport means 16 for transporting the substrate in the direction A, and a carry-in port 24 and a carry-out port 25 for carrying the substrate into and out of the heating space.
- the heating element 21 is not particularly limited as long as it can rapidly heat the base material, and an electric heating element, a heating element that generates gas by burning gas or other fuel, or the like can be used. .
- rapid heating has a heating value per unit area of 120 MJ / m 2
- the heating is preferably performed by a heating means of h or more, and more preferably 400 MJ / m 2 -h or more. Therefore, it is preferable to use a heating element capable of generating these calories. Further, the distance from the heating element to the surface of the base material may be appropriately determined within a range in which a sufficient amount of heat for rapid heating is applied to the base material, but it is generally about 5 mm to 300 mm. Therefore, it is preferable that the heating element is fixed or movable so that the distance between the base materials is within the above range.
- the heating space of the rapid heating device be sufficiently insulated by the heat insulating material 22 and that the influence of heat loss from the carry-in port 24 and the carry-out port 25 be reduced.
- the carry-in port 24 and the carry-out port 25 may be always open as shown in FIG. 5, but may be configured to open and close as the base material is carried in and out.
- the length of the region that is kept substantially constant may be determined as appropriate, but will generally be between 5 cm and 30 m.
- the transport device 16 may have any configuration as long as the substrate can be held and transported in the heating space, but a belt conveyor or a roller conveyor is preferably used. According to a preferred embodiment of the present invention, it is preferable that the transfer device 16 is configured so that the heating space is not unnecessarily thermally partitioned so that heat transfer in the heating space is performed well. For example, it is preferable to use a heat-resistant multi-hole belt having a surface aperture ratio of 20% or more, a belt conveyor composed of a group of rollers, or a roller conveyor as the conveying means.
- the conveying means is a belt conveyor made of a heat-resistant mesh having a mesh of 50 mm ⁇ 50 mm or less, or a group of continuous heat-resistant rollers having a pitch of 1 mm or more and 30 O mm or less. It is preferable to use a roller conveyor.
- the cooling device 10 cools the rapidly heated substrate to room temperature.
- This device has a function of lowering the temperature of a substrate to room temperature by placing the substrate in a room temperature atmosphere. As long as the substrate has the function of lowering the temperature of the substrate to room temperature, this device The temperature of the substrate may be reduced by forcibly blowing air at room temperature or slightly higher or lower than room temperature to the substrate. However, rapid cooling may cause cracks or the like on the surface of the antifouling material. Therefore, it is desirable to perform rapid cooling within a range that does not cause such adverse effects.
- FIG. 6 shows an apparatus provided with a pre-heating device for pre-heating the substrate before application of the coating composition.
- the substrate is heated by this preheating device, and the temperature of the substrate surface can be raised to a temperature at which the coating composition can be uniformly applied.
- the device shown in FIG. 6 shows a configuration in which the preheating device 11 is provided before the coating device 8.
- the surface of the base material be heated to 20 ° C. to 400 ° C. by the preheating device.
- an apparatus consisting of a molding apparatus 5, a glaze apparatus 6, and a firing apparatus 7 for producing a base material shown in FIG.
- the base material fired by the sintering apparatus 7 still has a high temperature, it is necessary to: Generally, no heating device is required. Therefore, this preheating device will usually be required when a separate substrate is manufactured and the substrate does not have a sufficient temperature.
- the apparatus shown in FIG. 6 is provided with a drying apparatus 12 for drying the substrate on which the coating composition has been applied by the application apparatus 8 before the rapid heating apparatus 9.
- the drying device 12 has a blowing means or a heating means, and removes excess water or solvent components from the surface of the base material.
- the rapid heating device 9 and the cooling device 10 may be the same as those shown in FIG. Example]
- a coating composition was prepared by dispersing 0.1% by weight of potassium silicate, 0.1% by weight of lithium silicate, and 0.01% by weight of alumina in water. This coating The coating composition was spray-coated at a coating amount of 25 g / m 2 on the surface of a glass substrate heated to a surface temperature of 100 ° C. This glass substrate was placed in a roller hearth kiln and subjected to heat treatment at a furnace atmosphere temperature of 350 ° C. for 30 minutes to form an inorganic film on the glass.
- the contact angle of water on this inorganic coating surface is 15 degrees
- the contact angle of oil is 25 degrees
- the center line average roughness Ra is 20 nm
- the charging half-life is 0.3 seconds
- the ⁇ potential at pH 7 is minus 20. mV.
- An oil stain made of a mixture of carbon black and oil was dropped on the surface of the glass, and water was dropped from both sides of the line.This soiled substance floated on the surface of the water and was easily removed from the glass surface.
- Example 1 The same heat treatment as in Example 1 was performed except that no inorganic coating was formed on the glass substrate surface.
- the contact angle of water on this glass surface was 31 degrees
- the contact angle of oil was 22 degrees
- the center line average roughness Ra was 2 nm
- the charge half-life was 120 seconds
- the ⁇ potential at pH 7 was 2 mV minus.
- an oil stain mixed with carbon black and oil was dripped on the line, and water was dripped from both sides of the line. The oil stain adhered to the glass surface and was easily removed from the glass surface. Not removed.
- Example A-2 An oil stain mixed with carbon black and oil was dripped on the line, and water was dripped from both sides of the line. The oil stain adhered to the glass surface and was easily removed from the glass surface. Not removed.
- a mixture containing copper-doped alkali-dispersed titanium oxide sol and silver nitrate was irradiated with ultraviolet light using a BLB lamp to produce a titanium oxide sol in which silver ions were supported on a metal by photocatalytic reduction.
- 0.2% by weight of this titanium oxide sol and 0.4% by weight of potassium silicate were dispersed in water to prepare a coating composition.
- This coating composition was spray-coated on the surface of a glazed tile heated to a surface temperature of 120 ° C. at a coating amount of 25 gZm 2 .
- This glazed tile was subjected to a rapid heating treatment at 850 ° C in the furnace for 15 seconds to form an inorganic coating on the glazed tile.
- Example A-3 An inorganic coating was formed on the surface of the glazed tile in the same manner as in Example A-2, except that a coating composition containing no silicate was used. The inorganic coating thus obtained easily peeled off from the glazed tile surface. Comparative Example A-3
- Example A-2 The coating composition used in Example A-2 was spray-coated on the surface of the glazed mat tile in the same manner as in Example A-2.
- the glazed tile was subjected to a heat treatment in a furnace at an ambient temperature of 800 ° C. for 60 minutes in a Laura Haas kiln to form an inorganic coating on the glazed tile.
- Example A-3 The contact angle of water on this surface was 31 degrees, the contact angle of oil was 21 degrees, and the charging half-life was 15 seconds.
- Example 1 When the same oil stain as in Example 1 was dripped on the glazed tile surface and water was dripped from both sides of the line, the dirt material adhered to the surface and was not easily removed from the glass surface.
- a coating composition was prepared by dispersing 0.2% by weight of potassium silicate and 0.4% by weight of lithium silicate in water. This coating composition was spray-coated at a coating amount of 25 g / m 2 on the surface of glass heated to 100 ° C.
- the glass substrate was subjected to a heat treatment at 350 ° C. in a furnace for 30 minutes with a roller hearth kiln to form an inorganic film on the glass surface.
- this inorganic coating surface frictionally 1 0 0 times under a pressure of 1 0 0 0 gf / cm 2 in a sand eraser, no strange inorganic coating No change was observed, and it remained firmly adhered to the glass substrate.
- Comparative Example A-4 Comparative Example A-4
- An inorganic coating was formed on a glass substrate in the same manner as in Example A-3, except that the furnace atmosphere temperature in the heat treatment was set at 130 ° C.
- the furnace atmosphere temperature in the heat treatment was set at 130 ° C.
- the inorganic thin film was separated from the glass substrate. That is, it was confirmed that the adhesion between the inorganic thin film and the glass substrate was weak.
- Example A-4 An inorganic coating was formed in the same manner as in Example A-3, except that the furnace atmosphere temperature in the heat treatment was set to 800 ° C. When the surface of the inorganic film was rubbed 100 times with a sand eraser under a pressure of 1000 gf Zcm 2 , the inorganic thin film was peeled off from the glass substrate.
- Example A-4 the furnace atmosphere temperature in the heat treatment was set to 800 ° C.
- a coating composition 0.1% by weight of an alkali-dispersed titanium oxide sol and 0.4% by weight of lithium silicate were dispersed in water to prepare a coating composition.
- the surface of the inorganic coated calcium carbonate plate was subjected to corona discharge treatment, and the surface temperature was heated to 80 ° C., and then the above coating composition was spray-coated on the surface at a coating amount of 25 g / m 2 .
- This calcium carbonate plate was subjected to a rapid heating treatment at a furnace atmosphere temperature of 500 ° C. for 20 seconds to form an inorganic coating on the inorganic coating calcium carbonate plate.
- the contact angle of water on the surface of the inorganic coating was 1 degree, the contact angle of oil was 20 degrees, the charging half-life was 0.1 second, and the zeta potential at pH 7 was minus 25 mV.
- An oil stain mixed with carbon black and oil was dropped on the surface of the inorganic painted calcium silicate plate, and water was dropped from both sides of the wire. Easily removed from the surface of the inorganic painted calcium silicate plate.
- the inorganic coated calcium silicate plate had a photocatalytic function and had a decomposing function such as antibacterial property, antifouling property and deodorant property.
- the strength (hardness) of the inorganic coating formed on the surface of the inorganic coated calcium silicate plate was 4 or more in Mohs hardness, and it was a strong film having excellent abrasion resistance and chemical resistance.
- lithium silicate manufactured by Nippon Chemical Co., Ltd., trade name: lithium silicate 35
- a surfactant Emalgen 707, manufactured by Kao Corporation
- a glaze was applied to the surface of the obtained base by a glaze device 6. Subsequently, the tiles were fired by passing them through a porch Iraha kiln, which is a firing apparatus 7 set at a firing temperature of 1150 ° C, for 40 minutes to obtain tiles.
- the coating composition prepared above was spray applied to the surface of the tile.
- the coating amount was 20 gZm 2 . Since the temperature of the tile was as high as 150 ° C, excess water evaporated instantaneously, and only the solid content was evenly deposited on the tile surface, forming a thin film of about 0.5 m.
- the tiles were carried into a furnace, which is a rapid heating device continuously arranged in the firing device 7. Heating elements in the furnace top is arranged at a high density, the furnace atmosphere temperature is about from 800 to 1 000 ° C, heat is approximately per area of the furnace 1600 MJ / m 2 ⁇ h, heated area 30 cm x 150 cm. The time the tiles were placed in the furnace was about 30 seconds, and the time the tiles were placed under the heating element was about 10 seconds. As a result, the thin film formed on the tile surface was completely immobilized on the tile surface.
- the surface temperature of the tiles removed from the furnace had risen from 300 ° C to 350 ° C.
- the evening rolls were then introduced into a cooling system that cools the tiles by blowing cool air from above and below the tiles, and was cooled to 100 ° C to 150 ° C within 3m.
- the tile of the antifouling material thus obtained had high antifouling properties against oil stains, and had even higher hydrophilicity.
- the strength (hardness) of the thin film formed on the tile surface is 4 or more in Mohs hardness, and furthermore, it has excellent abrasion resistance and chemical resistance It was a strong film.
- Potassium silicate (Snowtex K, manufactured by Nissan Chemical Co., Ltd.) was dispersed in water to prepare a coating composition of 1% by weight of potassium silicate. Further, 1 part by weight of a 3% copper acetate aqueous solution was mixed with 100 parts by weight of the potassium silicate sol.
- Example 1 a large tile (0.9 mx i. 8 m) was prepared. That is, after the ceramic raw material is extruded and formed by the forming apparatus 5 of the apparatus shown in FIG. 4 to obtain a base, a glaze is applied to the surface of the base by the glazing apparatus 6, and the firing temperature as the firing apparatus 7 is 1150 ° C. After passing through the roller hearth kiln set for 3 hours, it was fired to obtain large tiles.
- the coating composition was spray-coated on the tile surface in the same manner as in Example 1.
- the application amount was 15 gZm 2 . Since the temperature of the sunset was as high as 80 ° C, excess water evaporated instantaneously, and only the solid content was uniformly deposited on the tile surface, forming a thin film of about 0.2.
- the tiles were carried into a furnace, which is a rapid heating device continuously arranged in the firing device 7. Heating elements in the furnace top is arranged at a high density, the furnace atmosphere temperature is about 8 0 0 ⁇ 1 0 0 0 ° C , a heat of about 1 6 0 OMJ Zm 2 ⁇ h per area of the furnace The heating area was 1.5 m ⁇ 28 m. The time that the tiles were placed in the furnace was about 60 seconds, and the time that the tiles were placed under the heating element was about 50 seconds. As a result, the thin film formed on the tile surface was completely immobilized on the tile surface. The surface temperature of the tiles removed from the furnace had risen to 200 ° (: ⁇ 250 ° C. The evening rolls were subsequently introduced into a cooling system that cools the tiles by spraying water, for 10 m. At 10 Ot: cooled to ⁇ 150 ° C.
- the tile of the antifouling material obtained in this way had antibacterial and algal-proof functions.
- the strength (hardness) of the thin film formed on the tile surface was 4 or more in Mohs hardness, and it was a strong film with excellent wear resistance and chemical resistance.
- a lithium silicate boric acid mixture manufactured by Nippon Chemical Co., Ltd., trade name: SLN55
- a cerium oxide sol manufactured by Taki Chemical Co., Ltd., trade name: AS-520
- a glass plate having a size of lmX lm was prepared as a substrate.
- the surface temperature of the glass was heated to 40 ° C by a preheating device set at 40 ° C. Thereafter, the coating composition was spray applied to the glass surface. Coating cloth amount was 5 gZm 2. Since the glass temperature is as low as 40 ° C and the water is difficult to evaporate, it is dried at 100 ° C after coating and laminated by repeating coating and drying three times, and only the solid content is on the glass surface.
- the glass was carried into a furnace, which is a rapid heating device continuously arranged in a preheating device. The heating elements in the upper part of the furnace were arranged at a high density, and the atmosphere temperature in the furnace was about 550 ° C. The time for which the glass was placed in the furnace was about 2 seconds, and as a result, the thin film formed on the glass surface was completely fixed on the glass surface.
- the surface temperature of the glass removed from the furnace had risen from 250 ° C to 350 ° C.
- the glass was subsequently introduced into a cooling system that cooled the glass by forced air blowing, 50 for 3 m. Cooled to C-150 ° C.
- the obtained antifouling material had high surface smoothness, high ultraviolet absorbing ability, and excellent hydrophilicity and antifouling properties.
- the heat of wetting of the thin film with water was evaluated, it was as high as 500 e 1 -g Z cm 2 .
- the hardness (Mohs altitude) of the thin film formed on the glass surface was as high as 4 or more, and it was a strong film with excellent wear resistance and chemical resistance.
- An aqueous solution containing 0.5 wt% of potassium silicate was prepared as a coating composition.
- This coating composition was sprayed onto the tile surface heated to a surface temperature of 100 at a coating amount of 25 g Zm 2 .
- This tile was subjected to a heat treatment at a furnace atmosphere temperature of 150, 350 or 550 ° C. for 30 minutes by using a roller-hard heart kiln to form an inorganic coating on the tile surface.
- a cylinder with a diameter of 4 cm was fixed on these inorganic coatings, 30 g of distilled water was introduced into the cylinder, and the cylinder was allowed to stand at an ambient temperature of 50 ° C for 2 to 24 hours.
- the amount of potassium eluted at the standing time of 2, 6, and 24 hours was quantified by atomic absorption spectrometry.
- Figure 7 shows the evaluation results.
- this membrane contains a large amount of non-crosslinked oxygen (particularly ion-bonded M- ⁇ -X +) due to moderate development of the three-dimensional network structure. This is considered to be high in hydrophilicity and excellent in antifouling properties. That is, it has the best balance between antifouling property and abrasion resistance.
- the contact angle of oil in water was measured as an index of the oil-based dirt washability on the inorganic coating in the present invention.
- the same coating composition as in Example C-11 was spray-sprayed onto the tile surface heated to a surface temperature of 100 ° C. at an application amount of 25 g Zm 2 .
- the tile was heat-treated with a roller hearth kiln at a furnace atmosphere temperature of 150, 350, or 450 ° C. for 30 minutes to form an inorganic coating on the tile surface.
- Measurements of the contact angle of salad oil in water at 0 o (w) on each inorganic coating were performed.
- Figure 8 shows a schematic diagram of the measurement of the contact angle of oil in water. As shown in FIG.
- the oil 36 is dropped on the inorganic film 34 formed on the base material 33, and the glass container is passed through the pedestal 35 so that the oil-adhering surface comes down. It was immersed in water 32 in 31. At this time, the oil contact angle was measured. The contact angle was measured using a CA-XI50 contact angle meter manufactured by Kyowa Interface Science Co., Ltd. Salad oil, a widely used edible oil, oleic acid containing various animal and vegetable oils as main components, and n-octane as a hydrocarbon oil were used as oils. Comparative Example C—_l
- Example C-11 The same coating composition as in Example C-11 was spray-coated at a coating amount of 25 g Zm 2 on the surface of a dinner heated to a surface temperature of 100 ° C.
- the tile was heat-treated with a roller hearth kiln at a furnace atmosphere temperature of 800 ° C. for 30 minutes to form an inorganic coating on the tile surface.
- the contact angle ⁇ ⁇ ⁇ o (w) of the salad oil in water on each inorganic coating was measured.
- Example C-1 After the potassium silicate was dried at 100 ° C. for 2 days, thermogravimetric analysis was performed using TGZD TA320 by Seiko Electronic Industry Co., Ltd. The measurement temperature range was set at 800 ° C from room temperature, and the heating rate was set at 2 ° C / min.
- Example C-12 All of the contact angles in water in Example C-12 were as high as 120 ° or more, indicating excellent oily soil cleaning properties.
- the evaluation result in Comparative Example C-11 was a small underwater contact angle of 90 ° or less. From around the heat treatment temperature of 500 ° C, a sharp decrease in the contact angle in water was observed on the high temperature side. In the case of the inorganic coating described in Comparative Example C-11, it was not possible to remove oil stains adhered to the inorganic coating only by washing with water.
- the thermogravimetric analysis results of the caiodic acid realm in Example C-13 show that the sample undergoes a two-stage weight loss with increasing heat treatment temperature.
- the weight loss on the low temperature side is due to the dehydration of the physically adsorbed water of potassium silicate
- the weight loss on the high temperature side is due to the dehydration and the structural change of the chemically adsorbed water.
- a structural change of silica silicate dehydration due to condensation of hydroxyl groups remaining in the sample is mainly considered. It is expected that the three-dimensional network structure of Siri force will develop through such structural changes.
- Example C-12 and Comparative Example C-11 The temperature range in which the contact angle value of the salad oil in water significantly decreased in Example C-12 and Comparative Example C-11 was similar to the temperature reduction temperature range on the high temperature side in the thermogravimetric analysis of Example C-3. Yes, it is.
- thermogravimetric analysis and the dependence of the contact angle in water on the heat treatment temperature suggest that the structure of the silicic acid skeleton in the Alkali metal silicate greatly contributes to the excellent oil-based soil cleaning performance. I have. That is, it is considered that the inorganic coating according to the present invention expresses excellent oily soil cleaning properties by synergistic action of the alkali metal and the non-crosslinked oxygen atom.
- Example C-1 4
- a coating composition containing an alkali metal silicate having the composition shown in Table 1 was prepared.
- Tableware heated to a surface temperature of 100 ° C with these coating compositions The surface was spray-coated at a coating amount of 25 g / m 2 .
- the tableware was subjected to a heat treatment at 350 ° C. for 30 minutes in a furnace with a roller-Hirschirn to form an inorganic film on the tableware surface.
- the cleaning properties of the oily stains on these inorganic coatings were evaluated.
- the warm water immersion corresponds to the inorganic coating after repeated washing.
- the contact angle (0 w) and the contact angle of the salad oil in air (0) were measured.
- a coating composition was prepared by dispersing potassium silicate having the composition shown in Table 2 and an anatase-type titanium oxide sol in water. These coating compositions were spray-coated on the tile surface heated to a surface temperature of 100 ° C. at a coating amount of 25 g Zm 2 . This tile was subjected to a heat treatment at a furnace atmosphere temperature of 350 ° C. for 30 minutes by using a roller and a hearth kiln to form an inorganic coating on the tile surface.
- Example C_4 The same evaluation as in Example C_4 was performed on these inorganic coatings.
- titanium oxide is an oxide semiconductor having a photocatalytic function, and is known to exhibit superhydrophilicity and strong oxidizing power by photoexcitation. Therefore, excellent antifouling properties can be obtained in an environment exposed to sunlight.
- the evaluation was performed without performing any light irradiation for exciting titanium oxide.
- a coating composition was prepared by dispersing a metal silicate having the composition shown in Table 3 in water. These coating compositions were spray applied to the tile surface heated to a surface temperature of 100 ° C. at a coverage of 25 g Zm 2 . This tile was subjected to a rapid heat treatment at a furnace atmosphere temperature of 850 ° C. for 15 seconds to form an inorganic film on the tile surface. These inorganic coatings were evaluated in the same manner as in Example C-14. Table 3
- Comparative Example C-2 A coating composition was prepared by dispersing the Alkali metal silicate with the composition shown in Table 4 in water. These coating compositions were sprayed onto the tile surface heated to a surface temperature of 100 ° C. at a coating amount of 25 g Zm 2 . This tile was subjected to a heat treatment at 800 ° C. for 30 minutes in a furnace with a roller hearth kiln to form an inorganic coating on the tile surface. The same evaluation as in Example C-14 was performed on these inorganic coatings. Table 4
- Example C-14 The same evaluation as in Example C-14 was performed on an unprocessed tile having no inorganic film formed on the surface.
- An alkali metal silicate having the composition shown in Table 6 was dispersed in water to prepare a coating composition. These coating compositions were spray applied to the tile surface heated to a surface temperature of 100 ° C. at a coating amount of 25 g / m 2 .
- the tiles were subjected to a heat treatment in a furnace at a temperature of 35 (TC for 30 minutes) using a roller heater and a kiln to form inorganic coatings on the tile surfaces.
- the contact angles of oleic acid and n-octane in water before and after immersion in water for 6 hours were measured, and oleic acid and n-octane were used as oily stains to evaluate detergency.
- Example C-17 The results of Example C-17 were as shown in Table 7 7
- composition shown in Table 8 various alkali metal silicates alone, or even a T I_ ⁇ 2 were dispersed in water to prepare a coating composition.
- SLN73 manufactured by Nippon Chemical Industrial Co., Ltd. was also used as an alkali metal silicate containing a plurality of alkali metal species and also containing boron.
- These coating compositions were spray-coated on the tile surface heated to a surface temperature of 100 ° C. at a coating amount of 25 g_m 2 .
- This tile was heat-treated with a roller hearth kiln at a furnace atmosphere temperature of 350 ° C. for 30 minutes to form an inorganic coating on the tile surface.
- the contact angle (0 o (w)) of the salad oil in water before and after immersion in warm water at 50 ° C for 6 hours was measured, and the detergency was evaluated using oily dirt as the salad oil. Further, the strength of the inorganic coating was evaluated by a sliding test before and after the immersion in the warm water. In the sliding test, the surface state after rubbing 100 times with a sand eraser at a pressure of 1000 gf / cm 2 was evaluated by A to D.
- a coating composition was prepared by dispersing 3% by weight of alkali silicate (Nissan Chemical Lithium Silicate 35) in water. This coating composition was applied to the surface of a 15 cm square glazed tile (Tokyo Kikai, AB02E01) by a spray coating method. The tiles were fired at 850 ° C for 10 seconds at an ambient temperature of 300 to achieve a base coat surface temperature of 300. C. At this time, on the surface of the prepared glazed tile, the presence of zircon and unmelted silica particles in the glass layer was confirmed by EPMA analysis. It was clear. A film made of lithium silicate was formed thereon, and a coated sample was obtained. The thickness of the film was 3.
- alkali silicate Nasan Chemical Lithium Silicate 35
- the contact angle of the sample immediately after firing with water was measured using a contact angle measuring instrument (manufactured by Kyowa Interface Science Co., Ltd., model CA-X150, low-angle side detection limit of 1 degree).
- the contact angle with water was 5 degrees. there were. This contact angle was measured 30 seconds after a water drop was dropped on the sample surface from the micro syringe. After leaving the sample in place for one week, the contact angle with water was still 5 degrees. Next, a drop of salad oil was dropped on the tile and immersed in water. After 30 seconds, the contact angle of the oil in water was measured. The reading of the measuring instrument was 140 degrees, and the surface of the sample showed oil repellency in water.
- the ⁇ potential at ⁇ 7 was ⁇ 2 OmV, and the charging half-life was 8 seconds.
- Alkali silicate Nahon Kagaku 1K potassium silicate
- silica sol Nasan Kagaku Snowtex Co., Ltd.
- alumina sol Nasan Chemical AS520 0.001 weight% are dispersed in water.
- a coating composition was prepared. This coating composition was applied to the surface of a 15 cm square glazed tile (AB02E01) by the spray coating method. The tile was fired at a temperature of 400 ° C. for 40 minutes to obtain a sample covered with a coating made of Alkali resilicate.
- the initial diffuse reflectance of the sample surface was measured using a portable reflectometer (product name: PG-3D, manufactured by Nippon Denshoku Industries Co., Ltd.). This sample was placed in a container directly connected to the exhaust pipe of a diesel vehicle, and exhaust gas was introduced. Exhaust gas was introduced until the color difference on the sample surface reached about 20 or the diffuse reflectance was 55% or less, and the exhaust gas was forcibly attached to the sample surface. The engine rotation speed at this time was about 300 rpm, and the time required for adhesion was about 10 minutes.
- the tiles were washed by watering. Here, room temperature tap water was used as the washing water, the flow rate was about 400 cc Zm 2 with respect to the tile surface, and the water pressure was about 0.6 kgf / cm.
- the diffuse reflectance, the recovery rate of the diffuse reflectance, and the color difference were measured for the washed sample thus obtained.
- the antifouling material of the present invention has excellent antifouling properties.
- the criteria for the antifouling property are preferably set such that the diffuse reflectance after washing is 70% or more, the diffuse reflectance recovery rate is 90% or more, and the color difference is 2 or less. More preferably, some of the above samples also met this criterion.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Structural Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Wood Science & Technology (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/807,801 US6673433B1 (en) | 1998-10-19 | 1999-10-19 | Stainproof material and method for manufacturing the same, and coating composition and apparatus thereof |
AU61250/99A AU6125099A (en) | 1998-10-19 | 1999-10-19 | Stainproof material and method for manufacturing the same, and coating composition and apparatus therefor |
EP99947973A EP1136527A4 (en) | 1998-10-19 | 1999-10-19 | Stain-resistant material and method for producing the same, coating composition and device therefor |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP31684798 | 1998-10-19 | ||
JP10/316847 | 1998-10-19 | ||
JP1489699 | 1999-01-22 | ||
JP11/14896 | 1999-01-22 | ||
JP7252799 | 1999-03-17 | ||
JP11/72527 | 1999-03-17 | ||
JP22325599 | 1999-08-06 | ||
JP11/223255 | 1999-08-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000023528A1 true WO2000023528A1 (fr) | 2000-04-27 |
Family
ID=27456295
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1999/005766 WO2000023528A1 (fr) | 1998-10-19 | 1999-10-19 | Materiau resistant aux salissures, procede et dispositif de production et composition de revetement |
Country Status (6)
Country | Link |
---|---|
US (1) | US6673433B1 (ja) |
EP (1) | EP1136527A4 (ja) |
CN (2) | CN1198886C (ja) |
AU (1) | AU6125099A (ja) |
TW (1) | TWI230186B (ja) |
WO (1) | WO2000023528A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002080829A (ja) * | 2000-09-07 | 2002-03-22 | Toto Ltd | 親水性部材、その製造方法、およびその製造のためのコーティング剤 |
WO2006092941A1 (ja) * | 2005-03-03 | 2006-09-08 | Cleanup Corporation | 水使用住宅設備機器の製造方法および水使用住宅設備機器 |
JP2008525188A (ja) * | 2004-12-28 | 2008-07-17 | カウンシル オブ サイエンティフィック アンド インダストリアル リサーチ | 光触媒による汚れの自動洗浄工程 |
JP6043889B1 (ja) * | 2016-09-16 | 2016-12-14 | 日新製鋼株式会社 | 塗装金属板 |
KR20220063748A (ko) * | 2020-11-10 | 2022-05-17 | (주)엘엑스하우시스 | 도기 및 이의 제조방법 |
Families Citing this family (59)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6830785B1 (en) * | 1995-03-20 | 2004-12-14 | Toto Ltd. | Method for photocatalytically rendering a surface of a substrate superhydrophilic, a substrate with a superhydrophilic photocatalytic surface, and method of making thereof |
JP5181157B2 (ja) * | 1999-09-30 | 2013-04-10 | ハミダ・フォー・ライフ・ベスローテン・フェンノートシャップ | マイクロエレクトロニックアレイ上の生体分子付着部位 |
US6303082B1 (en) * | 1999-12-15 | 2001-10-16 | Nanogen, Inc. | Permeation layer attachment chemistry and method |
CN1246257C (zh) * | 2000-10-19 | 2006-03-22 | 株式会社伊奈 | 防污处理方法及具有玻璃层的制品、强化陶瓷器及其制造方法、具有玻璃层的制品及其制造方法 |
JP2002301378A (ja) * | 2001-04-04 | 2002-10-15 | Mitsui Eng & Shipbuild Co Ltd | 光触媒モジュール、その製造方法、光触媒反応装置 |
US6960298B2 (en) * | 2001-12-10 | 2005-11-01 | Nanogen, Inc. | Mesoporous permeation layers for use on active electronic matrix devices |
FR2855479A1 (fr) * | 2003-06-02 | 2004-12-03 | Valeo Systemes Dessuyage | Agencement pour le nettoyage d'un panneau vitre par association de revetements photocatalytique et hydrophile |
US20050005956A1 (en) * | 2003-07-11 | 2005-01-13 | Maytag Corporation | Fluorine gas treatment of washing machine parts |
CN101767039B (zh) * | 2003-10-16 | 2015-04-01 | 陶氏技术投资有限责任公司 | 用于烯化氧制备的具有提高稳定性、效率和/或活性的催化剂 |
US8906460B2 (en) * | 2004-01-30 | 2014-12-09 | Cristal Usa Inc. | Composition for use as NOx removing translucent coating |
WO2005083013A1 (en) * | 2004-01-30 | 2005-09-09 | Millennium Chemicals | Coating composition having surface depolluting properties |
AU2004316444B2 (en) * | 2004-01-30 | 2010-07-01 | Tronox Llc | Composition for use NOx removing translucent coating |
US20080118770A1 (en) * | 2004-04-06 | 2008-05-22 | Lg Electronics, Inc. | Method for Manufacturing Ultra-Hydrophilic Thin Film Coated Metal Product, and Ultra-Hydrophilic Thin Film Coated Metal Product |
WO2005103172A2 (en) * | 2004-04-15 | 2005-11-03 | Avery Dennison Corporation | Dew resistant coatings |
DE102004024630B3 (de) * | 2004-05-18 | 2005-12-29 | Schollglas Holding- und Geschäftsführungsgesellschaft mbH | Verfahren zur Herstellung einer antibakteriellen anorganischen Beschichtung auf einem Flachglas sowie danach hergestelltes beschichtetes Flachglas |
WO2006030250A2 (en) * | 2004-09-14 | 2006-03-23 | Millennium Chemicals, Inc. | Composition useful for providing nox removing coating on material surface |
US20060166285A1 (en) * | 2005-01-26 | 2006-07-27 | Jainamma Krotz | Charged permeation layers for use on active electronic matrix devices |
FR2881844B1 (fr) * | 2005-02-09 | 2007-04-13 | Saint Gobain | Structure diffusante a proprietes d'absorption dans l'ultraviolet |
US20080233408A1 (en) * | 2005-03-03 | 2008-09-25 | Katsutoshi Obata | Method for Manufacturing Water-Using Household Equipment and Water-Using Household Equipment |
US8344238B2 (en) * | 2005-07-19 | 2013-01-01 | Solyndra Llc | Self-cleaning protective coatings for use with photovoltaic cells |
US7901660B2 (en) * | 2005-12-29 | 2011-03-08 | The Board Of Trustees Of The University Of Illinois | Quaternary oxides and catalysts containing quaternary oxides |
WO2008005055A2 (en) * | 2005-12-29 | 2008-01-10 | The Board Of Trustees Of The University Of Illinois | Nanoparticles containing titanium oxide |
AU2006335491B2 (en) * | 2006-01-13 | 2011-01-27 | Nbc Meshtec Inc | Composite material having antifouling property |
US7687103B2 (en) * | 2006-08-31 | 2010-03-30 | Gamida For Life B.V. | Compositions and methods for preserving permeation layers for use on active electronic matrix devices |
US20080097018A1 (en) | 2006-10-18 | 2008-04-24 | John Stratton | Depolluting coating composition |
WO2008136866A2 (en) * | 2006-11-27 | 2008-11-13 | Micropyretics Heaters International, Inc. | Antimicrobal materials and coatings |
TWI497019B (zh) * | 2007-01-30 | 2015-08-21 | Sumitomo Osaka Cement Co Ltd | 烹調器具及其製造方法 |
US8017247B2 (en) * | 2007-03-30 | 2011-09-13 | Alcoa Inc. | Self cleaning aluminum alloy substrates |
EP2172438A1 (en) * | 2007-05-31 | 2010-04-07 | Sumitomo Osaka Cement Co., Ltd. | Sanitary ware and process for production thereof |
US8154032B2 (en) * | 2007-07-23 | 2012-04-10 | Seiko Epson Corporation | Electrooptical device, electronic apparatus, and method for producing electrooptical device |
US7910220B2 (en) * | 2007-07-25 | 2011-03-22 | Alcoa Inc. | Surfaces and coatings for the removal of carbon dioxide |
US9358502B2 (en) | 2007-08-31 | 2016-06-07 | Cristal Usa Inc. | Photocatalytic coating |
US7776954B2 (en) * | 2008-01-30 | 2010-08-17 | Millenium Inorganic Chemicals, Inc. | Photocatalytic coating compositions |
US20090281207A1 (en) * | 2008-05-06 | 2009-11-12 | John Stratton | De-polluting and self-cleaning epoxy siloxane coating |
TWI440505B (zh) * | 2008-05-27 | 2014-06-11 | Toto Ltd | Photocatalyst coating |
US20100193449A1 (en) * | 2009-02-02 | 2010-08-05 | Jian-Ku Shang | Materials and methods for removing arsenic from water |
US8617665B2 (en) * | 2009-08-03 | 2013-12-31 | Alcoa, Inc. | Self-cleaning substrates and methods for making the same |
US9221031B2 (en) | 2010-07-29 | 2015-12-29 | Toto Ltd. | Inorganic material comprising photocatalyst layer, method for producing same, and photocatalyst coating liquid for inorganic material |
DE102010063887B4 (de) * | 2010-12-22 | 2012-07-19 | BSH Bosch und Siemens Hausgeräte GmbH | Verfahren zum Herstellen eines pyrolysetauglichen Bauteils eines Gargeräts sowie pyrolysetaugliches Bauteil für ein Gargerät |
US9018089B2 (en) * | 2011-08-30 | 2015-04-28 | International Business Machines Corporation | Multiple step anneal method and semiconductor formed by multiple step anneal |
DK3511054T3 (da) | 2013-03-15 | 2020-11-09 | Oy Halton Group Ltd | Røgrensning med vandspray og efterspørgselsstyret drift |
JP5997204B2 (ja) * | 2014-06-03 | 2016-09-28 | 有限会社Aes | コンクリート保護材、コンクリート構造物の補修方法、コンクリート構造物の含浸誘導剤、及びコンクリート構造物の欠陥充填剤 |
TWI547315B (zh) * | 2014-10-17 | 2016-09-01 | 睿澤企業股份有限公司 | 光觸媒基材之製作方法及製作機台 |
TW201514010A (zh) * | 2014-11-11 | 2015-04-16 | Cheng-Tsung Tsai | 矽酸鈣板表層處理方法 |
DE102015101449A1 (de) * | 2015-02-02 | 2016-08-04 | AstenJohnson PGmbH | Industrielles Gewebe, Verfahren zur Herstellung eines Vliesstoffs sowie Verwendung eines industriellen Gewebes |
US10918110B2 (en) | 2015-07-08 | 2021-02-16 | Corning Incorporated | Antimicrobial phase-separating glass and glass ceramic articles and laminates |
CN105097152B (zh) * | 2015-07-20 | 2017-08-11 | 湖南稀土金属材料研究院 | 表面改性的瓷绝缘子及其制备方法 |
CN108026394B (zh) | 2015-07-29 | 2021-02-19 | 3M创新有限公司 | 包含二氧化硅纳米粒子和官能硅烷化合物的防污组合物及其涂覆制品 |
JP6750348B2 (ja) * | 2015-09-15 | 2020-09-02 | Toto株式会社 | 光触媒層を有する衛生陶器 |
US10064273B2 (en) | 2015-10-20 | 2018-08-28 | MR Label Company | Antimicrobial copper sheet overlays and related methods for making and using |
CN105948496B (zh) * | 2016-04-29 | 2018-08-07 | 中材江西电瓷电气有限公司 | 西北地区瓷绝缘子用无机防尘釉料及其制备方法和应用 |
DE102017220683B4 (de) * | 2017-11-20 | 2022-02-17 | Lynatox Gmbh | Verfahren zum bindemittelfreien Aufbringen photokatalytischer Beschichtungen auf Titandioxidbasis und Verwendung eines photokatalytisch beschichteten Trägers auf Titandioxidbasis |
JP7243730B2 (ja) * | 2018-09-13 | 2023-03-22 | 住友大阪セメント株式会社 | 防汚皮膜、ガラスセラミックス製品、防汚皮膜形成用塗料、ガラスセラミックス製品の製造方法 |
CN110436604A (zh) * | 2019-07-25 | 2019-11-12 | 山东大学 | 一种使甲基蓝溶液脱色的方法及其应用 |
CN111592781A (zh) * | 2020-04-29 | 2020-08-28 | 广州大学 | 一种超亲水功能涂料及其制备方法和应用 |
CN112961520A (zh) * | 2021-04-06 | 2021-06-15 | 广州大学 | 一种耐水长效无机氧化锌超亲水涂料及其制备方法与应用 |
CN113248284B (zh) * | 2021-06-10 | 2021-11-09 | 新明珠集团股份有限公司 | 一种易清洁陶瓷砖及其制备方法 |
CN115558392B (zh) * | 2022-09-26 | 2023-11-21 | 江苏通达家居用品有限公司 | 一种铝框镜及组装工艺 |
CN115786792B (zh) * | 2022-11-23 | 2024-01-02 | 九牧厨卫股份有限公司 | 一种阻垢靶材及其制备和应用 |
Citations (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS50104232A (ja) * | 1974-01-24 | 1975-08-18 | ||
JPS5243817A (en) * | 1975-10-06 | 1977-04-06 | Nissan Chem Ind Ltd | Inorganic coating composition |
JPS5418485A (en) * | 1977-07-12 | 1979-02-10 | Kansai Paint Co Ltd | Inorganic coating composition |
JPS54116032A (en) * | 1978-02-28 | 1979-09-10 | Matsushita Electric Works Ltd | Inorganic paint and method for applying the same |
JPS54150438A (en) * | 1978-05-19 | 1979-11-26 | Matsushita Electric Ind Co Ltd | Coated surface having catalytic action |
JPS553874A (en) * | 1978-06-24 | 1980-01-11 | Shikoku Kaken Kogyo Co Ltd | Painting method of inorganic paint |
JPS5575739A (en) * | 1978-12-04 | 1980-06-07 | Matsushita Electric Ind Co Ltd | Petroleum combustor |
JPS5580763A (en) * | 1978-12-12 | 1980-06-18 | Matsushita Electric Ind Co Ltd | Selffcleaning type coating layer |
GB2044806A (en) * | 1979-02-23 | 1980-10-22 | Pyrene Chemical Services Ltd | Producing non-metallic coatings on iron and steel |
JPS55161868A (en) * | 1979-06-04 | 1980-12-16 | Shikoku Kaken Kogyo Co Ltd | Coating composition |
GB2061309A (en) * | 1979-09-10 | 1981-05-13 | Ppg Industries Inc | Curable pigmented silicate compositions |
JPS5693768A (en) * | 1979-12-27 | 1981-07-29 | Shikoku Kaken Kogyo Co Ltd | Film-forming composition from which stain is easily removed |
JPS5798567A (en) * | 1980-12-12 | 1982-06-18 | Toshiba Corp | Formation of self-decontaminating coating layer |
JPS58187471A (ja) * | 1982-04-28 | 1983-11-01 | Toshiba Corp | 自己浄化型被覆層の形成方法 |
JPS5930865A (ja) * | 1982-08-12 | 1984-02-18 | Osaka Soda Co Ltd | 無機質塗料組成物 |
GB2125809A (en) * | 1982-07-16 | 1984-03-14 | Osaka Soda Co Ltd | Antifouling coating compositions |
EP0113189A1 (en) * | 1982-12-01 | 1984-07-11 | Uss Engineers And Consultants, Inc. | Method of marking hot metal products |
JPS6035065A (ja) * | 1983-08-04 | 1985-02-22 | Osaka Soda Co Ltd | 海水接触物の防汚方法 |
JPH02129269A (ja) * | 1988-11-09 | 1990-05-17 | Okuno Seiyaku Kogyo Kk | 無機質塗料組成物 |
JPH06116512A (ja) * | 1992-10-09 | 1994-04-26 | T T Shii:Kk | 低温硬化型無機コーティング剤の製造方法及び低温硬化型無機コーティング層の形成方法 |
JPH06329950A (ja) * | 1993-05-21 | 1994-11-29 | Kazuya Yamada | 無機塗料組成物 |
JPH06329949A (ja) * | 1993-05-21 | 1994-11-29 | Kazuya Yamada | 無機塗料組成物 |
GB2284822A (en) * | 1993-12-14 | 1995-06-21 | Daiei Kikai Kabushiki Kaisha | Anti-corrosive, non-toxic coating compositions |
JPH0860040A (ja) * | 1994-08-12 | 1996-03-05 | Koji Yamada | 抗菌性無機塗料組成物 |
WO1996029375A1 (fr) * | 1995-03-20 | 1996-09-26 | Toto Ltd. | Procede photocatalytique pour rendre la surface de base d'un materiau ultrahydrophile, materiau de base ayant une surface ultrahydrophile et photocatalytique, et procede pour produire ce materiau |
WO1997005228A1 (fr) * | 1995-07-27 | 1997-02-13 | Mitsubishi Chemical Corporation | Procede de traitement de la surface d'un substrat et composition de traitement de surface prevue a cet effet |
JPH09241531A (ja) * | 1996-03-05 | 1997-09-16 | Inax Corp | 無機質塗膜形成用組成物及び無機質塗膜の形成方法 |
JPH10215996A (ja) * | 1997-02-03 | 1998-08-18 | Toto Ltd | 食器、及び食器収納装置 |
JPH10225659A (ja) * | 1997-02-13 | 1998-08-25 | Nippon Paint Co Ltd | 無機塗膜形成方法 |
JPH10237354A (ja) * | 1997-02-25 | 1998-09-08 | Matsushita Electric Works Ltd | コーティング剤及び建材 |
JPH10330646A (ja) * | 1997-06-02 | 1998-12-15 | Shiro Tago | 水性無機質塗料用組成物および塗膜形成方法 |
JPH1192689A (ja) * | 1997-09-25 | 1999-04-06 | Tao:Kk | 無機コーティング剤 |
JPH11197600A (ja) * | 1998-01-13 | 1999-07-27 | Kansai Paint Co Ltd | 塗膜の汚染防止処理方法 |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3640712A (en) | 1969-12-08 | 1972-02-08 | Hughes Aircraft Co | Hydrophilic-hydrophobic photon-sensitive medium |
JPS5398324A (en) | 1977-02-10 | 1978-08-28 | Kansai Paint Co Ltd | Forming of inorganic film |
JPS53149281A (en) | 1977-06-02 | 1978-12-26 | Teijin Ltd | Laminate with hydrophilic film |
JPH0723478B2 (ja) | 1987-02-07 | 1995-03-15 | 平岡織染株式会社 | 非水滲透性材料の汚れ除去方法 |
US5616532A (en) | 1990-12-14 | 1997-04-01 | E. Heller & Company | Photocatalyst-binder compositions |
ES2036127B1 (es) * | 1991-05-16 | 1994-02-01 | Sers S A | Plancha para la impresion y procedimiento para su fabricacion. |
JPH05123639A (ja) | 1991-11-01 | 1993-05-21 | Daiken Trade & Ind Co Ltd | 無機質化粧板の製造方法 |
US5595813A (en) | 1992-09-22 | 1997-01-21 | Takenaka Corporation | Architectural material using metal oxide exhibiting photocatalytic activity |
AU676299B2 (en) | 1993-06-28 | 1997-03-06 | Akira Fujishima | Photocatalyst composite and process for producing the same |
WO1995015816A1 (fr) | 1993-12-10 | 1995-06-15 | Toto, Ltd. | Substance multifonction a effet photocatalytique et procede de production |
JP3709018B2 (ja) * | 1996-07-16 | 2005-10-19 | 株式会社神戸製鋼所 | 潤滑性、接着性および化成処理性に優れた亜鉛系めっき鋼板の製造方法 |
KR100213852B1 (ko) | 1995-11-13 | 1999-08-02 | 구마모토 마사히로 | 화성처리성이 우수한 윤활강판 및 그 제조방법 |
US6090489A (en) | 1995-12-22 | 2000-07-18 | Toto, Ltd. | Method for photocatalytically hydrophilifying surface and composite material with photocatalytically hydrophilifiable surface |
ES2208771T3 (es) * | 1995-12-22 | 2004-06-16 | Toto Ltd. | Procedimiento fotocatalitico para hacer hidrofila una superficie y material compuesto con una superficie hidrofila fotocataliticamente. |
JPH09227150A (ja) | 1996-02-16 | 1997-09-02 | Minolta Co Ltd | ガラス成形用型の保護膜及びその製造方法 |
JPH09227157A (ja) | 1996-02-26 | 1997-09-02 | Nissan Motor Co Ltd | 防曇性被膜形成基材、これを用いた防曇膜及びその製造方法 |
JPH09227158A (ja) | 1996-02-28 | 1997-09-02 | Nissan Motor Co Ltd | 防曇性被膜形成基材、これを用いた防曇膜及びその製造方法 |
JPH09235140A (ja) | 1996-03-04 | 1997-09-09 | Toyota Central Res & Dev Lab Inc | ガラス |
JPH09278431A (ja) | 1996-04-18 | 1997-10-28 | Central Glass Co Ltd | 親水性膜およびその製造方法 |
JP3852284B2 (ja) * | 1998-07-30 | 2006-11-29 | 東陶機器株式会社 | 光触媒機能を有する機能材の製造方法およびそのための装置 |
-
1999
- 1999-10-19 WO PCT/JP1999/005766 patent/WO2000023528A1/ja not_active Application Discontinuation
- 1999-10-19 CN CNB998145521A patent/CN1198886C/zh not_active Expired - Fee Related
- 1999-10-19 TW TW88118069A patent/TWI230186B/zh not_active IP Right Cessation
- 1999-10-19 AU AU61250/99A patent/AU6125099A/en not_active Abandoned
- 1999-10-19 EP EP99947973A patent/EP1136527A4/en not_active Withdrawn
- 1999-10-19 US US09/807,801 patent/US6673433B1/en not_active Expired - Fee Related
- 1999-10-19 CN CNB2005100543352A patent/CN100349660C/zh not_active Expired - Lifetime
Patent Citations (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS50104232A (ja) * | 1974-01-24 | 1975-08-18 | ||
JPS5243817A (en) * | 1975-10-06 | 1977-04-06 | Nissan Chem Ind Ltd | Inorganic coating composition |
JPS5418485A (en) * | 1977-07-12 | 1979-02-10 | Kansai Paint Co Ltd | Inorganic coating composition |
JPS54116032A (en) * | 1978-02-28 | 1979-09-10 | Matsushita Electric Works Ltd | Inorganic paint and method for applying the same |
JPS54150438A (en) * | 1978-05-19 | 1979-11-26 | Matsushita Electric Ind Co Ltd | Coated surface having catalytic action |
JPS553874A (en) * | 1978-06-24 | 1980-01-11 | Shikoku Kaken Kogyo Co Ltd | Painting method of inorganic paint |
JPS5575739A (en) * | 1978-12-04 | 1980-06-07 | Matsushita Electric Ind Co Ltd | Petroleum combustor |
JPS5580763A (en) * | 1978-12-12 | 1980-06-18 | Matsushita Electric Ind Co Ltd | Selffcleaning type coating layer |
GB2044806A (en) * | 1979-02-23 | 1980-10-22 | Pyrene Chemical Services Ltd | Producing non-metallic coatings on iron and steel |
JPS55161868A (en) * | 1979-06-04 | 1980-12-16 | Shikoku Kaken Kogyo Co Ltd | Coating composition |
GB2061309A (en) * | 1979-09-10 | 1981-05-13 | Ppg Industries Inc | Curable pigmented silicate compositions |
JPS5693768A (en) * | 1979-12-27 | 1981-07-29 | Shikoku Kaken Kogyo Co Ltd | Film-forming composition from which stain is easily removed |
JPS5798567A (en) * | 1980-12-12 | 1982-06-18 | Toshiba Corp | Formation of self-decontaminating coating layer |
JPS58187471A (ja) * | 1982-04-28 | 1983-11-01 | Toshiba Corp | 自己浄化型被覆層の形成方法 |
GB2125809A (en) * | 1982-07-16 | 1984-03-14 | Osaka Soda Co Ltd | Antifouling coating compositions |
JPS5930865A (ja) * | 1982-08-12 | 1984-02-18 | Osaka Soda Co Ltd | 無機質塗料組成物 |
EP0113189A1 (en) * | 1982-12-01 | 1984-07-11 | Uss Engineers And Consultants, Inc. | Method of marking hot metal products |
JPS6035065A (ja) * | 1983-08-04 | 1985-02-22 | Osaka Soda Co Ltd | 海水接触物の防汚方法 |
JPH02129269A (ja) * | 1988-11-09 | 1990-05-17 | Okuno Seiyaku Kogyo Kk | 無機質塗料組成物 |
JPH06116512A (ja) * | 1992-10-09 | 1994-04-26 | T T Shii:Kk | 低温硬化型無機コーティング剤の製造方法及び低温硬化型無機コーティング層の形成方法 |
JPH06329950A (ja) * | 1993-05-21 | 1994-11-29 | Kazuya Yamada | 無機塗料組成物 |
JPH06329949A (ja) * | 1993-05-21 | 1994-11-29 | Kazuya Yamada | 無機塗料組成物 |
GB2284822A (en) * | 1993-12-14 | 1995-06-21 | Daiei Kikai Kabushiki Kaisha | Anti-corrosive, non-toxic coating compositions |
JPH0860040A (ja) * | 1994-08-12 | 1996-03-05 | Koji Yamada | 抗菌性無機塗料組成物 |
WO1996029375A1 (fr) * | 1995-03-20 | 1996-09-26 | Toto Ltd. | Procede photocatalytique pour rendre la surface de base d'un materiau ultrahydrophile, materiau de base ayant une surface ultrahydrophile et photocatalytique, et procede pour produire ce materiau |
WO1997005228A1 (fr) * | 1995-07-27 | 1997-02-13 | Mitsubishi Chemical Corporation | Procede de traitement de la surface d'un substrat et composition de traitement de surface prevue a cet effet |
JPH09241531A (ja) * | 1996-03-05 | 1997-09-16 | Inax Corp | 無機質塗膜形成用組成物及び無機質塗膜の形成方法 |
JPH10215996A (ja) * | 1997-02-03 | 1998-08-18 | Toto Ltd | 食器、及び食器収納装置 |
JPH10225659A (ja) * | 1997-02-13 | 1998-08-25 | Nippon Paint Co Ltd | 無機塗膜形成方法 |
JPH10237354A (ja) * | 1997-02-25 | 1998-09-08 | Matsushita Electric Works Ltd | コーティング剤及び建材 |
JPH10330646A (ja) * | 1997-06-02 | 1998-12-15 | Shiro Tago | 水性無機質塗料用組成物および塗膜形成方法 |
JPH1192689A (ja) * | 1997-09-25 | 1999-04-06 | Tao:Kk | 無機コーティング剤 |
JPH11197600A (ja) * | 1998-01-13 | 1999-07-27 | Kansai Paint Co Ltd | 塗膜の汚染防止処理方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1136527A4 * |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002080829A (ja) * | 2000-09-07 | 2002-03-22 | Toto Ltd | 親水性部材、その製造方法、およびその製造のためのコーティング剤 |
JP2008525188A (ja) * | 2004-12-28 | 2008-07-17 | カウンシル オブ サイエンティフィック アンド インダストリアル リサーチ | 光触媒による汚れの自動洗浄工程 |
WO2006092941A1 (ja) * | 2005-03-03 | 2006-09-08 | Cleanup Corporation | 水使用住宅設備機器の製造方法および水使用住宅設備機器 |
KR101200628B1 (ko) * | 2005-03-03 | 2012-11-12 | 스미토모 오사카 세멘토 가부시키가이샤 | 물 사용 주택 설비 기기의 제조 방법 |
JP6043889B1 (ja) * | 2016-09-16 | 2016-12-14 | 日新製鋼株式会社 | 塗装金属板 |
WO2018051524A1 (ja) * | 2016-09-16 | 2018-03-22 | 日新製鋼株式会社 | 塗装金属板 |
KR20220063748A (ko) * | 2020-11-10 | 2022-05-17 | (주)엘엑스하우시스 | 도기 및 이의 제조방법 |
KR102412789B1 (ko) | 2020-11-10 | 2022-06-24 | (주)엘엑스하우시스 | 도기 및 이의 제조방법 |
Also Published As
Publication number | Publication date |
---|---|
EP1136527A1 (en) | 2001-09-26 |
CN1330692A (zh) | 2002-01-09 |
US6673433B1 (en) | 2004-01-06 |
CN1654133A (zh) | 2005-08-17 |
TWI230186B (en) | 2005-04-01 |
CN1198886C (zh) | 2005-04-27 |
CN100349660C (zh) | 2007-11-21 |
AU6125099A (en) | 2000-05-08 |
EP1136527A4 (en) | 2003-07-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2000023528A1 (fr) | Materiau resistant aux salissures, procede et dispositif de production et composition de revetement | |
TWI229617B (en) | Method for manufacturing functional material having photo-catalystic functional and apparatus therefor | |
EP1712530B1 (en) | Method of cleaning a substrate having an ultrahydrophilic and photocatalytic surface | |
JP5128733B2 (ja) | 機能的な、特に疎水性の、メソ多孔質被覆を有するガラス | |
TW517082B (en) | A process for pre-treating the surface of a substrate before the formation of a photocatalytically hydrophilifiable coating, the cleaning agent used therein and the undercoating composition. | |
JP2008506624A (ja) | 耐久親水特性を有するオキシ炭化ケイ素コーティング | |
JPH09227169A (ja) | 転写シート、及び光触媒性親水性薄膜の転写方法 | |
CZ301921B6 (cs) | Použití složeného materiálu pro odstranení oxidu dusíku, amoniaku, oxidu uhelnatého a/nebo oxidu síry ze vzduchu | |
KR101769228B1 (ko) | 부착 오염에 대한 자기 세정 능력이 우수한 피막을 형성하는 수계 친수성 도료 조성물 및 부착 오염에 대한 자기 세정 능력이 우수한 피막을 형성한 표면 처리재 | |
WO2011118780A1 (ja) | 光触媒塗装体および光触媒コーティング液 | |
CN102653639A (zh) | 复合二氧化钛光触媒溶胶涂料组成物及涂布方法 | |
JPH1150006A (ja) | 光触媒性親水性被膜形成前の表面の前処理法並びにそれに用いられる洗浄剤およびアンダーコート組成物 | |
JP2009262153A (ja) | 光触媒塗装体およびそのための光触媒コーティング液 | |
JP4011705B2 (ja) | 光触媒配合物と光触媒含有物並びに光触媒機能発揮材およびその製造方法 | |
EP2094397A1 (en) | Method for forming an inorganic coated layer having high hardness | |
TWI430841B (zh) | With the use of photocatalyst layer of composite materials | |
JPH09295363A (ja) | 基材及び基材の表面清潔度維持方法 | |
KR100654299B1 (ko) | 방오성 기능성 세라믹 코팅 조성물 | |
WO2018054299A1 (en) | A coating liquid, coating composition and the substrate coated with the same | |
JP2001098187A (ja) | 光触媒性親水性コーティング組成物、及び光触媒性親水性部材の製造方法 | |
JP2007302527A (ja) | 光触媒膜付きガラス施工体および光触媒膜付きガラス施工体を用いた構築構造体 | |
JPH10180948A (ja) | 転写シ−ト、及び光触媒性親水性薄膜の転写方法 | |
JPH10237416A (ja) | 親水性付与材と親水性発揮材およびその製造方法 | |
JP4897781B2 (ja) | 光触媒塗装体およびそのための光触媒コーティング液 | |
JP2004290974A (ja) | 光触媒配合物と光触媒含有物並びに光触媒機能発揮材およびその製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 99814552.1 Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
ENP | Entry into the national phase |
Ref document number: 2000 577245 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1999947973 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 09807801 Country of ref document: US |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWP | Wipo information: published in national office |
Ref document number: 1999947973 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1999947973 Country of ref document: EP |